Poly-methylated, fluorine-free superhydrophobic compositions, methods, and / or uses thereof

Abstract

Provided are polymers comprising a metal coordination complex comprising a repeating unit of an alkylated azolate, wherein the alkylated azolate comprises more than one alkyl group, and nitrogen atoms of the alkylated azolate are coordinated to metals (M), and methods of making and using them. Provided are coordination polymers, or methylated metal-organic frameworks (MOFs), comprising methylated azolates such as 3,5-dimethyl-1,2,4-triazolate, and metal cations. Polymers as provided herein are superhydrophobic, or extremely water-repellent, and are coated onto or added to a substrate to impart superhydrophobic or water-repellent properties to a substrate, for example, a packaging surface, a container, a textile or fabric a plastic, a paper, a metal, a wood, or a bioderived or synthetic polymer. Provided are polymers comprising large octopus-type aryl-bridged poly-azolate ligands and different metals from Ag(I) such as Cu(I), Cu(II), Zn(II), Zr(IV), Ni(II), etc., that can be employed in MOFs.

Description

[0001]PATENT 6343*161006PCT / Omary-M17 POLY-METHYLATED, FLUORINE-FREE SUPERHYDROPHOBIC COMPOSITIONS, METHODS, AND / OR USES THEREOF RELATED APPLICATIONS This Patent Convention Treaty (PCT) International Application claims the benefit of priority under 35 U.S.C. § 119(e) of U.S. Provisional Application Serial No. (USSN) 63 / 685,194, Aug.20, 2024; and USSN 63 / 821,146, filed June 10, 2025. The aforementioned applications are expressly incorporated herein by reference in their entirety and for all purposes. All publications, patents, patent applications cited herein are hereby expressly incorporated by reference for all purposes. STATEMENT AS TO FEDERALLY SPONSORED RESEARCH This invention was made with government support under 31310023M0019 awarded by the U.S. Nuclear Regulatory Commission; under W911NF2210201 awarded by the U.S. Department of Defense; under CHE-1413641 awarded by the U.S. National Science Foundation. The government has certain rights in the invention. TECHNICAL FIELD This invention generally relates to chemistry and materials science. In alternative embodiments, provided are polymers comprising a metal coordination complex comprising a repeating unit of an alkylated azolate, wherein the alkylated azolate comprises more than one alkyl group, and nitrogen atoms of the alkylated azolate are coordinated to metals (M), and methods of making and using them. In alternative embodiments, provided are coordination polymers, named methylated metal-organic frameworks or MeMOFs, comprising methylated azolates such as 3,5-dimethyl-1,2,4- triazolate, and metal cations such as silver (I) and copper (II) ions. In alternative embodiments, provided are polymers comprising large octopus-type aryl-bridged poly- azolate ligands and different metals from Ag(I) such as Cu(I), Cu(II), Zn(II), Zr(IV), Ni(II), etc., that can be employed in MOFs. In alternative embodiments, polymers as provided herein are superhydrophobic, or extremely water-repellent. In alternative embodiments, polymers as provided herein are coated onto or added to a substrate to impart superhydrophobic or water-repellent properties to a substrate, where the substrate can be for example, a packaging surface, a textile, a plastic, a paper, a metal, or a bioderived or synthetic polymer. PATENT 6343*161006PCT / Omary-M17 BACKGROUND Superhydrophobicity is a feature of surfaces of materials that are extremely water- repellent. Superhydrophobic materials have extremely high contact angles with water droplets (usually greater than about 130 degrees to 150 degrees, see FIG.1). This means that water droplets on these surfaces will bead up and roll away rather than spreading out or adhering to the surface. Fluorous metal-organic frameworks such as FMOF-1, which is 3,5- bis(trifluoromethyl)-1,2,4-triazolatosilver(I), have received significant interest for its extraordinary properties that include exceptional superhydrophobicity and excellent hydrothermal stability. These properties have been linked mostly to the presence of fluorine atoms contained within its structure. However, significant environmental and health concerns have been raised recently regarding per-and polyfluoroalkyl substances (PFAS). FMOFs contain only -CF3 moieties as opposed to long perfluoroalkyl chains typical in PFAS and have significant nitrogen (N3-aromatic heterocycle) and metal content that impart multiple decomposition pathways that render an inconsistent behavior to the “forever chemicals” PFAS reputation. Nevertheless, these assurances notwithstanding, one would worry that someday the same concerns that came about PFAS multiple decades following their introduction to market may be encountered if FMOFs were to be adopted commercially. Thus, there is a need for superhydrophobic and superhydrophobicizing surfaces lacking -CF3 moieties. SUMMARY In alternative embodiments, provided are polymers (wherein optionally the polymer comprises repeat unit coordination polymers) comprising a metal coordination complex comprising a repeating unit of an alkylated azolate, wherein the alkylated azolate comprises more than one alkyl group, and nitrogen atoms of the alkylated azolate are coordinated to metals (M), and methods of making and using them. In alternative embodiments, provided are coordination polymers, named methylated metal-organic frameworks or MeMOFs, comprising methylated azolates such as 3,5-dimethyl-1,2,4- triazolate, and metal cations such as silver (I) and copper (II) ions. In alternative embodiments, provided are polymers comprising large octopus-type aryl-bridged poly- azolate ligands and different metals from Ag(I) such as Cu(I), Cu(II), Zn(II), Zr(IV), Ni(II), etc., that can be employed in MOFs. In alternative embodiments, polymers as PATENT 6343*161006PCT / Omary-M17 provided herein are superhydrophobic, or extremely water-repellent. In alternative embodiments, polymers as provided herein are coated onto or added to a substrate to impart superhydrophobic or water-repellent properties to a substrate, where the substrate can be for example, a packaging surface, a textile, a plastic, a paper, a metal, or a bioderived or synthetic polymer. In alternative embodiments, superhydrophobic behavior of methylated metal- organic framework (MeMOF) containing materials as provided herein lead to contact angles that are even higher than those in analogous FMOF-containing materials (by approximately 10° greater contact angle, or a contact angle of between about 165-175°, or greater ) even in hybrid materials with about 1% (wt or V) MeMOF / matrix order of magnitude. In alternative embodiments MeMOFs as provided herein exhibit similar thermal stability, up to about 365°C, to that of FMOF-1. In alternative embodiments, provided are large octopus-type aryl-bridged poly- azolate ligands and different metals from Ag(I) such as Cu(I), Cu(II), Zn(II), Zr(IV), Ni(II), etc., as typically done in MOFs. In alternative embodiments provided are metal coordination complexes comprising a repeating unit of an alkylated azolate, wherein the alkylated azolate comprises more than one alkyl group, and nitrogen atoms of the alkylated azolate are coordinated to metals (M). In some aspects, the metal coordination complex of claim 1, wherein the metal coordination complex is represented by Formula I or II: wherein, each J is J1, J2, N, or CRzwherein Rzis H or –(C1-C6)alkyl; each J1is: each J2is N---M, wherein N is the nitrogen atom of the triazole ring of Formula I; PATENT 6343*161006PCT / Omary-M17 each M is independently a metal ion; or each M is independently a metal(0); each Ar is an aromatic ring spacer or absent, or each Ar is phenyl optionally substituted with substituents from the group consisting of –(C1-C6)alkyl and halo; each R1and R2are independently –(C1-C6)alkyl, halo, or H; and each R3and R4are independently –(C1-C6)alkyl, halo, or H; wherein the alkylated azolate of Formula I or II is substituted with at least two – (C1-C6)alkyl groups; wherein the metal coordination complex is an oligomeric or polymeric metal coordination complex of Formula I when J is J1or J2; or the metal coordination complex is a cyclic trinuclear or cyclic tetranuclear metal coordination complex of Formula I when J is N or CRz. In alternative embodiments provided are methods for forming a superhydrophobic surface comprising: a) coating a substrate with the metal coordination polymer or oligomer described above; or b) mixing a substance with the metal coordination polymer or oligomer described above then coating a substrate with the mixture; wherein the superhydrophobic surface is capable of forming a contact angle of at least about 130 degrees with a water drop. In alternative embodiments provided are metal coordination complexes that are polymers, oligomers or cyclic complexes of Formulas I, IA-IC, II, IIA, III, and IV, intermediates for the synthesis of such metal coordination complexes of Formulas I, IA- IC, II, IIA, III, and IV, as well as methods of preparing such metal coordination complexes of Formulas I, IA-IC, II, IIA, III, and IV. In alternative embodiments provided are metal coordination complexes of Formulas I, IA-IC, II, IIA, III, and IV that are useful as intermediates for the synthesis of other useful polymers, oligomers or cyclic complexes. In alternative embodiments provided are uses of such metal coordination complexes of Formulas I, IA-IC, II, IIA, III, and IV. While the invention is not limited by any particular mechanism of action, in alternative embodiments substituting poly-fluoroalkyl groups with poly-methyl groups in metal-azolate coordination polymers or oligomers renders similar or better hydrophobicity, whereas adding two or more methyl groups on the azolate ring beyond PATENT 6343*161006PCT / Omary-M17 none or a single group would further enhance the material’s hydrophobicity (from mere hydrophobic to superhydrophobic). This is illustrated by the contrast between common materials in the left side to an alternative embodiment on the right side of the representative Formulas III and IV, respectively. Exemplary Zeolitic Imidazolate Frameworks: In alternative embodiments provided are various uses of the compositions described herein, including but not limited to: a) water purification particularly from an aliphatic and / or an aromatic organic contaminant, and includes methods for milder de-contamination as in drinking water or heavy de-contamination as in agricultural or post-fracking produced industrial water; PATENT 6343*161006PCT / Omary-M17 b) moisture, oxygen, and / or UV barriers on plastic, a wood, a glass, paper, or a metal, including metal, plastic or paper food / beverage / consumer product containers; c) decreasing the oil content in fried food products such as potato chips or French fries, corn tortilla chips, etc., upon contact with biocompatible amounts of the hydrophobic materials herein via biocompatible carriers (for example CO2 or ethanol) in the vapor, solution, or supercritical phase; d) corrosion protection of metallic and non-metallic substrates (for example, steel and other metals / ceramics used in construction and cookware, aluminum and carbon fiber used in airplane fuselage manufacture); and e) medical therapy, including the manufacture of medicaments useful for the treatment of bacterial infections in a mammal, such as a human, and treating cancer. In alternative embodiments, provided are polymers (wherein optionally the polymers comprise repeat unit coordination polymers), clusters and oligomers, comprising at least one metal coordination complex comprising a repeating unit of an alkylated azolate comprising nitrogen atoms, wherein the alkylated azolate comprises more than one alkyl group or a plurality of alkyl groups, and each nitrogen atom of each alkylated azolate is coordinated to a metal (M). In alternative embodiments, of polymers, or polymers comprising repeat unit coordination polymers, as provided herein: - the metal coordination complex is represented by or has a structure as set forth in Formula I or Formula II: I; Formula II, wherein, each J is J1, J2, N, or CRzwherein Rzis H or –(C1-C6)alkyl; each J1is: PATENT 6343*161006PCT / Omary-M17 each J2is N---M, wherein N is the nitrogen atom of the triazole ring of Formula I; each M is independently a metal ion or each M is independently a metal(0); each Ar is an aromatic ring spacer or absent, or each Ar is a phenyl, optionally a phenyl substituted with substituents selected from the group consisting of –(C1-C6)alkyl and halo; each R1and R2are independently –(C1-C6)alkyl, halo, or H; and each R3and R4are independently –(C1-C6)alkyl, halo, or H; wherein the alkylated azolate of Formula I or II is substituted with at least two – (C1-C6)alkyl groups; wherein the metal coordination complex is an oligomeric or polymeric metal coordination complex of Formula I when J is J1or J2; or the metal coordination complex is a cyclic trinuclear or cyclic tetranuclear metal coordination complex of Formula I when J is N or CRz. In alternative embodiments, of polymers, or polymers comprising repeat unit coordination polymers, as provided herein: - the metal ion is a transition metal ion, or the metal ion is silver, copper, zinc, zirconium, iron, nickel, chromium, manganese, cobalt, or vanadium; - the metal coordination complex of Formula I is represented by or has a structure as set forth in Formula IA: Formula IA; and / or - the metal coordination complex of Formula I is represented by or has a structure as set forth in Formula IB: or PATENT 6343*161006PCT / Omary-M17 Formula IB, wherein each Ra, Rb, Rc, and Rdare independently –(C1-C6)alkyl, halo, or H. In alternative embodiments, of polymers, or polymers comprising repeat unit coordination polymers, as provided herein: - two or more of R1, R2, R3, and R4are CH3, or two or more of Ra, Rb, Rc, and Rdare CH3; - the metal coordination complex of Formula I is represented by or has a structure as set forth in Formula IC: wherein each R1, R2, R3, and R4are independently –(C1-C6)alkyl, halo, or H; - two or more of R1, R2, R3, and R4are CH3; - the metal coordination complex of Formula II is represented by or has a structure as set forth in Formula IIA: Formula IIA, wherein each Ra, Rb, Rc, and Rdare independently –(C1-C6)alkyl, halo, or H; and / or - two or more of Ra, Rb, Rc, and Rdare CH3. In alternative embodiments, of polymers, or polymers comprising repeat unit coordination polymers, as provided herein, the metal coordination complex comprises: 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)-2,3,5,6-tetramethylbenzene coordinated to copper(II); 1,4-bis(4,4’-pyrazolato)-2,3,5,6-tetramethylbenzene coordinated to copper(II); PATENT 6343*161006PCT / Omary-M17 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)benzene coordinated to copper(II); bis(4,4’-[3,5-dimethyl]pyrazolate) coordinated to copper(II); 1,4-bis(4,4’-tetrazolato)-2,3,5,6-tetramethylbenzene coordinated to copper(II); or 3,5-dimethyl-1,2,4-triazolate coordinated to copper(II); or wherein the metal coordination complex comprises: 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)-2,3,5,6-tetramethylbenzene coordinated to silver(I); 1,4-bis(4,4’-pyrazolato)-2,3,5,6-tetramethylbenzene coordinated to silver(I); 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)benzene coordinated to silver(I); bis(4,4’-[3,5-dimethyl]pyrazolate) coordinated to silver(I); 1,4-bis(4,4’-tetrazolato)-2,3,5,6-tetramethylbenzene coordinated to silver(I); or 3,5-dimethyl-1,2,4-triazolate coordinated to silver(I). In alternative embodiments, of polymers, or polymers comprising repeat unit coordination polymers, as provided herein, the metal coordination complex of Formula I is represented by or has a structure comprising a cyclic trinuclear metal coordination complex of Formula III or a cyclic tetranuclear metal coordination complex of IV: wherein, PATENT 6343*161006PCT / Omary-M17 each J is N or CRz; each Rzis H or –(C1-C6)alkyl; each R1and R2are independently –(C1-C6)alkyl, halo, or H; and each M is independently a metal(0). In alternative embodiments, of polymers, or polymers comprising repeat unit coordination polymers, as provided herein, the cyclic trinuclear metal coordination complex of Formula III is: . In alternative embodiments, of polymers, or polymers comprising repeat unit coordination polymers, as provided herein, the cyclic tetranuclear metal coordination complex of Formula IV is: . In alternative embodiments, provided are methods for forming a superhydrophobic surface comprising: (a) coating a substrate with the polymer as provided herein; or (b) mixing a substance with the metal coordination complex as provided herein to form a mixture, then coating a substrate with the mixture; wherein the superhydrophobic surface is capable of forming a contact angle of at least 130 degrees with a water drop. In alternative embodiments of methods as provided herein: PATENT 6343*161006PCT / Omary-M17 - the substrate or substance comprises polyethylene terephthalate, Nylon 6 / 6, poly(p-phenylene oxide) / polystyrene blend, activated carbon, carbon fiber, low carbon steel, aluminum, a metal ion or a transition metal, a glass, a plastic, a wood or a paper; - the aluminum is an aluminum alloy, or the metal ion is iron, nickel, chromium, manganese, cobalt, vanadium or copper; the metal coordination complex is thermally stable at a process melt temperature of the substance; the superhydrophobic surface is corrosion resistant; the superhydrophobic surface is a barrier to or is impervious to moisture, air, ultraviolet light, or a combination thereof, or the superhydrophobic surface acts as a barrier that substantially blocks moisture, air, ultraviolet light, or a combination thereof; - the superhydrophobic neat or additive in hybrid material or surface absorbs oil so as to decrease the oil content in fried food products, optionally potato chips or French fries corn tortilla chips; and / or - the superhydrophobic neat or additive in hybrid material or surface absorbs oil so as to purify water, including lightly-contaminated drinking water or heavily- contaminated agricultural or industrial water, optionally the heavily-contaminated agricultural or industrial water comprises post-fracking produced water and / or oil spill- contaminated water. In alternative embodiments, provided are: a packaging surface, a container, a textile, a plastic, a paper, a metal, a wood, a glass, or a bioderived or synthetic polymer, comprising or having a coating applied thereon one, two or more surfaces of the packaging surface, container, textile, plastic, paper, metal, wood, glass, or bioderived or synthetic polymer, or substantially most of or all surfaces of the packaging surface, container, textile, plastic, paper, metal, wood, glass, or bioderived or synthetic polymer, wherein the coating comprises a polymer as provided herein. In alternative embodiments, the container is a food container, a beverage container, or a consumer product container. The details of one or more exemplary embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims. PATENT 6343*161006PCT / Omary-M17 All publications, patents, patent applications, American Type Culture Collection (ATCC) deposits and NCBI reference sequences cited herein are hereby expressly incorporated by reference in their entireties for all purposes. DESCRIPTION OF THE DRAWINGS The following drawings form part of the specification and are included to further demonstrate certain embodiments or various aspects of the invention. In some instances, embodiments of the invention can be best understood by referring to the accompanying drawings in combination with the detailed description presented herein. The description and accompanying drawings may highlight a certain specific example, or a certain aspect of the invention. However, one skilled in the art will understand that portions of the example or aspect may be used in combination with other examples or aspects of the invention. FIG.1A-C schematically illustrates water drop contact angles θ definitions for hydrophilic (FIG.1A), hydrophobic (FIG.1B), and superhydrophobic materials (FIG. 1C). FIG.2A-E illustrates images showing representative contact angle data for pure MeMOF embodiments or hybrids thereof with plastic substrates, demonstrating impressive hydrophobicity despite not having any perfluoroalkyl groups: it is a desirable class of material for applications requiring water repellency, such as coatings, membranes, or protective layers, due to this property: FIG.2A: MeMOF alone; FIG.2B PET (polyethylene terephthalate) alone; FIG.2C: Sanded PET (PET control); FIG.2D: Sanded PET followed by dry coating (Treated PET 2); and, FIG.2E: MeMOF Sanded into the PET (Treated PET 2). FIG.3 graphically illustrates a compilation and comparison summary of water drop contact angle data for MeMOF-coated vs uncoated PET (as average ^ standard deviation for each sample type). FIG.4 graphically illustrates hydrophobicity of x% MeMOF / AC hybrid samples (AC = activated carbon). The percentages shown are the percentages by mass of MeMOF in the hybrid sample relative to the total mass (dry mix). FIG.5 graphically illustrates thermal stability demonstration for the MeMOF- 1 / FF-1 composition = [Ag(3,5-(CH3)2-1,2,4-triazolate)]n. Thermogravimetric analysis (TGA) shown here suggests the thermal stability to be up to approximately 370 C. Therefore, this MeMOF-1 material should be quite stable thermally so as to “survive” in PATENT 6343*161006PCT / Omary-M17 situ processing as an additive to plastic or paper substrates during their manufacture that requires stability at < 370oC (Plastic processing: Nylon 6 / 6: 500-560oF (260-293oC); PET - Bottle: 520-560oF (271-293oC); PPO: 480-580oF (249-304oC. Paper processing: Torrefaction at 392oF (200oC), 428oF (220oC), 464oF (240oC), and 500oF (260oC), respectively). FIG.6A graphically shows UV / Vis absorption / turbidity data for the performance of neat MeMOF-1 vs different neat AC materials (derived from the following biomass tree sources: Bamboo, Kenaf, and two samples of Pine: one with higher and the other lower surface area, HSA and LSA, respectively). FIG.6B and FIG.6C graphically illustrate UV / vis data and demonstrates the use of x% MeMOF-1 / AC hybrid materials used for water filtration of heavily-contaminated post-fracking water. Notice that considerable improvement is observed vs neat AC with increased x values (from as little as 0.1-10% attaining improvement such that the UV / Vis signal for the organic contaminant is reduced much beyond the gravimetric weight % increase of the added MeMOF weight relative to the AC weight). This promises scale-up opportunities for high-performing x% MeMOF-1 / AC hybrid materials at little price increase when small x% values in the 0.1-10% of the more expensive MeMOF material vs the inexpensive AC material that would constitute 90-99.9% of the weight. FIG.7 graphically illustrates UV / vis data demonstrates the use of MeMOF-based materials for oil extraction from fried chips to reduce their oil content by greater than (>) 50%. Considerable improvement is observed vs the neat solvent (for example, ethanol here; also works for CO2 in gas or supercritical phase). FIG.8A-B illustrate a demonstration of biocompatibility testing for MeMOFs: a concentration of 50 µg / mL shows cell viability greater than 85%, exceeding the 70% widely-acceptable threshold for biocompatibility required for novel materials’ uses that entail food contact; FIG.8A graphically illustrates data, and FIG.8B summarizes data in table form: the embodiments herein have been validated for effectiveness at such concentrations whereby the dilution is via the various matrices discussed above (biomass- based AC or raw plant extract, plastic or paper substrate, ethanol, CO2, etc.). FIG.9A-B illustrate representative contact angle data for two representative pure MeCTC embodiments, again demonstrating impressive hydrophobicity despite not having any perfluoroalkyl groups, as in the MeMOF data in FIG.2-4 ; FIG.9A illustrates water drops on the exemplary [Ag(I)-bis(isopropyl)pyrazolate]3 CTC; and FIG.9B illustrates water drops on the exemplary [Ag(I)-bis(tert-butyl)pyrazolate]4 CTC. PATENT 6343*161006PCT / Omary-M17 FIG.10A-B illustrate representative contact angle data for two representative pure F-free alkyl- and aryl-substituted ZIFs, again demonstrating impressive hydrophobicity despite not having any perfluoroalkyl groups, as in the MeMOF data in FIG.2-4; MeZIF analogues exhibit yet further enhanced hydrophobicity upon poly-methyl substituents on the respective alkyl or aryl carbons; FIG.10A illustrates water drops on ZIF-8; and FIG. 10B illustrates water drops on ZIF-7. FIG.11A-C illustrate representative contact angle data for three representative fluorinated CTC / FMOF “positive controls” vis-à-vis MeCTC / MeMOF embodiments. Note the contact angles here are similar to, indeed slightly smaller than, those for the corresponding F-free MeCTCs and MeMOFs in FIG.s 2-4 and 9, respectively, hence demonstrating that impressive hydrophobicity can still be attained upon poly-methylation without the need for any fluoro-alkylation; FIG.11A illustrates positive control #1, water drops on [Ag(I)-bis(trifluoromethyl)pyrazolate]3 CTC; FIG.11B illustrates positive control #2, water drops on [Cu(I)-bis(trifluoromethyl)pyrazolate]3 CTC; FIG.11A illustrates positive control #3, water drops on neat FMOF-1 and x% FMOF-1 / AC hybrids. FIG.11A-D illustrate representative contact angle data for four pure samples of the azole free ligands used in the construction of MeMOFs (FIG.11A), MeCTCs (FIG. 11B), and F-free ZIFs (FIG.11C-D), respectively; this demonstrates that the impressive hydrophobicity of the MeMOF, MeCTC, and F-free ZIF embodiments illustrated in FIG.s 2-4, 9 and 10, respectively, requires metal coordination and cannot be attained by F-free alkylation or arylation on the azole free ligand alone. FIG.13 illustrates “chart 1”, or structures of exemplary MeMOF ligands. FIG.14 illustrates “chart 2”, or illustrates structures of representative polymethylated ZIF-8 analogues. FIG.15A-B illustrate crystal structures of exemplary compounds: (FIG.15A) FMOF-1c and (FIG.15B) MeMOF-1c, as discussed in detail in Example 2, below. FIG.16A-B illustrate CO2 and CH4 adsorption isotherms of (FIG.16A) FMOF-1c and (FIG.16B) MeMOF-1c at 288, 298, and 308 K, as discussed in detail in Example 2, below. FIG.17A-B illustrate: (FIG.17A) Comparison of CO2and CH4adsorption isotherms of FMOF-1c and MeMOF-1c at 298 K. (FIG.17B) CO2 adsorption isotherms of MeMOF-1c using two different charge methods at 298 K, as discussed in detail in Example 2, below. PATENT 6343*161006PCT / Omary-M17 FIG.18A-F illustrates images of snapshots at 1, 5, and 40 bar, respectively, of FMOF-1c for (FIG.18A-C) CO2 occupancy (red spheres) and (FIG.18D-F) CH4 occupancy (blue spheres), as discussed in detail in Example 2, below. FIG.19A-F illustrates images of snapshots at 1, 5, and 40 bar, respectively, of MeMOF-1c for (FIG.19A-C) CO2 occupancy (red spheres) and (FIG.19D-F) CH4 occupancy (blue spheres), as discussed in detail in Example 2, below. FIG.20A-B graphically illustrates simulated isosteric heats of adsorption, Qst, for CO2 and CH4 of FMOF-1c and MeMOF-1c: (FIG.20A) as a function of uptake and (FIG. 20B) as a function of pressure at 298 K, as discussed in detail in Example 2, below. FIG.21A-B graphically illustrate: (FIG.21A) Henry’s constant, KH, and (FIG. 21B) isosteric heat of adsorption at infinite dilution, Qst0, for CO2 and CH4 at various temperatures in MeOF-1c and FMOF-1c structures, obtained from Widom insertion method, as discussed in detail in Example 2, below. FIG.22A-B graphically illustrate the breakdown of (FIG.22A) total potential energy and (FIG.22B) percentage of total potential energy into host-guest and guest- guest contribution for CO2 and CH4 adsorptions in FMOF-1c, obtained from GCMC simulations at 298 K, as discussed in detail in Example 2, below. FIG.23A-D illustrate images of adsorption sites of (FIG.23A) CO2 and (FIG. 23B) CH4 in FMOF-1c; (FIG.23C) CO2 and (FIG.23D) CH4 in MeMOF-1c. Initial andfinal (after minimization) positions of CO2 are represented by orange and dark-redspheres, respectively, while analogous symbols for CH4 are shown as cyan and dark-blue spheres, respectively; gray spheres represent different positions of molecules during minimization with some points omitted for clarity purposes, as discussed in detail in Example 2, below. FIG.24A-D schematically illustrates DFT-optimized structures of the parent CF3- substituted linker with (FIG.24A) CO2 and (FIG.24B) CH4; and methyl-functionalized linker with (FIG.24C) CO2 and (FIG.24D) CH4. Color code (O: red, F: pink, N: blue, C: gray, and H: white), as discussed in detail in Example 2, below. FIG.25A-B graphically illustrate (FIG.25A) Henry’s constant (KH) for H2O, CO2, and CH4at 298 K; (FIG.25B) adsorption selectivity of CO2and CH4over water for various MOFs at 298 K, as discussed in detail in Example 2, below. FIG.26 graphically illustrates water uptake for FMOF-1c and MeMOF-1c at 298 degrees K, as discussed in detail in Example 2, below. PATENT 6343*161006PCT / Omary-M17 FIG.27 graphically illustrates adsorption isotherms of pure component CH4 and a binary mixture of CH4 and H2O at 80% relative humidity in FMOF-1c at 298 K, as discussed in detail in Example 2, below. FIG.28A-B graphically illustrates adsorption isotherms of (FIG.28A) pure component CO2 and a binary mixture of CO2 and H2O at 80% relative humidity and (FIG. 28B) pure component CH4 and a binary mixture of CH4 and water at 80% relative humidity in MeMOF-1c at 298 K, as discussed in detail in Example 2, below. FIG.29A-B graphically illustrate: (FIG.29A) PXRD pattern of the synthesized MeMOF-2 herein (b) overlaid with the published PXRD pattern by Zhai et al. (a)67and (FIG.29B) experimental PXRD pattern of the experimentally-prepared MeMOF-2 sample herein (b) overlaid with the simulated PXRD patterns corresponding to the experimental crystal structure of FMOF-145(d) and the hypothetical MeMOF-1c analogue thereof (c) , as discussed in detail in Example 2, below. FIG.30 graphically, and in images, illustrates water-drop contact angle data for PET only, PET control (sanded), treated PET_1 (FMOF-1@PET), and treated PET_2 (MeMOF-2@PET) from left-to-right, respectively, as discussed in detail in Example 2, below. Like reference symbols in the various drawings indicate like elements. DETAILED DESCRIPTION In alternative embodiments, provided are polymers comprising a metal coordination complex comprising a repeating unit of an alkylated azolate, wherein the alkylated azolate comprises more than one alkyl group, and nitrogen atoms of the alkylated azolate are coordinated to metals (M), and methods of making and using them. In alternative embodiments, provided are coordination polymers, named methylated metal-organic frameworks or MeMOFs, comprising methylated azolates such as 3,5- dimethyl-1,2,4-triazolate, and metal cations such as silver (I) and copper (II) ions. In alternative embodiments, provided are polymers comprising large octopus-type aryl- bridged poly-azolate ligands and different metals from Ag(I) such as Cu(I), Cu(II), Zn(II), Zr(IV), Ni(II), etc., that can be employed in MOFs. In alternative embodiments, polymers as provided herein are superhydrophobic, or extremely water-repellent. In alternative embodiments, polymers as provided herein are coated onto or added to a substrate to impart superhydrophobic or water-repellent properties to a substrate, where PATENT 6343*161006PCT / Omary-M17 the substrate can be for example, a packaging surface, a textile, a plastic, a paper, a metal, or a bioderived or synthetic polymer. FMOFs such as FMOF-1, which is 3,5-bis(trifluoromethyl)-1,2,4- triazolatosilver(I), have received significant interest for their extraordinary properties, including exceptional superhydrophobicity. These properties have been linked mostly to the presence of fluorine atoms within their structure. In alternative embodiments, provided herein are fluorine-free materials for a similar benefit in hydrophobicity, dubbed “MeMOF-1.” In alternative embodiments provided are superhydrophobic compositions of a metal organic framework (MOFs) comprising a dimethyl triazole ligand or analogues thereof and a metal. In various embodiments, the metal is selected from aluminum, steel, silver, copper, zinc, zirconia, nickel, alloys thereof and combinations thereof. Definitions. The following definitions are included to provide a clear and consistent understanding of the specification and claims. As used herein, the recited terms have the following meanings. All other terms and phrases used in this specification have their ordinary meanings as one of skill in the art would understand. Such ordinary meanings may be obtained by reference to technical dictionaries, such as Hawley’s Condensed Chemical Dictionary 14thEdition, by R.J. Lewis, John Wiley & Sons, New York, N.Y., 2001. In alternative embodiments the term "contacting" refers to the act of touching, making contact, or of bringing to immediate or close proximity, including at the cellular or molecular level, for example, to bring about a physiological reaction, a chemical reaction, or a physical change, for example, in a solution, in a reaction mixture, in vitro, or in vivo. In alternative embodiments the term “substantially” as used herein, is a broad term and is used in its ordinary sense, including, without limitation, being largely but not necessarily wholly that which is specified. For example, the term could refer to a numerical value that may not be 100% the full numerical value. The full numerical value may be less by about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15%, or about 20%. In alternative embodiments the term "halo" or "halide" refers to fluoro, chloro, bromo, or iodo. Similarly, the term "halogen" refers to fluorine, chlorine, bromine, and iodine. PATENT 6343*161006PCT / Omary-M17 In alternative embodiments the term "alkyl" refers to a branched or unbranched hydrocarbon having, for example, from 1-20 carbon atoms, and often 1-12, 1-10, 1-8, 1-6, or 1-4 carbon atoms; or for example, a range between 1-20 carbon atoms, such as 2-6, 3- 6, 2-8, or 3-8 carbon atoms. As used herein, the term “alkyl” also encompasses a “cycloalkyl”, defined below. Examples include, but are not limited to, methyl, ethyl, 1- propyl, 2-propyl (iso-propyl), 1-butyl, 2-methyl-1-propyl (isobutyl), 2-butyl (sec-butyl), 2-methyl-2-propyl (t-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-2- butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2-methyl-3-pentyl, 2,3- dimethyl-2-butyl, 3,3-dimethyl-2-butyl, hexyl, octyl, decyl, dodecyl, and the like. The alkyl can be unsubstituted or substituted, for example, with a substituent described below or otherwise described herein. The alkyl can also be optionally partially or fully unsaturated. As such, the recitation of an alkyl group can include an alkenyl group or an alkynyl group. The alkyl can be a monovalent hydrocarbon radical, as described and exemplified above, or it can be a divalent hydrocarbon radical (i.e., an alkylene). In alternative embodiments an alkylene is an alkyl group having two free valences at a carbon atom or two different carbon atoms of a carbon chain. Similarly, alkenylene and alkynylene are respectively an alkene and an alkyne having two free valences at two different carbon atoms, or an alkenylene can have the two free valences on the same carbon. In alternative embodiments the term "cycloalkyl" refers to cyclic alkyl groups of, for example, from 3 to 10 carbon atoms having a single cyclic ring or multiple condensed rings. Cycloalkyl groups include, by way of example, single ring structures such as cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, and the like, or multiple ring structures such as adamantyl, and the like. The cycloalkyl can be unsubstituted or substituted. The cycloalkyl group can be monovalent or divalent and can be optionally substituted as described for alkyl groups. The cycloalkyl group can optionally include one or more cites of unsaturation, for example, the cycloalkyl group can include one or more carbon-carbon double bonds, such as, for example, 1-cyclopent-1-enyl, 1-cyclopent-2-enyl, 1-cyclopent- 3-enyl, cyclohexyl, 1-cyclohex-1-enyl, 1-cyclohex-2-enyl, 1-cyclohex-3-enyl, and the like. In alternative embodiments the term “heteroatom” refers to any atom in the periodic table that is not carbon or hydrogen. Typically, a heteroatom is O, S, N, P. The heteroatom may also be a halogen, metal or metalloid. PATENT 6343*161006PCT / Omary-M17 In alternative embodiments the term "heterocycloalkyl" or “heterocyclyl” refers to a saturated or partially saturated monocyclic, bicyclic, or polycyclic ring containing at least one heteroatom selected from nitrogen, sulfur, oxygen, preferably from 1 to 3 heteroatoms in at least one ring. Each ring is preferably from 3- to 10-membered, more preferably 4 to 7 membered. Examples of suitable heterocycloalkyl substituents include pyrrolidinyl, tetrahydrofuranyl, tetrahydrothiofuranyl, piperidinyl, piperazinyl, tetrahydropyranyl, morpholinyl, 1,3-diazapanyl, 1,4-diazapanyl, 1,4-oxazepanyl, and 1,4- oxathiapanyl. The group may be a terminal group or a bridging group. The term "aromatic" refers to either an aryl or heteroaryl group or substituent described herein. Additionally, an aromatic moiety may be a bisaromatic moiety, a trisaromatic moiety, and so on. A bisaromatic moiety has a single bond between two aromatic moieties such as, but not limited to, biphenyl, or bipyridine. Similarly, a trisaromatic moiety has a single bond between each aromatic moiety. In alternative embodiments the term "aryl" refers to an aromatic hydrocarbon group derived from the removal of at least one hydrogen atom from a single carbon atom of a parent aromatic ring system. The radical attachment site can be at a saturated or unsaturated carbon atom of the parent ring system. The aryl group can have from 6 to 30 carbon atoms, for example, about 6-10 carbon atoms. The aryl group can have a single ring (for example, phenyl) or multiple condensed (fused) rings, wherein at least one ring is aromatic (for example, naphthyl, dihydrophenanthrenyl, fluorenyl, or anthryl). Typical aryl groups include, but are not limited to, radicals derived from benzene, naphthalene, anthracene, biphenyl, and the like. The aryl can be unsubstituted or optionally substituted with a substituent described below. For example, a phenyl moiety or group may be substituted with one or more substituents RXwhere RXis at the ortho-, meta-, or para- position, and X is an integer variable of 1 to 5. In alternative embodiments the term "heteroaryl" refers to a monocyclic, bicyclic, or tricyclic ring system containing one, two, or three aromatic rings and containing at least one nitrogen, oxygen, or sulfur atom in an aromatic ring. The heteroaryl can be unsubstituted or substituted, for example, with one or more, and in particular one to three, substituents, as described in the definition of "substituted". Typical heteroaryl groups contain 2-20 carbon atoms in the ring skeleton in addition to the one or more heteroatoms, wherein the ring skeleton comprises a 5-membered ring, a 6-membered ring, two 5- membered rings, two 6-membered rings, or a 5-membered ring fused to a 6-membered ring. Examples of heteroaryl groups include, but are not limited to, 2H-pyrrolyl, 3H- PATENT 6343*161006PCT / Omary-M17 indolyl, 4H-quinolizinyl, acridinyl, benzo[b]thienyl, benzothiazolyl, ^-carbolinyl, carbazolyl, chromenyl, cinnolinyl, dibenzo[b,d]furanyl, furazanyl, furyl, imidazolyl, imidizolyl, indazolyl, indolisinyl, indolyl, isobenzofuranyl, isoindolyl, isoquinolyl, isothiazolyl, isoxazolyl, naphthyridinyl, oxazolyl, perimidinyl, phenanthridinyl, phenanthrolinyl, phenarsazinyl, phenazinyl, phenothiazinyl, phenoxathiinyl, phenoxazinyl, phthalazinyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolyl, quinoxalinyl, thiadiazolyl, thianthrenyl, thiazolyl, thienyl, triazolyl, tetrazolyl, and xanthenyl. In one embodiment the term "heteroaryl" denotes a monocyclic aromatic ring containing five or six ring atoms containing carbon and 1, 2, 3, or 4 heteroatoms independently selected from non-peroxide oxygen, sulfur, and N(Z) wherein Z is absent or is H, O, alkyl, aryl, or (C1-C6)alkylaryl. In some embodiments, heteroaryl denotes an ortho-fused bicyclic heterocycle of about eight to ten ring atoms derived therefrom, particularly a benzo-derivative or one derived by fusing a propylene, trimethylene, or tetramethylene diradical thereto. In alternative embodiments the term "substituted" or “substituent” is intended to indicate that one or more (for example, in various embodiments, 1-10; in other embodiments, 1-6; in some embodiments 1, 2, 3, 4, or 5; in certain embodiments, 1, 2, or 3; and in other embodiments, 1 or 2) hydrogens on the group indicated in the expression using “substituted” (or “substituent”) is replaced with a selection from the indicated group(s), or with a suitable group known to those of skill in the art, provided that the indicated atom’s normal valency is not exceeded, and that the substitution results in a stable compound. Suitable indicated groups include, for example, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, hydroxyalkyl, aryl, heteroaryl, heterocyclyl, cycloalkyl, alkanoyl, alkoxycarbonyl, amino, alkylamino, dialkylamino, carboxyalkyl, alkylthio, alkylsulfinyl, and alkylsulfonyl. Substituents of the indicated groups can be those recited in a specific list of substituents described herein, or as one of skill in the art would recognize, can be one or more substituents selected from alkyl, alkenyl, alkynyl, alkoxy, halo, haloalkyl, hydroxy, hydroxyalkyl, aryl, heteroaryl, heterocycle, cycloalkyl, alkanoyl, alkoxycarbonyl, amino, alkylamino, dialkylamino, trifluoromethylthio, difluoromethyl, acylamino, nitro, trifluoromethyl, trifluoromethoxy, carboxy, carboxyalkyl, keto, thioxo, alkylthio, alkylsulfinyl, alkylsulfonyl, and cyano. Suitable substituents of indicated groups can be bonded to a substituted carbon atom include F, Cl, Br, I, OR', OC(O)N(R')2, CN, CF3, OCF3, R', O, S, C(O), S(O), methylenedioxy, ethylenedioxy, PATENT 6343*161006PCT / Omary-M17 N(R')2, SR', SOR', SO2R', SO2N(R')2, SO3R', C(O)R', C(O)C(O)R', C(O)CH2C(O)R', C(S)R', C(O)OR', OC(O)R', C(O)N(R')2, OC(O)N(R')2, C(S)N(R')2, (CH2)0-2NHC(O)R', N(R')N(R')C(O)R', N(R')N(R')C(O)OR', N(R')N(R')CON(R')2, N(R')SO2R', N(R')SO2N(R')2, N(R')C(O)OR', N(R')C(O)R', N(R')C(S)R', N(R')C(O)N(R')2, N(R')C(S)N(R')2, N(COR')COR', N(OR')R', C(=NH)N(R')2, C(O)N(OR')R', or C(=NOR')R' wherein R’ can be hydrogen or a carbon-based moiety (for example, (C1- C6)alkyl), and wherein the carbon-based moiety can itself be further substituted. When a substituent is monovalent, such as, for example, F or Cl, it is bonded to the atom it is substituting by a single bond. When a substituent is divalent, such as O, it is bonded to the atom it is substituting by a double bond; for example, a carbon atom substituted with O forms a carbonyl group, C=O. In alternative embodiments the term, “repeat unit”, “repeating unit”, or “block” as used herein refers to the moiety of a polymer that is repetitive. The repeat unit may comprise one or more repeat units, labeled as, for example, repeat unit A, repeat unit B, repeat unit C, etc. Repeat units A-C, for example, may be covalently bound together to form a combined repeat unit. Monomers or a combination of one or more different monomers can be combined to form a (combined) repeat unit of a polymer or copolymer. In alternative embodiments the term “molecular weight” for the copolymers disclosed herein refers to the average number molecular weight (Mn). The correspondingweight average molecular weight (Mw) can be determined from other disclosedparameters by methods (for example, by calculation) known to the skilled artisan. Exemplary Embodiments A) MeMOFs: Divergent coordination sites to bridge metal / metal cluster centers / nodes to warrant coordination polymer or oligomer formation are indicated for each ligand with dashed lines; see Chart 1, illustrated in FIG.13, illustrating structures of exemplary MeMOF ligands. These alterations will include using more indigenous metals such as Cu(II) or Zn(II) vs isoelectronic Ag(I) or Au(I) metal centers in existing MeMOF materials, as well as using Me-substituted poly-azolates as opposed to a single methylated triazolate in the organic ligands. Exemplary Embodiments comprise: 1. A metal coordination polymer or oligomer comprising a repeating unit of an alkylated azolate, wherein nitrogen atoms of the alkylated azolate are coordinated to metal ions. PATENT 6343*161006PCT / Omary-M17 2. The metal coordination polymer or oligomer of embodiment 1, wherein the alkylated azolate is represented by Formula I or II: J2is N---M, wherein N is the nitrogen atom of the triazole ring of Formula I; each M is independently a metal ion; Ph is phenyl or absent, wherein phenyl is optionally substituted with substituents from the group consisting of –(C1-C6)alkyl and halo; R1and R2are each independently –(C1-C6)alkyl or H; R3and R4are each independently –(C1-C6)alkyl or H; and R5and R6are each independently H or –(C1-C6)alkyl, wherein the alkylated azolate of Formula I or II is substituted with at least two – (C1-C6)alkyl groups. 3. The metal coordination polymer or oligomer of embodiment 1 or 2, wherein the metal ion is a transition metal ion. 4. The metal coordination polymer or oligomer of any one of embodiments 1-3, wherein the metal ion is a copper ion or silver ion. 5. The metal coordination polymer or oligomer of any one of embodiments 1-4, wherein R1, R2, R3and R4are CH3 when J is J1of Formula I. 6. The metal coordination polymer or oligomer of any one of embodiments 1-4, wherein R1, R2, R3and R4are H when J is J1of Formula I. 7. The metal coordination polymer or oligomer of any one of embodiments 1-6, wherein the alkylated azolate is represented by Formula IA: PATENT 6343*161006PCT / Omary-M17 wherein Ra, Rb, Rc, and Rdare each independently –(C1-C6)alkyl, halo, or H. 8. The metal coordination polymer or oligomer of any one of embodiments 1-6, wherein the alkylated azolate is represented by Formula IB: 9. The metal coordination polymer or oligomer of any one of embodiments 1-4, wherein the alkylated azolate is represented by Formula IC: wherein Ra, Rb, Rc, and Rdare each independently –(C1-C6)alkyl, halo, or H. 10. The metal coordination polymer or oligomer of any one of embodiments 1-4, wherein the alkylated azolate is represented by Formula ID: 11. The metal coordination polymer or oligomer of embodiment 9 or 10, wherein R5and R6of Formula IC are H; or R1and R2of Formula ID are H. 12. The metal coordination polymer or oligomer of any one of embodiments 1-11, wherein Ra, Rb, Rcand Rdare CH3. 13. The metal coordination polymer or oligomer of any one of embodiments 1-11, wherein Ra, Rb, Rcand Rdare H. 14. The metal coordination polymer or oligomer of embodiment 1, wherein the metal coordination polymer or oligomer comprises: 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)-2,3,5,6-tetramethylbenzene coordinated to copper(II); PATENT 6343*161006PCT / Omary-M17 1,4-bis(4,4’-pyrazolato)-2,3,5,6-tetramethylbenzene coordinated to copper(II); 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)benzene coordinated to copper(II); bis(4,4’-[3,5-dimethyl]pyrazolate) coordinated to copper(II); 1,4-bis(4,4’-tetrazolato)-2,3,5,6-tetramethylbenzene coordinated to copper(II); or 3,5-dimethyl-1,2,4-triazolate coordinated to copper(II); or wherein the metal coordination polymer or oligomer comprises: 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)-2,3,5,6-tetramethylbenzene coordinated to silver(I); 1,4-bis(4,4’-pyrazolato)-2,3,5,6-tetramethylbenzene coordinated to silver(I); 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)benzene coordinated to silver(I); bis(4,4’-[3,5-dimethyl]pyrazolate) coordinated to silver(I); 1,4-bis(4,4’-tetrazolato)-2,3,5,6-tetramethylbenzene coordinated to silver(I); or 3,5-dimethyl-1,2,4-triazolate coordinated to silver(I). 15. A method for forming a superhydrophobic surface comprising: a) coating a substrate with the metal coordination polymer or oligomer of any one of embodiments 1-14; or b) mixing a substance with the metal coordination polymer or oligomer of any one of embodiments 1-14 then coating a substrate with the mixture; wherein the superhydrophobic surface is capable of forming a contact angle of at least 130 degrees with a water drop. 16. The method of embodiment 15, wherein the substrate or substance is polyethylene terephthalate, Nylon 6 / 6, poly(p-phenylene oxide) / polystyrene blend, activated carbon, carbon fiber, low carbon steel, aluminum, aluminum alloy, or a transition metal. 17. The method of embodiment 15 or 16, wherein the metal coordination polymer or oligomer is thermally stable at a process melt temperature of the substance. 18. The method of embodiments 15-17, wherein the superhydrophobic surface is corrosion resistant. 19. The method of embodiments 15-18, wherein the superhydrophobic surface is a barrier to moisture, air, ultraviolet light, or a combination thereof. 20. The method of embodiments 15-19, wherein the superhydrophobic surface absorbs oil; or the superhydrophobic surface purifies water. B) MeZIFs: PATENT 6343*161006PCT / Omary-M17 Zeolitic imidazolate frameworks such as ZIF-8 (with a single Me group on the ligand) are well-known sub-type of porous coordination polymers or oligomers and are known to be more hydrophobic than the more ubiquitous variant, MOFs (most commonly containing polycarboxylated aromatic ligands instead of imidazolates). Here we can utilize additional Me groups on one or more C atoms in the imidazolate ligand in order to render greater hydrophobicity than that of ZIF-8, as illustrated in Chart 2, illustrated as FIG.14. Chart 2, illustrated as FIG.14, illustrates structures of representative polymethylated ZIF-8 analogues. See the Methods / Section 1B below for the detailed synthetic procedure of the Me2ZIF-8 alternative embodiment. C) MeCTCs: Convergent coordination of azolate ligands to bridge metal / metal cluster centers / nodes to warrant coordination oligomer formation represents a third approach for the polymethylated superhydrophobic materials in this invention. Chart 3 shows representative examples of such Cu(I) or Ag(I) cyclic trinuclear (or tetranuclear) complexes (CTCs). Chart 3 illustrates exemplary structures of representative polymethylated pyrazolate (Pz) or triazolate (Tz) ligands in (a) and (b), respectively, whereas their corresponding trinuclear or tetranuclear CTCs are shown in (c). See the Methods / Section1C below for the detailed synthetic procedure of the Me2CTC-1 preferred embodiment. iPr2Tz PATENT 6343*161006PCT / Omary-M17 D) Hybrid materials of A-C as additives to or coatings on other matrix / substrate materials: In some embodiments, the composition may be spread onto or otherwise deposited on a surface that may be used for various purposes described herein. For example, the surface may comprise a polymer surface, a plastic surface, or a glass surface. In other embodiments, the surface may be any material including a ceramic substance, a glass, a plastic, a polymer or co-polymer, any combinations thereof, or a coating of one material on another. Such surfaces may include glass materials such as soda-lime glass, PYREX™ glass, VYCOR™ glass, quartz glass; silicon; plastics or polymers, including dendritic polymers, such as poly(vinyl chloride), poly(vinyl alcohol), poly(methyl methacrylate), poly(vinyl acetate-maleic anhydride), poly(dimethylsiloxane) monomethacrylate, cyclic olefin polymers, fluorocarbon polymers, polystyrenes, polypropylene, polyethyleneimine; copolymers such as poly(vinyl acetate-co-maleic anhydride), poly(styrene-co-maleic anhydride), poly(ethylene-co-acrylic acid) or derivatives of these or the like. In some embodiments, the surface may be formed of materials including, for example, polystyrene, polypropylene, acrylate polymers, nylon, nitrocellulose, SEPHAROSE™, and so forth. In some exemplary embodiments, the ligand is 3,5-(CH3)2-1,2,4-triazolate (L1). In various other embodiments the analogues of L1 comprise ligands L2-L6 (Chart 1). In yet other embodiments, the metal is replaced by porous silicon, polyethylene terephthalate (PET) and plastic. In still other exemplary embodiments, the waterdrop contact angle (θ) is > 135o, > 150o, or 165oor greater. In various other exemplary embodiments, the structural formula is C4H6AgN3. PATENT 6343*161006PCT / Omary-M17 Exemplary embodiments In alternative embodiments, provided are: 1. The composition comprising a metal coordination polymer or oligomer comprising a repeating unit of an alkylated azolate, wherein one or more nitrogen atoms of the alkylated azolate are coordinated to metal ions and the alkylation comprises more than one methyl (Me = CH3) group. 2. The metal coordination polymer or oligomer of aspect 1, wherein the alkylated azolate is represented by Formula I or II: J2is N---M, wherein N is the nitrogen atom of the triazole ring of Formula I; each M is independently a metal ion; Ar is an aromatic ring spacer (for example, an unsubstituted ditopic p- C6H4- ring or with Me-substitution of some or all of the four H atoms) or absent, wherein phenyl is optionally substituted with substituents from the group consisting of –(C1-C6)alkyl and halo; R1and R2are each independently –(C1-C6)alkyl or H; and R3and R4are each independently –(C1-C6)alkyl or H, wherein the alkylated azolate of Formula I or II is substituted with at least two – (C1-C6)alkyl groups. 3. The metal coordination polymer or oligomer of aspect 1 or 2, wherein the metal ion is a transition metal ion. 4. The metal coordination polymer or oligomer of any one of aspects 1-3, wherein the metal ion is a silver ion or copper ion. PATENT 6343*161006PCT / Omary-M17 5. The metal coordination polymer or oligomer of any one of aspects 1-4, wherein the alkylated azolate is represented by Formula IA, where J = J2= N---M, and R1and R2and are –(C1-C6)alkyl, halo, or H: 6. The uses of the known metal coordination polymer or oligomer composition of aspect 5 wherein R1and R2are both CH3 and M = Ag. 7. The metal coordination polymer or oligomer of any one of aspects 1-4, wherein R1, R2, R3, R4or Ra, Rb, Rc, and Rdare each independently –(C1-C6)alkyl, halo, or H when J is J1of Formula IB: 8. The metal coordination polymer or oligomer of aspect 7, wherein two or more among R1, R2, R3, and R4or Ra, Rb, Rc, and Rdare CH3. 9. The metal coordination polymer or oligomer of any one of aspects 1-4, wherein Ra, Rb, Rc, and Rdare each independently –(C1-C6)alkyl, halo, or H when J is J1of Formula IC: 10. The metal coordination polymer or oligomer of aspect 9, wherein two or more among Ra, Rb, Rc, and Rdare CH3. 11. The metal coordination polymer or oligomer of any one of aspects 1-4, wherein R1, R2, R3, and R4are each independently –(C1-C6)alkyl, halo, or H when J is J1of Formula ID: PATENT 6343*161006PCT / Omary-M17 12. The metal coordination polymer or oligomer of aspect 11, wherein two or more among R1, R2, R3, and R4are CH3. 13. The metal coordination polymer or oligomer of aspect 1 and uses of known counterparts, wherein the metal coordination polymer or oligomer comprises: 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)-2,3,5,6-tetramethylbenzene coordinated to copper(II); 1,4-bis(4,4’-pyrazolato)-2,3,5,6-tetramethylbenzene coordinated to copper(II); 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)benzene coordinated to copper(II); bis(4,4’-[3,5-dimethyl]pyrazolate) coordinated to copper(II); 1,4-bis(4,4’-tetrazolato)-2,3,5,6-tetramethylbenzene coordinated to copper(II); or 3,5-dimethyl-1,2,4-triazolate coordinated to copper(II); or wherein the metal coordination polymer or oligomer comprises: 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)-2,3,5,6-tetramethylbenzene coordinated to silver(I); 1,4-bis(4,4’-pyrazolato)-2,3,5,6-tetramethylbenzene coordinated to silver(I); 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)benzene coordinated to silver(I); bis(4,4’-[3,5-dimethyl]pyrazolate) coordinated to silver(I); 1,4-bis(4,4’-tetrazolato)-2,3,5,6-tetramethylbenzene coordinated to silver(I); or 3,5-dimethyl-1,2,4-triazolate coordinated to silver(I). 14. The metal coordination oligomer of aspect 1, wherein the alkylated azolate is represented by the cyclic trinuclear or tetranuclear complex (CTC) of Formula III or IV, respectively: wherein, J is J1= C-R3 unsubstituted (R3 = H) or substituted (R3 ^ H), representing the carbon atom of the pyrazole ring, or J2= N, representing the nitrogen atom of the triazole ring; R1, R2, and R3 are each independently –(C1-C6)alkyl, aryl, alkyl-aryl, halo, or H. PATENT 6343*161006PCT / Omary-M17 15. The uses of the known poly-methylated CTC of aspect 14, wherein M = Ag, J = J1, R3 = H, R1 and R2 are both i-Pr = -CH(CH3)2, corresponding to Formula IIIA: 16. The uses of the known poly-methylated CTC of aspect 14, wherein M = Ag, J = J1, R3 = H, R1 and R2 are both t-Bu = -C(CH3)3, corresponding to Formula IVA: 17. The metal coordination oligomer of aspect 1, wherein the alkylated azolate is represented by the poly-methylated zeolitic imidazolate framework (MeZIF) of Formula V or VI, respectively: wherein, R, R’, and R” or RI, RII, RIII, RIV, and RVare each independently –(C1- C6)alkyl, aryl, alkyl-aryl, halo, or H. 18. The ZIF of aspect 17, wherein M = Zn, R = i-Pr = CH(CH3)2, R’ = H, and R” = H, corresponding to Formula VA: 19. The ZIF of aspect 17, wherein M = Zn, R = i-Pr = CH(CH3)2, R’ = H, and R” = H, corresponding to Formula VIA: PATENT 6343*161006PCT / Omary-M17 20. The uses of both and known compositions comprising a metal coordination polymer or oligomer comprising a repeating unit of an alkylated azolate, wherein one or more nitrogen atoms of the alkylated azolate are coordinated to metal ions and the alkylation comprises more than one methyl (Me = CH3) group. 21. A method for forming a superhydrophobic surface comprising: a) coating a substrate with the metal coordination polymer or oligomer of any one of aspects 1-15; or b) mixing a substance with the metal coordination polymer or oligomer of any one of aspects 1-15 then coating a substrate with the mixture; wherein the superhydrophobic surface is capable of forming a contact angle of at least 130 degrees with a water drop. 22. The method of aspect 16, wherein the substrate or substance is polyethylene terephthalate, Nylon 6 / 6, poly(p-phenylene oxide) / polystyrene blend, activated carbon, carbon fiber, low carbon steel, aluminum, aluminum alloy, or a transition metal. 23. The method of aspect 15 or 16, wherein the metal coordination polymer or oligomer is thermally stable at a process melt temperature of the substance. 24. The method of aspects 15-17, wherein the superhydrophobic surface is corrosion resistant. 25. The method of aspects 15-18, wherein the superhydrophobic surface is a barrier to moisture, air, ultraviolet light, or a combination thereof. 26. The method of aspects 15-19, wherein the superhydrophobic surface absorbs oil; or the superhydrophobic surface purifies water. Exemplary embodiments 1. A superhydrophobic coordination polymer or oligomer material, comprising a three- dimensional network formed by the coordination of at least one or more poly-methylated ligand, alone or with another co-ligand, and a metal center. PATENT 6343*161006PCT / Omary-M17 2. The superhydrophobic coordination polymer or oligomer material of Aspect 1 in which the poly-methylated ligand is a poly-methylated azolate, whereby the azolate is mono- or poly-triazolate, -pyrazolate, tetrazolate, or -imidazolate. 3. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is 3,5-Dimethyl-1,2,4-triazolate. 4. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is 3,5-Dimethyl-1,2,4-triazolate and the metal is Ag(I). 5. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is 1,4-bis(4,4’-tetrazolato)-2,3,5,6-tetramethylbenzene. 6. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is 1,4-bis(4,4’-tetrazolato)-2,3,5,6-tetramethylbenzene and the metal is Cu(II). 7. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is 1,4-bis(4,4’-tetrazolato)-2,3,5,6-tetramethylbenzene and the metal is Ag(I). 8. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is 1,4-bis(4,4’-pyrazolato)-2,3,5,6-tetramethylbenzene. PATENT 6343*161006PCT / Omary-M17 9. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is 1,4-bis(4,4’-pyrazolato)-2,3,5,6-tetramethylbenzene and the metal is Cu(II). 10. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is 1,4-bis(4,4’-pyrazolato)-2,3,5,6-tetramethylbenzene and the metal is Ag(I). 11. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)-2,3,5,6- tetramethylbenzene. 12. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)-2,3,5,6- tetramethylbenzene and the metal is Cu(II). 13. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)-2,3,5,6- tetramethylbenzene and the metal is Ag(I). 14. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)benzene. PATENT 6343*161006PCT / Omary-M17 15. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)benzene and the metal is Cu(II). 16. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)benzene and the metal is Ag(I). 17. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is bis(4,4’-[3,5-dimethyl]pyrazolate). 18. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is bis(4,4’-[3,5-dimethyl]pyrazolate) and the metal is Cu(II). 19. The superhydrophobic coordination polymer or oligomer material of Aspect 2 in which the poly-methylated ligand is bis(4,4’-[3,5-dimethyl]pyrazolate) and the metal is Ag(I). 20. A method of producing a superhydrophobic surface, comprising applying a MeMOF material among those described in Aspects 1-19 to a substrate and allowing it to form a coating with a higher water drop contact angle than that of the substrate itself to attain the superhydrophobic range of at least 130 degrees. 21. The method of producing a superhydrophobic surface, comprising applying the MeMOF material described in Aspect 7 to a plastic substrate and allowing it to form a PATENT 6343*161006PCT / Omary-M17 coating with water drop contact angles in the superhydrophobic range of at least 130 degrees. 22. The method of Aspect 21 in which the plastic substrate is PET (polyethylene terephthalate) to form a coating with superhydrophobic water drop contact angles between 165 and 175 degrees. 23. A method of producing a superhydrophobic surface, comprising mixing a MeMOF material among those described in Aspects 1-19 within a substrate matrix and allowing it to form a coating with a higher water drop contact angle than that of the unmixed substrate itself to attain the superhydrophobic range of at least 130 degrees. 24. The method of Aspect 23 in which the substrate material is activated carbon. 25. A method of producing a superhydrophobic surface, comprising admixing a MeMOF material among those described in Aspects 1-19 within a plastic substrate matrix, as an in situ additive such that the thermal stability of the MeMOF additive is higher than the process melt temperature of the polymer substrate material, to form a coating with a higher water drop contact angle than that of the unmixed substrate itself to attain the superhydrophobic range of at least 130 degrees. 26. The method of Aspect 25 in which the additive is the MeMOF described in Aspect 7 (thermal stability = 369.72 °C) and the polymer substrate is PET (polyethylene terephthalate; process melt temperature = 271-293°C). 27. The method of Aspect 25 in which the additive is the MeMOF described in Aspect 7 (thermal stability = 369.72 °C) and the polymer substrate is Nylon 6 / 6 (process melt temperature = 260-293 °C). 28. The method of Aspect 25 in which the additive is the MeMOF described in Aspect 7 (thermal stability = 369.72 °C) and the polymer substrate is Poly(p-phenylene oxide) / Polystyrene blend (process melt temperature = 249-304 °C). 29. The use of the method and embodiments in Aspect 20 in which the substrate is metallic to impart corrosion resistance in absence of the coating material. 30. The use of Aspect 29 in which the substrate is the low-carbon steel such as that commonly used in construction. 31. The use of Aspect 29 in which the substrate is aluminum or aluminum alloy such as that used in airplane fuselage material’s manufacturing. 32. The use of the method and embodiments in Aspect 20 in which the substrate is carbon fiber, such as that used in airplane fuselage material’s manufacturing, to impart corrosion resistance in absence of the coating material. PATENT 6343*161006PCT / Omary-M17 33. The use of the method and embodiments in Aspect 23 for water purification columns. 34. The use of the method and embodiments in Aspect 24 for water purification columns. 35. The use of the method and embodiments in Aspect 23 for extracting frying oil from fried food products such as potato chips or French fries, corn tortilla chips, etc. to decrease their lipid content.. 36. The use of the method and embodiments in Aspect 24 for extracting frying oil from fried food products such as potato chips or French fries, corn tortilla chips, etc. to decrease their lipid content. 37. The use of the method and embodiments in Aspect 20 for water / moisture, oxygen, and / or ultraviolet light barrier on various food packaging substrates in order to increase the shelf life of the food / drink. 38. The use of the method and embodiments in Aspect 21 for water / moisture, oxygen, and / or ultraviolet light barrier on various food packaging substrates in order to increase the shelf life of the food / drink. 39. The “uses” of the same poly(3,5-dimethyl-1,2,4-triazolatosilver(I)) chemical composition and same non-porous 3D structure. 40. Both the “embodiments’ materials” and the “uses” thereof for related embodiments with the same poly(3,5-dimethyl-1,2,4-triazolatosilver(I)) chemical composition but alternative structural isomers, including polymorph and other crystallographic isomers with different 3D structures, including porous MeMOF embodiments that we have designed and evaluated their adsorption and hydrophobic / omniphobic via grand canonical Monte Carlo (GCMC) simulations. We also have validated the simulations by using MeMOF-1 in both neat and hybrid form upon another substrate to realize its superhydrophobicity. In particular, our investigation revealed extremely strong superhydrophobic capabilities, characterized by water droplet contact angles between 165 and 175 degrees for the MeMOF-1 composition to validate GCMC predictions, surpassing even the rather strict threshold of 150 degrees for superhydrophobicity. 41. Both the “embodiments’ materials” and the “uses” thereof for other ligand / metal combinations we have designed to impart other MeMOFs with higher surface area and other tunable hydrophobicity and / or omniphobicity (both water and oil repellent akin to PFAS). The theory-guided experimental design and synthesis of MeMOFs composed of one or more of the ligands are shown in Chart 1, alone or with another co-ligand. Other G2+ generations of Me-MOFs are expected to attain higher surface areas as realized in the extensive MOF literature upon increasing the linker size with the same other PATENT 6343*161006PCT / Omary-M17 structural factors (metal / metal cluster node identity, coordination mode, and 3D topology). We claim the chemical composition, embodiment structures, and uses of G1 and G2+ MeMOFs that will take advantage of the hydrophobicity and / or omniphobicity of each MeMOF in both neat form and hybrid form (as additive or coating upon another substrate including plastic, paper, a wood, a glass, bioderived polymer, metal, etc.). Hydrophobic materials are essential in various industrial applications, including coatings, textiles, and packaging, where water repellence is desired. Traditional materials achieving superhydrophobicity often contain fluorine atoms, such as PFAS, which pose environmental and health risks due to their persistence and bioaccumulation. MeMOFs, which are coordination polymers or oligomers composed of methylated ligands such as methylated azolates and metal cations such as silver (I) and copper (II) ions, such as MeMOF-1 = poly(3,5-dimethyl-1,2,4-triazolatosilver(I)), offer a class of promising PFAS alternatives. Some MeMOF-type compositions are known, including the aforementioned poly(3,5-dimethyl-1,2,4-triazolatosilver(I)) reported by Zhai et al. in 2009; however, this material had not been recognized for its hydrophobic properties we have discovered therein. This disclosure provides a class of materials, MeMOFs, whose members exhibit superhydrophobic properties despite the absence of fluorine atoms. This discovery opens avenues for environmentally-friendly hydrophobic applications. MeMOFs’ superhydrophobicity was first predicted by Grand Canonical Monte Carlo (GCMC) simulations and subsequently confirmed through real-world experimentation. Exemplary embodiments 1) Composition: MeMOFs, which are coordination polymers or oligomers composed of methylated ligands such as methylated azolates and metal cations such as silver (I) and copper (II) ions, such as MeMOF-1 = poly(3,5-dimethyl-1,2,4- triazolatosilver(I)); see Chart 1 for representative structural variations of both existing (G1) and newly-conceptualized / designed but yet to be synthesized (G2) MeMOF embodiments. 2. Superhydrophobic Properties: Representative existing embodiments we have designed and synthesized have been found to exhibit water droplet contact angles between 165 and 175 degrees in both neat and hybrid forms (coating or additive on another substrate). 3) Environmental Advantage: Contains no fluorine atoms, reducing environmental and health risks associated with traditional PFAS materials. 4) Verification: Superhydrophobic properties were validated by both GCMC simulations and experimental results for a spectrum of MeMOF embodiments including G1 materials PATENT 6343*161006PCT / Omary-M17 with the same composition but different 3D structure / porosity, as well as with variable compositions. Exemplary Uses and Applications MeMOFs’ superhydrophobic properties render them suitable for various proposed applications, including but not limited to: Water-repellent coatings for textile or fabric surfaces; anti-corrosion coatings for metals; self-cleaning materials; oil / water separation technologies; extracting frying oil from potato chips / other fried food products; H2O / O2 / hv (water or moisture / oxygen / UV light) barriers on various food packaging substrates; Water purification (at least 10x the efficiency of BPL / other commercial adsorbents in fridge / under the sink columns) for both aliphatic and aromatic pollutants – even at 0.1-1% mixing ratios by wt or V. Advantages Over Existing Technologies. 1) Non-Fluorinated: Unlike traditional PFAS, all G1 and G2 MeMOFs do not contain environmentally harmful fluorine atoms or any C-F bonds; 2) High Efficiency: Demonstrate superior water repulsion with contact angles exceeding 150 degrees; 3) Versatility: Applicable in various industries requiring superhydrophobic materials. Synthesis and Safety. In alternative embodiments, the FF-MOF exemplary product is synthesized using silver nitrate, ammonium hydroxide, and ligand X = 3,5- (CH3)2-1,2,4-triazolate. All components of our material are approved to varying degrees for food contact, except for X. Therefore, disclosed herein we provide information on X. Benzotriazole (CAS 95-14-7*, a molecule similar to X (would produce a similar FF-MOF product but not as hydrophobic) is approved for indirect food additives. Silver nitrate is safely added to drinking water; -- at low concentrations for its potential antimicrobial actions. We anticipate extremely low Ag content in the final hybrid material (FF-MOF@KH paper / plastic) such that even if Ag ions leach out (unlikely), the Ag+ ion concentration will be well below FDA / EPA / OSHA / CDC levels; i.e., < 0.05 mg Ag+ / L H2O = 50 ppb. The amount of silver added will not exceed 17 micrograms per kilogram. Benzotriazole may be safely used in surface lubricants employed in the manufacturing of metallic articles that contact food and the total residual lubricant PATENT 6343*161006PCT / Omary-M17 remaining on the metallic article in the form in which it contacts food does not exceed 0.015 milligram per square inch of metallic food-contact surface. Stability. Outstanding thermal stability performance at high temperatures (complete decomposition only occurs at 400 C and only polymorphism w / o weight loss occurs at lower temperatures) suggests that the material could be incorporated into plastic and other substrates that require heating up to at least 300-350 C, as an in situ additive as opposed to a coating. In either case (additive or coating), we believe the relative weight or volume of the material to produce the superhydrophobic behavior will be < 1%. Use of MeMOFs / FMOFs and / or hybrid materials thereof w / AC, plastic, and other substrates: 1) Extracting frying oil from Lays / other potato chips / fried food products. Use unsalted potato chips to increase extraction efficiency (chloride ions could deactivate some of the active materials’ content). Use supercritical carbon dioxide (sc-CO2, more environmentally-friendly than ethanol and may allow milder processing such that the chips may be used intact without grinding). Use MeMOFs instead of FMOFs, which should increase sc-CO2 solubility per GCMC computational predictions. 2) Moisture / oxygen / light (H2O / O2 / hv) barriers on various food packaging substrates. 3) Water purification (at least 10x the efficiency of BPL / other commercial adsorbents in fridge / under the sink columns) for both aliphatic and aromatic pollutants – even at 0.1-1% mixing ratios. 4) Contact angles of 153-165° upon dry-coating fluorine-free pure or additive superhydrophobic materials herein (MeMOFs / MeZIFs / MeCTCs / etc.) on a commercial paper bag from a grocery store. Conclusion. The discovery of MeMOFs’ superhydrophobic properties provides a significant advancement in the development of environmentally-friendly hydrophobic materials. This invention not only offers a viable alternative to PFAS but also opens possibilities for multi-faceted applications across various industries. The combination of computational predictions and experimental validation underscores the reliability and effectiveness of current-generation (G1) and next-generation (G2+) MeMOFs as superhydrophobic materials with a flexible chemical design that would fine-tune the hydrophobicity, omniphobicity, or other properties needed for each application so as to render more effective use of the materials vs PFAS and other state-of-the-art materials for a given application. PATENT 6343*161006PCT / Omary-M17 The following Example is intended to illustrate the above invention and should not be construed as to narrow its scope. One skilled in the art will readily recognize that the Examples suggest many other ways in which the invention could be practiced. It should be understood that numerous variations and modifications may be made while remaining within the scope of the invention. EXAMPLES Example 1. Exemplary Methods. 1. Exemplary Synthetic Procedures: 1A) Embodiment #1, MeMOF-1 = [Ag(3,5-(CH3)2-1,2,4-triazolate)]n: MeMOF-1 is formed by the coordination of ligand L1 to silver (I) ions, creating a three-dimensional polymeric network. The unique spatial arrangement and chemical interactions within this structure impart its superhydrophobic characteristics. The pure MeMOF-1 used here were synthesized with modification to the method published by Zhai et al. in 2009,7including polymorphic structure variations anticipated by the inventors’ work (Yasmeen et al. in 2025)9that are readily obtained by varying crystal growth and other synthetic methods to increase or alter porosity parameters. For all such crystallographic polymorphs of the same [Ag(3,5-(CH3)2-1,2,4-triazolate)]n chemical formula, a 1:1 ratio of the ligand and silver salt was dissolved in 10 mL of methanol with 5 mL NH4OH added. The resulting solution was refluxed at 55 °C for 72 hrs. The precipitate was filtered, washed with cold ethanol and allowed to dry in the air. AC and MeMOF were mixed using a method comprising: hybrid materials were made from an activated carbon / MeMOF-1 blend (typically in the 1% order of magnitude wt.% MeMOF-1 in activated carbon matrix) to render the superhydrophobic properties. This was accomplished by thoroughly mixing both MeMOF-1 dry powder and activated carbon ground in a mortar and pestle at various mass ratios. 1B) Embodiment #2, MeMOF-1b = [Cu(3,5-iPr2-1,2,4-triazolate )]n: is formed by reacting 0.2 mmol 3,5-iPr2-1,2,4-triazolate and 0.1 mmol of a Cu(I) precursor, which could be [Cu(NH3)2]OH, [Cu(CH3CN) 4]X (for example, X = BF4 or PF6), or Cu2O, in a suitable solvent / solvent mixture (for example, mixed ammonia / methanol) under N2 atmosphere at room temperature overnight. The precipitate is filtered and washed in a non-dissolving solvent (for example, methanol) and other workup steps as needed. 1C) Embodiment #3, Me2ZIF-8 = [Zn(2-isopropylimidazolate)]n: MeZIF-1 is formed by the reaction of 1.0 g of zinc(II) nitrate and 6.42 g of 2-isopropylimidazole; the PATENT 6343*161006PCT / Omary-M17 two reagents were dissolved in 50 mL of dimethylformamide (DMF) and stirred until complete dissolution. Then, the mixed solution was poured into a hydrothermal reactor and reacted at 130°C for 12 h. The resulting precipitate was centrifuged three times with methanol to remove unreacted material. Finally, the washed powder was dried under vacuum at 100°C for 12 h to remove methanol and water molecules, and the obtained product collected. 1D) Embodiment #4, Me2CTC-1 = cyclo-[Ag([3,5-iPr2]Pz]3: Me2CTC-1 is formed by the reaction of 604.39 mg of isopropyl pyrazole and 85.75 mg of sodium hydride (NaH); the two reagents were dissolved in diethyl ether and stirred for 2 h, after which 675.9 mg of an Ag(I) salt (for example, AgNO3 or Ag(acetate) = AgAc) were added to the solution and stirred for 24 h in the dark. After completing the reaction, the solution was evaporated under reduced pressure, followed by the removal of NaNO3 (or NaAc) by dissolving the product in dichloromethane (or 1,2-dichloromethane as a less-regulated alternative) and mixing with water. NaNO3 (or NaAc) was removed in water with separatory funnel and the separated dichloromethane was dissolved in MgSO4. Dichloromethane was further separated from MgSO4 through filtration, followed by vacuum evaporation to obtain a white powdered product of cyclo-[Ag([3,5-iPr2]Pz]3. The product was further crystallized from dichloromethane / acetonitrile. 1E) Embodiment #5, MeMOF-2 = [Ag(bis(4,4’-[3,5-dimethyl])pyrazolate]n)] is formed by heating 0.24 g (1.25 mmol) of bis(4,4’-[3,5-dimethyl])pyrazolate, 0.17 g (1 mmol) of an Ag(I) salt (for example, silver nitrate or acetate), and 5 mL of DI water to 150°C overnight in a Teflon-lined steel autoclave. Then followed by a stepwise cooling to room temperature for 3 days. The product is then collected by filtering. 1F) Embodiment #6, MeMOF-2b = [Cu(bis(4,4’-[3,5-dimethyl])pyrazolate]n)] is formed by heating 0.1 mmol of bis(4,4’-[3,5-dimethyl])pyrazolate, 0.25 mmol of a Cu(II) precursor (for example, copper(II) nitrate x-hydrate (for example, x = 0, 2.5 or 6), copper(II) acetate, or copper sulfate), and 10 mL of deionized water plus 4 mL NaOH to 70°C overnight in a Teflon-lined steel autoclave. This is then followed by stepwise cooling to room temperature for 3 days. The product is then collected by filtering. 1G) Embodiment #7, MeMOF-3 = [Ag(1,4-bis(4,4’-[3,5- dimethyl]pyrazolato)benzene)n] is formed by heating a solution containing 0.50 mmol of an Ag(I) salt (for example, silver nitrate or acetate) in 2 mL methanol with a solution containing 0.25 mmol of 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)benzene in 1 mL DMF at 200 °C for 2 days in a Teflon-lined steel autoclave. Then followed by a stepwise cooling PATENT 6343*161006PCT / Omary-M17 to room temperature for 3 days. The product is then collected by filtering, washing with methanol, and drying in vacuum oven at 100 °C. 1H) Embodiment #8, MeMOF-3b = [Cu(1,4-bis(4,4’-[3,5- dimethyl]pyrazolato)benzene)n] is formed by heating a solution containing 0.25 mmol of a Cu(II) precursor (for example, copper(II) nitrate x-hydrate (for example, x = 0, 2.5 or 6), copper(II) acetate, or copper sulfate) in 2 mL methanol with a solution containing 0.25 mmol of 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)benzene in 1 mL DMF at 200 °C for 2 days in a Teflon-lined steel autoclave. Then followed by a stepwise cooling to room temperature for 3 days. The product is then collected by filtering, washing with methanol, and drying in vacuum oven at 100 °C. 1I) Embodiment #9, MeMOF-4 = [Ag(1,4-bis(4,4’-tetrazolato)-2,3,5,6- tetramethylbenzene)n] is formed by heating a mixture of 0.4 mmol of silver nitrate hexahydrate (0.095 g, 0.4 mmol) or another Ag(I) salt (for example, silver acetate), 0.1 mmol of p-tert-butylthiacalix[4]arene, 0.1 mmol of 1,4-bis(4,4’-tetrazolato)-2,3,5,6- tetramethylbenzene and 10 mL methanol at 130 °C for 3 days in a 25 mL TEFLON™- lined autoclave. Then followed by a stepwise cooling to room temperature for 3 days. The product is then collected by filtering, washing with methanol, and drying in air. 1J) Embodiment #10, MeMOF-4b = [Cu(1,4-bis(4,4’-tetrazolato)-2,3,5,6- tetramethylbenzene)n] is formed by dissolving 0.35 mmol,4-bis(4,4’-tetrazolato)-2,3,5,6- tetramethylbenzene in 5 mL DMF in a Schlenk tube, then raising the temperature up to 60°C, after which 0.35 mmol of a Cu(II) precursor (for example, copper(II) nitrate x- hydrate (for example, x = 0, 2.5 or 6), copper(II) acetate, or copper sulfate), methylated polysiloxane, approximately 10 wt% in an organic solvent such as tetrahydrofuran (THF)). Step-by-Step Process: 1. Surface Pretreatment: i. Clean glass substrates thoroughly via ultrasonication sequentially in acetone, ethanol, and distilled water (each step ~10 min). ii. Dry substrates under nitrogen flow followed by heating at 100 °C for 10 minutes to remove residual moisture and solvents. 2. Preparation of Coating Mixture: i. Disperse MeMOF powder (5–10 wt%) uniformly in the polymer solution via ultrasonication for ~20 min to ensure homogeneity and prevent particle agglomeration. PATENT 6343*161006PCT / Omary-M17 3. Coating Procedure: i. Use spin-coater apparatus (such as Laurell WS-650 or similar). ii. Dispense approximately 100 µL of the polymer-MeMOF mixture onto the glass substrate placed at the center of the spin coater. iii. Spin at 2000 rpm for 60 s. This typically yields coatings with thicknesses in the range of 0.5–1.5 µm, controllable by polymer viscosity and spinning parameters. 4. Drying Process: i. Place coated substrates into an oven at 80–100 °C for 1–2 hours to evaporate residual solvent completely and ensure adequate film curing. Alternative Exemplary Method: • Dip-coating can also be used if larger substrates or thicker coatings (~2–10 µm) are desired. Simply immerse the cleaned substrate in the polymer-MeMOF suspension, withdraw at a controlled rate (for example, 5–20 mm / min), followed by oven drying at similar temperatures as spin coating. 2B) Exemplary procedure #2, Spray Coating onto Metallic Substrate (for example, Aluminum) Materials: • MeMOF particles (~100–300 nm) •Polymer resin (for example, epoxy resin or methylated polysiloxane solution at15–20 wt% in organic solvent such as xylene or acetone) Step-by-Step Process: 1. Surface Pretreatment: i. Sand the aluminum surface gently (using 400–800 grit sandpaper), followed by chemical degreasing in acetone. ii. Rinse thoroughly with distilled water and dry under air or nitrogen flow. iii. Optional chemical etching in mild acidic solution (for example, diluted sulfuric acid) to enhance adhesion, followed by neutralization with distilled water and thorough drying. 2. Preparation of Coating Mixture: i. Mix polymer resin with MeMOF particles (~5–15 wt%) using mechanical stirring or ultrasonication for 30 min to obtain homogeneous suspension. 3. Spray Coating Procedure: PATENT 6343*161006PCT / Omary-M17 i. Utilize airbrush spray or pneumatic spray gun (HVLP spray gun system, typical industrial spray-coating equipment). ii. Maintain spray distance of about 15–20 cm from substrate at a pressure of 1.5–2.5 bar. iii. Coat in multiple thin layers (3–5 passes), allowing intermediate drying (~10 min air drying) to avoid runs or uneven distribution. iv. Target thickness: typically 5–30 µm depending on the number of passes and concentration of the coating suspension. 4. Drying and Curing: i. Initially allow coated substrate to air dry at room temperature (~30 min). ii. Further cure the coating in a convection oven at 120–150 °C for 1–2 hours to achieve optimal mechanical integrity and solvent removal. Alternative Exemplary Method: • Roller coating or blade coating can serve as alternatives for large-area substrates, offering controlled and uniform films with thicknesses from 10–50 µm. 2C) Exemplary procedure #3, Coating a Plastic material Since the MeMOF-1 is insoluble in most organic solvents, the drop casting method or method wherein we need to dissolve in an organic solvent and spin coat have failed to give consistent and desirable results. To overcome this method- The PET plastics were dry coated via two methods: A. A 1-inch ^ 1-inch polyethylene terephthalate (PET) plastic substrate was cut out. With a 3M pro-grade precision P220 abrasive (or a less coarse abrasive), the PET surface was gently sanded once in all four directions. ~10mg of MeMOF-1 was spread onto the surface of the sanded PET plastic, ensuring a consistent coat. B. A 1-inch ^ 1-inch polyethylene terephthalate (PET) plastic substrate was cut out and with ~10mg of MeMOF-1 on the surface of a 3M pro-grade precision P220 abrasive (or a less coarse abrasive), the MeMOF was sanded into the PET plastic. Methods A and B produce a superhydrophobic surface, with water drops contact angles in the superhydrophobic range of about ~151 and ~172 degrees, respectively. Method A and B, however, failed the Water vapor transmission rate (MVTR) test, which tends to measure the passage of water vapor through a material. This is most likely due to the non- PATENT 6343*161006PCT / Omary-M17 continuous film formed by these two methods. To overcome this challenge, a method C has been developed: C. Poly(methyl methacrylate) (PMMA)-based coating This approach can be utilized for different polymers, requiring adjustments to the polymer solution, in terms of preparation, solvent, and curing time. This is achieved by adding about 1 g of PMMA to 10 mL of acetone (10% w / v solution). Stir on a magnetic stirrer for 15-30 minutes or until fully dissolved. Add about 5–20 wt% of MeMOF-1 relative to PMMA into the PMMA solution. Ultrasonicate for 5–10 min while avoiding agglomeration. Use a small amount of PEG to act as a surfactant to aid dispersion if needed. Cut and clean PET sheets with ethanol or isopropanol using lint-free wipes or under nitrogen / air to pre-treat the PET surface. Apply the coating by i. Spin Coating: Drop 100–200 µL of solution on PET while spinning at 1000–3000 rpm for 30–60 seconds. ii. Dip Coating: Dip the PET vertically into the solution and pull out slowly iii. Spray Coating: Use an airbrush or spray gun to apply a thin, even layer. Place the coated PET on a hot plate or in an oven at 40–60^°C for 10–30 minutes, until the solvent has fully evaporated and the film is dry. 3. Exemplary method of making AC-MeMOF hybrid Hybrid materials were made from an activated carbon / MeMOF-1 blend (typically in the 1% order of magnitude wt.% MeMOF-1 in activated carbon matrix) to render the superhydrophobic properties. This was accomplished by thoroughly mixing both MeMOF-1 dry powder and activated carbon ground in a mortar and pestle at various mass ratios. Alternative Exemplary Methods: Hybrid materials were made from an activated carbon / MeMOF-1 blend (typically in the 1% order of magnitude wt.% MeMOF-1 in activated carbon matrix) to render the superhydrophobic properties. This was accomplished by weighing both MeMOF-1 dry and fine powder and well-grounded activated carbon into a small vail at various mass ratios and thoroughly mixing with the help of a shaker, vortex mixer, or manually by hand for about 1-2 minutes. 4. Exemplary methods for water purification and water purification columns Method A: Different w / w% MeMOF-1 and finely grounded AC powder with a total weight of 10-20 mg were weighed into a 20 mL vial and thoroughly mixed for PATENT 6343*161006PCT / Omary-M17 homogeneity by a vortex mixer or by hand.10 mL of produced water or simulated BTEX contaminated water was added into the vial and capped. (BTEX contaminated water refers to water that contains detectable levels of a group of volatile organic compounds (VOCs) known as BTEX. This acronym stands for: benzene, toluene, ethylbenzene, a mixture of xylenes (a mixture of ortho-, meta-, and para-xylenes)). The resulting mixture was put in a shaker for at least 2hours and at most overnight at mid agitation. After the incubation time, the mixture was let to rest for about 30 minutes to 1 hour and then filter material is filtered off to get the cleaned water. The same process was repeated for pure AC only and MeMOF-1 only. In an alternative method: Method B: Different w / w% MeMOF-1 and finely grounded AC powder with a total weight of 10-20 mg were weighed into a 20 mL vial and thoroughly mixed for homogeneity by a vortex mixer or by hand.10 mL of produced water or simulated BTEX contaminated water was added into the Vail and capped. The resulting mixture was allowed to sit for at least 2hours and at most overnight without disturbing. After the incubation time, the filter material is filtered off to get the cleaned water. The same process was repeated for pure AC only and MeMOF-1 only. In an alternative method: Method C: A 50 mL burette was first layered with a clean dry cotton wool and then packed with the hybrid MeMOF-AC mixed filter material up to about 2.5 mL and once again layered with cotton wool. The produced water or simulated BTEX contaminated water is allowed to run through the column and collected. The same process was repeated for pure AC only and MeMOF-1 only. In an alternative method: Method D: A 50 mL burette was first layered with a clean dry cotton wool and then packed with the hybrid MeMOF-AC mixed filter material up to about 2.5 mL and once again layered with cotton wool. The produced water or simulated BTEX contaminated water is added to the column with the stop cock closed and allowed to sit for at least 2hours and at most overnight without disturbing. After the incubation time, the water is then collected by opening the stop cock. The same process was repeated for pure AC only and MeMOF-1 only. In an alternative method: Method E: Methods C and D use a layer-by-layer method to layer AC and MeMOF instead of using the hybrid filter material. Other steps remain the same. PATENT 6343*161006PCT / Omary-M17 5. Exemplary method for in situ additive to the PET molding process: MeMOF-1 described in Aspect 7 (thermal stability = 369.72 °C) and is compatible with the PET processing temperature window of 271-293°C. MeMOF as an in situ additive to the PET molding process is achieved by drying the PET pellet / powder in a vacuum or conventional oven at 100-120 degrees Celsius for about 5 hours, as well as the MeMOF powder for about 2 hours at 80 to 100 degrees Celsius to ensure complete dryness. Then, dry blend or tumble mix a desirable percentage or weight-to-weight (w / w%) amount of PET powder and MeMOF powder for uniform mixing. This mixture is then used in the melt process via extrusion or internal mixing at the PET grade temperature zone, pelletized if needed, and molded or cast into the final product. 2. Hydrophobicity Testing. The superhydrophobic nature of MeMOF-1 was assessed using standard water drop contact angle measurements. Samples were placed upon a double-sided sticky tape on a glass slide, flattened, and then exposed to a drop of water. MeMOF-1 consistently demonstrated contact angles ranging from 165 to 175 degrees in line with the GCMC calculations. To test this as a possible coating material, PET plastics were treated with the MeMOF by sanding. The AC / MeMOF-1 hybrid sample also show significant hydrophobic properties in its contact angle measurement. Other G1 and G2 MeMOFs are even expected to be more hydrophobic due to the presence of more CH3 groups. 3. Computational Predictions and Experimental Verification. Recognizing the problem at hand, our initial insights into MeMOF-1 hydrophobicity led us to model the problem using Grand Canonical Monte Carlo (GCMC) simulations that predicted strong water repulsion properties (i.e., higher CO2 / H2O and CH4 / H2O Henry’s coefficient ratios in MeMOF-1 than analogous FMOF-1 with the same structure other than changing CF3 to CH3 for three different structural polymorphs). These theoretical predictions were substantiated by experimental observations, confirming MeMOF-1 superhydrophobicity. Other GCMC calculations for the L2-G1 and G2 versions are ongoing. 4. Design. The design of the Me-MOF material was not a mere conjecture but a result of meticulous computational anticipation through grand canonical Monte Carlo (GCMC) simulations. These simulations, in a predictive manner, demonstrated that replacing fluorine in FMOF-1 with hydrogen not only maintains but, in fact, enhances Henry’s coefficient for the uptake of CO2 or CH4 over water by approximately 5x and 2x, respectively. PATENT 6343*161006PCT / Omary-M17 Encouraged by these theoretical predictions, we set forth synthesizing pure and hybrid materials of MeMOFs. The pure MeMOF used here were synthesized according to the method published by Zhai et al. in 2009, except that it was synthesized in Methanol at 55oC. Hybrid materials were made from an activated carbon-MeMOF blend to provide hydrophobic properties. This was accomplished by thoroughly mixing both MeMOF-1 dry powder and activated carbon ground in a mortar and pestle at various mass ratios. After mixing, the samples were placed upon a double-sided sticky tape on a glass slide, flattened, and then exposed to a drop of water. The hybrid sample shows significant hydrophobic properties in its contact angle measurement. To test this as a possible coating material, PET plastics were treated with the MeMOF by sanding. The superhydrophobic behavior of the MeMOF material led to contact angles that are even higher than those in analogous FMOF-containing materials (by approximately 10°, up to 165-175°) even in hybrid materials with about 1% (weight or volume) (wt or V) MeMOF / matrix order of magnitude. Example 2: Effects of De-Fluorination on Hydrophobicity and on CO2 and CH4 Adsorption Under High Humidity in MeMOFs, Methylated Analogues of FMOFs In this Example we report carbon dioxide (CO2) and methane (CH4) adsorption behavior in MeMOFs, methylated analogues of exemplary FMOFs with CF3 groups altered to CH3, utilizing Grand Canonical Monte Carlo (GCMC) simulations at 288, 298, and 308 K and P ≤ 40 bar and density-functional theory (DFT) computations of adsorption energies. Isosteric heat of adsorption (Qst), Henry’s constants (KH) and interaction energies were used to analyze the adsorbate-adsorbent interaction strengths and gas uptakes of guest molecules. Qst of CO2 was found to be 1.29-1.73x higher in MeMOF-1 than in FMOF-1, vs 1.30-1.47x for CH4, hence demonstrate higher guest affinity to MeMOF-1 than the same FMOF-1 polymorph. Simulated isotherms were further fitted with Langmuir, Langmuir-Freundlich and Tóth models to calculate the isosteric heat of adsorption at infinite dilution (Qst0), using the Clausius-Clapeyron equation. The data were then compared with those obtained from force-field based Monte Carlo (MC) simulations to determine the consistency. The Tóth model presented excellent characterization of CO2and CH4adsorption, implying both FMOF-1 and MeMOF-1 materials have inhomogeneous surfaces. The order of the Qst0 values obtained using the Clausius-Clapeyron equation were persistent with the order of the Qst0 values obtained from MC and confirmed the higher uptake of CO2 and CH4 in MeMOF-1 predicted by PATENT 6343*161006PCT / Omary-M17 GCMC. The presence of H2O vapor, up to 80% relative humidity, did not affect the CO2 and CH4 adsorption in MeMOF-1 structures, as found in the analogous FMOF-1 parent structure. The larger pore size and surface area upon substituting CF3 with CH3 groups allows for significantly greater CO2 and CH4 uptake in MeMOFs vs FMOFs with no water uptake even at high humidity. The findings were applied for MeMOF analogues of multiple FMOF-1 polymorphs known to date and, thus, are expected to withhold for MeMOF analogues of other FMOF and MOFF structures reported by the Omary and Miljanić teams, respectively. Experimental data have validated the superhydrophobic nature of the MeMOF-1 composition via a polymorphic form with a different topology, FMOF-2, attaining approximately 100° increase in water-drop contact angles, from approximately 74° for a control plastic substrate to approximately 172° upon dry-coating it with MeMOF-2. Experimentally synthesized MeMOF-2 possesses the same {Ag(3,5- (CH3)2-1,2,4-triazolate)} empirical formula of simulated MeMOF-1 structures, albeit with a different crystal structure and lower porosity. Global warming and climate change represent adverse impacts of CO2, CH4, and other greenhouse gas emissions.1CO2 concentration has been noticeably increasing over time in the atmosphere mostly because of the combustion of fossil fuels.2–5Natural gas, which is predominantly composed of CH4, has been argued to be a promising alternative to other fossil fuels (for example, gasoline and coal) on the premise that its combustionproduces approximately 50% less CO2, albeit that ignores other environmental impacts ofthe hydraulic fracturing (fracking) process in expending and contamination of water resources. Nevertheless, the concomitant presence of CO2 and N2 in natural gas with the more desired CH4 to decrease the energy production efficiency also adds to the challenges for using that technology.6,7Consequently, CO2 capture and separation from CH4 represent significant scientific and technological challenges with both environmental and economic significance.8Amine scrubbing,9,10membrane separation,11,12and solid adsorbent separation13–15are the three most widely-used methods for CO2 removal. Among the traditional porous materials such as silica, activated carbons, and zeolites considered for selective carbon capture, adsorption processes using metal-organic frameworks (MOFs) has been garnering significant attention, in part due to the unique geometrical structures and tunable chemical properties of MOFs.16–19In order to enhance the CO2 adsorption of MOFs, several methods have been considered, such as creating narrow pores by structural interpenetration,20,21pore chemistry adjustment through cation exchange,22–24introducing “open” (coordinatively-unsaturated) metal sites,25,26and pore PATENT 6343*161006PCT / Omary-M17 surface modification by ligand functionalization.27–32According to Li et al., the ligand functionalization is a promising approach to tune the adsorbate-adsorbent interaction,23which could enhance CO2 adsorption in MOFs without significantly altering the overall structure of the parent MOF. However, pore structure, porosity and pore surface functionality could be greatly influenced due to the functionalization and should be considered when designing MOF functionalization. Another important consideration upon investigating MOF-based solutions for enhanced CO2 and CH4 adsorption is to investigate the hydrophobicity and the selective adsorption of CO2 and CH4 over water of the structures because the presence of water in humid or aqueous environments can adversely affect the CO2 and CH4 uptake.33–36Fluorous metal-organic frameworks, such as the most heavily-investigated FMOF-1 composition = Ag2[Ag4Tz6], where Tz = 3,5-(CF3)2-1,2,4-triazolate, is a superhydrophobic MOF whose CO2 uptake is not affected by the presence of water vapor at all.37In this paper, the ligand functionalization effect of -CH3 upon CO2 and CH4 adsorption in MeMOF analogues of FMOF structures have been investigated using grand canonical Monte Carlo (GCMC) simulations. FMOF-1 was considered as the parent structure. To the best of our knowledge, CO2 adsorption in FMOF-1 at 298 K was studied previously,37but neither CH4 adsorption nor the effect of functionalization have been investigated before. As such, the aims of this study are two-fold: (1) to study the effect offunctionalization by -CH3 instead of -CF3 groups on the CO2 and CH4 adsorption in theresultant hypothetical MeMOF-1 structures at three different temperatures (288, 298, and 308 K) up to 40 bar; and (2) to examine the hydrophobicity and selectivity of CO2 and CH4 over water in the resultant MeMOFs vs their parent FMOF counterparts. We have simulated the CO2 and CH4 adsorption in both the parent and Me-functionalized FMOFs and investigated the Henry’s constant (KH) and isosteric heat of adsorption at infinite dilution (Qst0) in order to understand the adsorbate-adsorbent interactions. These energy parameters acquired during the simulation were compared with the KH values obtained by using the Tóth isotherm model and Qst0 values using Clausius-Clapeyron equation. By comparing the results, we summarized that the -CH3 for -CF3 substitution can greatly improve the CO2and CH4adsorption capacity in MeMOF-1, much more so than the merely subtle compromise in water rejection, hence resulting in not only similar but indeed greater CO2 / H2O and CH4 / H2O selectivity in MeMOFs vs FMOFs. The selective adsorption of CO2 and CH4 over water and the hydrophobicity of the structures were examined under high relative humidity conditions (RH = 80%). PATENT 6343*161006PCT / Omary-M17 Overall, the computational findings as described herein allow for design of alternatives of fluorinated hydrophobic materials. Provided herein are new chemical composition for fluorine-free adsorbents, coatings, or additives that may prove promising for this national / international endeavor to identify alternatives to Teflon, FMOF, ZIF, per- and poly-fluoroalkyl substances (PFAS), and other hydrophobic substances without compromise (indeed with potential improvement) of their pertinent desired properties and uses. Discussed herein is the impact of de-fluorination of fluorinated metal-organic frameworks, by replacing F atoms with H atoms (for example, CF3 → CH3) in some known structures, on the water-rejection ability of the resulting frameworks during their CO2 and CH4 adsorption. Polymorphic forms of FMOF-1 and methylated counterparts (MeMOFs) are discussed, including FMOF and MOF structures reported by the Omary38,39and Miljanić40–44, respectively. Provided herein are novel classes of hydrophobic and / or omniphobic materials based on for example: ZIFs, COFs, FMOFs, MOFFs, PFAS, and the like. Grand Canonical Monte Carlo (GCMC) simulations of methylated metal-organic frameworks (MeMOFs, whereby known FMOF structures have their CF3 groups altered to CH3) suggest that de-fluorination enhances adsorption uptake and adsorption energy for both CO2 and CH4 vs analogous FMOF data. Additionally, akin to FMOFs’ behavior, GCMC-simulated adsorption isotherms of MeMOFs for CO2 and CH4 under very high (80%) relative humidity at 298 K are essentially identical as under dry conditions, consistent with experimental validation of the superhydrophobicity of the MeMOF-1 composition that afforded approximately 172° water-drop contact angle of a MeMOF-1 coating on a plastic substrate. 2. Methods 2.1 Adsorbent Model Yang et al. first synthesized FMOF-1 that consists of a perfluorinated structure.45FMOF-1c is the first adsorbent in this study which was acquired at 290 K and 61 bar under a carbon dioxide stream; CO2 guest molecules were manually removed.37FMOF-1c (FIG.15A) has a tetragonal crystal structure with the space group I 4̅ 2 d and the latticeparameters are a = b = 14.0733 A ֩, c = 37.675 A֩, α = β = γ = 90⁰. Considering FMOF-1cas the primary structure, MeMOF-1c was constructed by replacing the -CF3 groups by - PATENT 6343*161006PCT / Omary-M17 CH3 while retaining the parent FMOF-1c 3D structure otherwise. After the replacement, the preliminary MeMOF-1c structure was optimized by using the FORCITE™ module of MATERIAL STUDIO™ (MATERIALS STUDIO™ is a comprehensive modeling and simulation software suite developed by BIOVIA™ (Dassault Systèmes)46shown in Figures S1-S2 (Supporting Information). Universal Force Field47describing the bonded and non-bonded interactions between the framework atoms was considered during the structure optimization. The final MeMOF-1c, see FIG.15B, structure was obtained after finishing the two-step optimization process. We followed the same procedures for the optimization of MeMOF-1a and MeMOF-1b (Figure S3-S4), which represent analogous modification of FMOF-1a and FMOF-1b structures that correspond to the structures of FMOF-1 obtained under vacuum at 100 K and under a nitrogen stream at 90 K, respectively (N2 molecules were manually removed from the FMOF-1b structure). Material Studio has the efficiency to generate feasible crystal structures and many researchers have been using this software to characterize MOF structures prior to their synthesis.48–50MeMOF-1c has tetragonal crystal structure with the space group I 4̅ 2 dand the lattice parameters are a = b = 13.1532 A ֩, c = 37.2022 A֩, α = β = γ = 90⁰. Both theFMOF-1c and MeMOF-1c possess two types of pores- smaller and larger. Smaller pores are marked by a solid circle, whereas larger pores are denoted by a dot circle, see FIG.15. Geometrical properties of the structures are shown in Table 1. The energy of the initial structure and the optimized MeMOF-1c are compared in Table S1. FIG.15A-B illustrate crystal structures of exemplary compounds: (FIG.15A) FMOF-1c and (FIG.15B) MeMOF-1c. Color code (Ag: cyan, F: pink, N: blue, C: gray, and H: white). 2.2 Interaction Potential To study the CO2 and CH4 adsorption in the pertinent MOFs herein, we account for theoretical models of the adsorbates and adsorbent and a force field that illustrates the adsorbate-adsorbent energetic interactions.51A combination of short-range Lennard-Jones (LJ) and long-range Coulomb potential was used to describe the non-bonded interactions, shown in Equation (1). -- where the interacting atoms are indicated by i and j, rij is their interatomic distance, qi and qj are the partial atomic charges of i and j, respectively, and ^^^^^^are the LJ potential parameters describing the well depth and repulsion distance between i and j, PATENT 6343*161006PCT / Omary-M17 and ^^0is the dielectric constant. The LJ parameters for the framework atoms were taken from the Universal Force Field (UFF).47,52The Lorentz-Berthelot mixing rules53were used to calculate the ε and σ parameters between different atom types. A cutoff length of 12.8 Å was considered for all LJ interactions and the tail corrections were ignored. Partial atomic charges are responsible for electrostatic interactions. The long-range electrostatic interactions were calculated by using the Ewald summation method.54The partial charges of -CF3 groups in FMOF structures were taken from the work of Dalvi et al.,55whereas the Moghadam et al. work37provided the partial charges for the remaining FMOF atoms. In the functionalized structures (MeMOF-1a, MeMOF-1b, and MeMOF-1c), the partial charges of -CH3 groups were calculated by using the connectivity-based atom contribution method (CBAC) described by Qing and Chongli.56CO2 was modeled as a linear three-site rigid model with the C-O bond distance of 1.16 Å according to the TraPPE force field.57CH4 was considered as a spherical single site model. LJ parameters and the partial charges of the framework atoms and adsorbates are represented in Table S3-S5. The Lennard-Jones parameters of CH4 guest molecules were taken from TraPPE model58while water was described according to the TIP4P model.59The simulation box consisted of a supercell (2 × 2 × 1 unit cell) with periodic boundary conditions in all three directions for both structures. We modeled the MOFs as rigid; i.e., all framework atoms were kept fixed during the GCMC simulation. To explore the effect of framework flexibility on the adsorption properties, we performed simulations on three different MeMOF-1 crystal structures. 2.3 Simulation Details Grand canonical Monte Carlo (GCMC)53simulations were performed by using the RASPA2 code60to study CO2 and CH4 adsorption isotherms. For each GCMC run, the number of gas molecules in the adsorbed phase was allowed to fluctuate while the chemical potential (μ), volume (V), and temperature (T) were kept constant. The isotherms were obtained by changing the pressure (P) and calculating the average number of adsorbed molecules (n) as an output of the simulations. Each MC simulation considered random insertion, deletion, rotation, and translation with equal probabilities. Fugacities (f) and bulk densities of CO2 and CH4 were calculated according to the Peng- Robinson61equation of states. Excess adsorption isotherms were simulated by considering void fraction of both the structures (details can be found in the Supporting Information). At each pressure point, 1.0 ×105cycles were used for equilibration and further 1.0 ×105cycles for the adsorption properties determination of both CO2 and CH4. PATENT 6343*161006PCT / Omary-M17 For pure and mixture water simulations, we have taken 5.0 ×105cycles for equilibration followed by another 5.0 ×105cycles for production runs. Isosteric heat of adsorption at infinite dilution and the change of heat of adsorption with pressure were calculated using Equations (2) and (3) respectively:^^^^^^0 = −^^^^ = 〈^^ℎ^^〉 − 〈^^ℎ〉 − 〈^^^^〉 − ^^^^ (2) -- where 〈Uhg〉, 〈Uh〉 and 〈Ug〉 are the average energies of the single guest molecule inside the host, the average energy of the host, the average energy of a single guest molecule in the gas phase, and N is the number of adsorbates in the system respectively. Henry’s constant (KH) of CO2 and CH4 were determined using the Widom particle insertion method62with 100,000 configurational biased insertions. KH values were also obtained from the slope of the isotherms generated by using the Tóth parameters in the low-pressure regime. By applying the parameters aT, bT and m acquired from the Tóth fit, we created loading (n)- pressure (p) data at the low-pressure region where there is a linear relation between n and p. Energy minimizations for a single adsorbate molecule inside FMOF-1c and MeMOF-1c were employed to investigate the contributions of van der Waals and Coulombic interactions to the adsorption energy. Baker’s minimization method63,64for 100 independent minimization attempts with the stopping criteria of Root Mean Square (RMS) gradient of 1.0 ×10-6were considered. The geometrical properties of MOFs such as density, void fraction, pore volume, and channel diameter were computed using Zeo++ software.65The RASPA2 simulation code60was used to run all GCMC simulations. The selective adsorption of CO2 and CH4 over water in FMOF-1c was calculated by using the Henry’s constant ratio (Equation 4) and from the GCMC simulations (Equation 5). -- where ^^^^,^^^^^^^^^^^^^^^^^^and ^^^^,^^2^^are the Henry’s constants of the adsorbate (CO2 or CH4) and water, respectively. -- where qi is the uptake of component i in mol / kg and pi is the partial pressure of component i in Pa. PATENT 6343*161006PCT / Omary-M17 To validate the forcefield used in this study, we have first simulated the CO2 adsorption in FMOF-1c at 298 K and compared it with the previously-simulated data (Figures S5-S6).37Our simulated data give rise to intermediate uptake and Qst magnitudes between previously-reported isotherms, and exhibit similar trends and adsorption profiles. The isosteric heat of adsorption data showed better agreement with experimental data at very low loading and started to deviate around 2.300 mol / kg. Density Functional Theory (DFT) utilizing the B97D / CEP-31G functional / basis set combination has been used to calculate the interaction energies. For the self-consistent field (SCF) convergence, we set the convergence criteria to 10-Nmeaning that the convergence was achieved when the root mean square (RMS) change in the density matrix was less than 10-8and a maximum change in the density matrix was less than 10-6. The calculations were performed using the Gaussian 16 code;66further computational details can be found in Section 3.5. 2.4 Experimental Details for Synthesis and Contact Angle Measurements MeMOF-2 is formed by the coordination of the ligand 3,5-dimethyl-1,2,4- triazolate to silver(I) ions, creating a three-dimensional coordination polymer network. The pure MeMOF-2 sample herein was synthesized upon modification of the method published by Zhai et al. in 2009.67A mixture of 1:1 molar ratio of 3,5-Me2(1,2,4-TzH) and AgNO3 (97.1 mg: 169.9 mg) was dissolved in 10 mL of methanol. To this, 5 mL ofNH4OH was added to de-protonate the triazole. The resultant solution was refluxed at 55°C for 72 hrs. The precipitate was filtered, washed with cold ethanol and allowed to dry in the air to obtain a pure sample. Contact angle measurements were performed for a dry- coated surface of a 1 cm ^ 1 cm polyethylene terephthalate (PET) plastic substrate after sanding it with a 3M pro-grade precision P220 abrasive, following a procedure described by Chen et al.68Results and Discussion Table 1. Geometric properties of the MOF structures studied in this work. Pore Channel Density Surface Area Void Structure3 2Volume Diameter (g / cm ) (m / g) Fraction (cm3 / g) (A֯) FMOF-1a 1.76a817a0.40a0.22a6.20a PATENT 6343*161006PCT / Omary-M17 MeMOF-1a 1.26a1338a0.48a0.39a6.44aFMOF-1b 1.61a903a0.44a0.28a6.80aMeMOF-1b 1.27a1304a0.46a0.36a6.21a1.66a826a0.41a0.25a6.73aFMOF-1c − 782b0.41b− 6.30b1.76c842c0.40c0.23c− MeMOF-1c 1.24a1425a0.53a0.42a6.67aaThis work;bMoghadam et al.;37 cBabarao et al.693.1 Adsorption Isotherms Pure CO2 and CH4 adsorption isotherms were simulated in FMOF-1c and MeMOF-1c at 288, 298, and 308 K under a pressure range up to 40 bar. All simulation results are reported as excess quantities unless otherwise specified. FIG.16 represents the CO2 and CH4 uptake in FMOF-1c and MeMOF-1c. The order of CO2 or CH4 uptake was found to be much higher for MeMOF-1c than in FMOF-1c with the gas uptake of CO2 ˃ CH4 for both FMOF-1 and MeMOF-1 materials at all temperatures. FIG.16A -B illustrate CO2 and CH4 adsorption isotherms of (FIG.16A) FMOF- 1c and (FIG.16B) MeMOF-1c at 288, 298, and 308 K. The result shows the effect of temperature on CO2 and CH4 adsorption capacity in the structures. For both FMOF-1c and MeMOF-1c, CO2 and CH4 uptake decreases with the increase in temperature, as expected for most porous materials. The CO2 adsorption trend is found to be different from that of CH4. Thus, our GCMC simulations herein suggest a gradual increase of CO2uptake up to 20 bar, then reaching a plateau. Compared to CO2, CH4 exhibits almost linear isotherms up to 10 bar and does not saturate at 10 bar (in case of MeMOF-1c), not even at 35 bar (in case of FMOF-1c), consistent with the excellent experimental compressibility reported for this material upon extrapolating the experimental uptake within 0-55 bar up to 300 bar using the Tóth equation.70FIG.17A shows a comparison of CO2 vs CH4 adsorption isotherms of FMOF-1c and MeMOF-1c at 298 K. We notice a very sharp rise in CO2 uptake for MeMOF-1c up PATENT 6343*161006PCT / Omary-M17 to 10 bar, whereas FMOF-1c exhibits a continuous increase of CO2 uptake up to 20 bar and then saturates gradually. However, a nearly linear increment of CH4 uptake is suggested by these GCMC simulations in the low-pressure region for both structures. The very sharp rise of CO2 uptake indicates a stronger CO2–MeMOF-1c interaction than that of CO2–FMOF-1c. The adsorption capacity of both CO2 and CH4 in MeMOF-1c is higher compared to FMOF-1c at 298 K. Similar trends are suggested at the two other temperatures simulated herein (288 and 308 K), as shown in Figures S7-S8. When computing gas adsorption isotherms in MOFs, consideration of electrostatic interactions between the gas molecules and the framework atoms is crucial. To consider the electrostatic interactions, we must assign charges to the framework atoms. We have studied the influence of point charges on CO2 adsorption for FMOF-1c at 298 K (Figure S5). CO2 was considered for our study as it possesses a permanent quadrupole moment, whereas CH4 is a zero-quadrupole-moment material. Consequently, CO2 adsorption is sensitive to the charges of framework atoms, unlike CH4 adsorption. In this study, FMOF- 1c is considered the reference material, and MeMOF-1c is the methylated analogue of FMOF-1c. For the CO2 adsorption isotherms in FMOF-1c, we used the charges from a previous simulation,37whereby -CF3 charges were taken from Dalvi et al.55But for MeMOF-1c, we used charges based on the Connectivity-Based Atom Contribution (CBAC) method of Xu and Zhong56for the -CH3 group; this method assigns charges to representative atoms of MOF building blocks with the same bonding environment. To make our analysis consistent, we used CBAC charges56for -CF3 to simulate CO2 adsorption isotherms in FMOF-1c and compared the results (Figure S5) with our former simulation. We observe a similar trend for CO2 adsorption isotherm in FMOF-1c to both our previous simulation and experiment, indicating that the CBAC charge method has been validated for simulating the CO2 adsorption isotherm in MeMOF-1c. We then studied the influence of point charges on CO2 adsorption for MeMOF-1c at 298 K (FIG. 17B) using two different charge methods, CBAC56and another common method for MOFs, the Extended Charge Equilibration (EQeq) method of Wilmer et al.71(by assigning point charges that minimize an energy function that describes properties such as electronegativities or ionization potentials specifically developed / optimized for MOFs). We observe a similar trend for those isotherms with little variation in CO2 uptake, which suggests that both methods have been validated. Though different charge methods might have different predictions for the amount of gas uptake, we did not observe any significant differences in CO2 adsorption isotherms in the MeMOF-1c structure. PATENT 6343*161006PCT / Omary-M17 FIG.17A-B illustrate: (FIG.17A) Comparison of CO2 and CH4 adsorption isotherms of FMOF-1c and MeMOF-1c at 298 K. (FIG.17B) CO2 adsorption isotherms of MeMOF-1c using two different charge methods at 298 K. In order to achieve a qualitative molecular level perspective of the guest molecules’ adsorption behavior in each of the two MOFs, snapshots of CO2 and CH4 adsorption obtained from GCMC simulation in both the structures at 298 K and different pressures are displayed in FIG.18 and FIG.19, respectively. According to FIG.18, at low pressure, CO2 and CH4 are preferentially adsorbed in the large cylindrical channel of FMOF-1c. As pressure increases, the guest molecules start to emerge near the small- cavity region. When the pressure is elevated further, both the cylindrical channel and the small cages would be gradually populated per these GCMC simulation. It is worth mentioning that the small cavities are not accessible in FMOF-1c at 278 K as per the simulation of Moghadam et al.37For MeMOF-1c shown in FIG.19, it can be observed that both the guest molecules would have occupancy near the small-cavity area at low pressure, in contrast with FMOF-1c. Gradually, the cylindrical channels and the small cages would be filled upon pressure increase. We also simulated the CO2 and CH4 adsorption isotherms in MeMOF-1a and MeMOF-1b and compared them with the values obtained for MeMOF-1c at 298 K (Figure S9). As per Figure S9, greater CO2 and CH4 uptakes are obtained for MeMOF-1c(expanded structure under CO2 atmosphere) compared to MeMOF-1a (rigid, guest-free,reference structure) or MeMOF-1b (expanded structure under N2 atmosphere). While we compare adsorption capacities of MeMOF-1b and MeMOF-1c, we notice MeMOF-1c exhibits significantly higher CO2 uptake than that of MeMOF-1b. We speculate this is due to the higher surface area of MeMOF-1c, 1425 m2 / g, vs 1308 m2 / g for MeMOF-1b. FIG.18A-F illustrates images of snapshots at 1, 5, and 40 bar, respectively, of FMOF-1c for (FIG.18A-C) CO2 occupancy (red spheres) and (FIG.18D-F) CH4 occupancy (blue spheres). FIG.19A-F illustrates images of snapshots at 1, 5, and 40 bar, respectively, of MeMOF-1c for (FIG.19A-C) CO2 occupancy (red spheres) and (FIG.19D-F) CH4 occupancy (blue spheres). 3.2 Isosteric Heats of Adsorption, Qst The isosteric heat of adsorption (Qst) values at each isotherm pressure point were directly obtained during the adsorption isotherm simulations. The adsorption amount could be predicted by the magnitude of the isosteric heat of adsorption. The Qst values for PATENT 6343*161006PCT / Omary-M17 CO2 and CH4 adsorption of FMOF-1c and MeMOF-1c at 298 K are shown in Figure 6. In particular, FIG.20A compares Qst of CO2 and CH4 adsorption as a function of uptake, whereas FIG.20B presents Qst as a function of pressure at 298 K. It is apparent that, for both structures, the Qst value of CO2 is larger than that of CH4. So, the order of isosteric heat of adsorption is CO2 ˃ CH4, consistent with the order of the adsorption capacity. The Qst value of CO2 for FMOF-1c rises evenly from approximately 14 to 23 kJ / mol (at 298 K), which slightly underestimates the reported Qst values of CO2 for FMOF-1c (Figure S6)., The Qst values of CH4 also exhibit an increasing trend from approximately 11 to 14 kJ / mol for FMOF-1c. This increasing behavior is probably due to the lateral interactions of the guest molecules with the rise in pressure (or the adsorbate concentration).72–74On the other hand, the Qst value of CO2 adsorption for MeMOF-1c first declines from 24 to 22 kJ / mol, up to around 2.5 mol / kg (FIG.20A) or 1.2 bar (FIG.20B). After that, it increases rapidly. This indicates that the CO2–MeMOF-1c interactions dominate the adsorption at low loading levels, whereas the contribution of CO2–CO2 interactions escalates after preferential site occupation. The Qst values of CH4 adsorption remains almost unchanged over the entire pressure range due to adsorption sites saturation.75,76For MeMOF-1c, we observe a larger number of guest molecules (both CO2 and CH4) than that for FMOF-1c, ensuing a higher condensed phase at a particular pressure compared to FMOF-1c. Subsequently, the isosteric heats of adsorption for both CO2 and CH4 ofMeMOF-1c is larger than that of FMOF-1c. Since Qst values are lower than 40 kJ / mol,therefore the CO2 and CH4 adsorptions in the considered MOF structures is a physisorption process.77The Qst values at the other two temperatures are depicted in Figures S10-S12. FIG.20A-B graphically illustrates simulated isosteric heats of adsorption, Qst, for CO2 and CH4 of FMOF-1c and MeMOF-1c: (FIG.20A) as a function of uptake and (FIG. 20B) as a function of pressure at 298 K. We also studied the Qst of CO2 and CH4 adsorption for MeMOF-1a and MeMOF- 1b followed by comparing them with MeMOF-1c data at 298 K (Figure S14). Table 2 displays the Qst0 values of the CO2 and CH4 adsorbates at 298 K. For all the adsorbents, the Qstvalues of CO2adsorption initially exhibit a decreasing trend up to 1.4 mol / kg (corresponding to 2 bar) and then an increasing trend is attained. The Qst values of CH4 adsorption remains almost unchanged throughout the entire loading / pressure range. According to Figure S14, MeMOF-1c exhibits the highest Qst0 values vs the other two adsorbents, both for CO2 and CH4. Generally, the smaller pores of porous materials PATENT 6343*161006PCT / Omary-M17 usually display higher Qst values, as smaller pores have shorter distances between the pore walls that result in stronger adsorbate-adsorbent interactions.78,79The highest Qst values at low loading for MeMOF-1c is due to the strong adsorption of adsorbates (CO2 and CH4) in the small-cavity region (FIG.19). While we compare Qst of MeMOF-1a and MeMOF-1b, we notice MeMOF-1b exhibits higher values vs those for MeMOF-1a. We speculate this to be due to the smaller small-pore diameter of MeMOF-1b (6.21 Å) than MeMOF-1a (6.44 Å), even though the large-channel diameters have the opposite trend. Table 2. Qst0 values for CO2 and CH4 in methyl-functionalized MeMOFs, structural analogues of FMOF structures. Qst0(kJ / mol) Adsorbent CO2 CH4 MeMOF-1a 20.20 14.16 MeMOF-1b 21.36 15.08 MeMOF-1c 24.51 17.02 Adsorbate-adsorbent interaction strength can also be characterized by studying the heat of adsorption at infinite dilution, Qst0. A stronger interaction between the gas adsorbate molecule and the host MOF material is reflected by greater Qst0.80Likewise, Henry’s constant, KH, can portray the adsorbate affinity to the adsorbent. The large KH value represents greater affinity of the adsorbate. Both KH and Qst0 were estimated from Widom insertion method, and the results are presented in FIG.21A and FIG.21B, respectively. FIG.21A-B graphically illustrate: (FIG.21A) Henry’s constant, KH, and (FIG. 21B) isosteric heat of adsorption at infinite dilution, Qst0, for CO2 and CH4 at various temperatures in MeOF-1c and FMOF-1c structures, obtained from Widom insertion method. The Henry’s constant of CO2 in the studied MOFs was found to be about one-and- a-half-fold larger than that of CH4, whereas the ratio of CO2 / CH4 isosteric heats of adsorption at infinite dilution was around 1.2-fold larger. According to this finding, the order of the affinity is CO2 ˃ CH4, which could be due to the permanent quadrupole moment of the CO2 molecule that generates an electrostatic force.80The KH values for CO2 adsorption in MeMOF-1c are found to be more sensitive to temperature changes in PATENT 6343*161006PCT / Omary-M17 comparison with FMOF-1c slowly decreased with increased temperature. At 298 K, the KH and Qst0 values for CO2 adsorption in FMOF-1c are 1.81 × 10-6mol / kg / Pa and 13.71 kJ / mol, respectively. The analogous values obtained for CO2 adsorption in MeMOF-1c are 1.56 × 10-5mol / kg / Pa and 24.51 kJ / mol, respectively. Likewise, our MC simulations predict larger KH and Qst0 values for the CH4 adsorption in MeMOF-1c than that in FMOF-1c. Hence, it can be summarized that CO2 and CH4 exhibit greater affinity and stronger interaction strength in MeMOF-1c than in FMOF-1c, which can be attributed to the Me group ligand functionalization. Figure S15 displays the percentage increase of both CO2 and CH4 uptake and isosteric heat of adsorption at infinite dilution as a contribution of -CH3 functionalization in MeMOF-1c. The (NMeMOF-1c - NFMOF-1c) / NFMOF-1c ratio was used to calculate the increased percentages of adsorption. Here, NMeMOF-1c and NFMOF-1c denote the amounts of adsorbates adsorbed in functionalized (MeMOF-1c) and parent (FMOF-1c) MOFs, respectively, at 1 bar and 298 K. For isosteric heat of adsorption at infinite dilution, the comparison was via the (Qst0-MeMOF-1c - Qst0-FMOF-1c) / Qst0-FMOF-1c ratio, where Qst0-MeMOF-1c and Qst0-FMOF-1c represent the isosteric heat for the methyl-functionalized MeMOF and the parent FMOF, respectively. The larger uptake of CO2 in MeMOF-1b compared to MeMOF-1a at the low- pressure region (Figure S9) could be described by KH values for CO2 in the 298 Kstructures (Figure S16). Since KH describes adsorbate-adsorbent interactions ignoringadsorbate-adsorbate interactions, the larger KH for CO2 in MeMOF-1b indicates larger CO2–MeMOF-1b interaction compared to CO2–MeMOF-1a interaction, resulting in higher uptake in MeMOF-1b up to around 5 bar, whereby adsorbate-adsorbent interactions play the dominant role for the CO2 adsorption. 3.3 Interaction Energy Effects The interaction energy contributions to the adsorption mechanism of CO2 and CH4 in FMOF-1c and MeMOF-1c at 298 K, as presented in FIG.22A-B and S17-S26, are consistent with the discussion in Section 3.2. The percentage portion of the guest-guest and host-guest energy contribution to the total energy values shows that the host-guest interaction energy decreases vs increased pressure up to 40 bar. In contrast, the guest- guest interaction energy rises during CO2 and CH4 adsorption for both structures, up to the 40 bar pressure range. FIG.22A-B graphically illustrate the breakdown of (FIG.22A) total potential energy and (FIG.22B) percentage of total potential energy into host-guest and guest- PATENT 6343*161006PCT / Omary-M17 guest contribution for CO2 and CH4 adsorptions in FMOF-1c, obtained from GCMC simulations at 298 K. Figure S27 exhibits the relative contribution of van der Waals (vdW) and Coulombic interactions of the total adsorption energy of CO2 and CH4 in FMOF-1c and MeMOF-1c. The CO2 interaction is significantly stronger than the CH4 interaction in analogous FMOF and MeMOF structures. Additionally, MeMOF-1c displays stronger interactions compared to those in FMOF-1c for both CO2 and CH4 adsorptions. The CH4 model used in our simulation’s possess no charges. Therefore, no electrostatic interactions are present among the CH4 molecules and MOF atoms. Consequently, the adsorption energy for CH4 stems purely from the van der Waals interactions. For CO2, on the other hand, the collective interaction consists of both vdW and Coulombic interactions -- with the Coulombic interaction contribution being relatively small vs vdW interaction (20% vs 80%, respectively). All these data establish that the functionalization / de-fluorination of FMOF-1c to MeMOF-1c (i.e., replacing -CF3 by - CH3 groups) leads to increased adsorption energy. FIG.23A-D illustrates images depicting the adsorbate positions in FMOFs after Baker’s minimization.63,64The nearest distances between CO2---F_CF3 and CH4---F_CF3 are 3.88 and 4.45 Å, respectively, in FMOF-1c. On the other hand, the nearest distances between CO2---H_CH3 and CH4---H_CH3 are 3.18 and 3.82 Å, respectively, in MeMOF-1c after minimization. Apparently, CO2 and CH4 molecules are much closer to the H_CH3in MeMOF-1c compared to the F_CF3 in FMOF-1c, with the values of 0.70 and 0.63 Å, respectively. It should be noted that the covalent radii of F and H are 0.71 and 0.37 Å, respectively.81Given that the differences between the Guest---H and Guest---F distances (0.70 and 0.63 Å) are higher than the difference between the covalent radii of F and H (0.34 Å), these results suggest genuinely stronger interactions of both adsorbates with MeMOF than with FMOF adsorbents. FIG.23A-D illustrate images of adsorption sites of (FIG.23A) CO2 and (FIG. 23B) CH4 in FMOF-1c; (FIG.23C) CO2 and (FIG.23D) CH4 in MeMOF-1c. Initial and final (after minimization) positions of CO2 are represented by orange and dark-red spheres, respectively, while analogous symbols for CH4are shown as cyan and dark-blue spheres, respectively; gray spheres represent different positions of molecules during minimization with some points omitted for clarity purposes. 3.4 Isotherm Models PATENT 6343*161006PCT / Omary-M17 The adsorption isotherms obtained from the molecular simulations were fitted using three different models: Langmuir, Langmuir-Freundlich (L-F) and Tóth models. The goodness-of-fitting in each model with respect to the adsorption isotherms were assessed from the residual root mean square error and the chi-square test -- i.e., RMSE and χ2, respectively. Details can be found in the Supporting Information. Figures S28-S30 depict the fitting curves of adsorbates for FMOF-1c at 288, 298, and 308 K. The fitting parameters and goodness-of-fitting parameters are presented in Tables S6 (Langmuir), S7 (Freundlich-Langmuir), and S8 (Tóth) for FMOF-1c. As summarized in Table S8, the comparison of aT parameter at all temperatures suggests aT (CO2) ˃ aT (CH4), indicating CO2 reaches saturation and exhibits higher maximum uptake vs CH4. The order of magnitude of the pressure required by the gas to attain the stable point also entails CH4 > CO2, suggested by bT, which is inversely proportional to the pressure needed for saturation. As a result, one notices a higher CO2 adsorption vs CH4 in the low-pressure region. The smallest RMSE and χ2values for the Tóth model entails the best fitting for CO2 and CH4 isotherms in FMOF-1c vs the other models. For CO2, the Langmuir model underestimates the uptake near 1.0×106Pa to 3.0×106Pa while it overpredicts at very low and high-pressure regions. All models show better fitting for CH4 vs CO2. From the Tóth model in FMOF-1c, we observe a deviation of the heterogeneity parameter from unity, suggesting that FMOF-1c acts as a heterogenous surface during the adsorption for both adsorbates. The same summary can be made while comparing the models for MeMOF-1c, as shown in Figures S49- S51 and from the fitting parameters given in Tables S9 (Langmuir), S10 (Langmuir-Freundlich) and S11 (Tóth). The isosteric heats of adsorption at infinite dilution (Qst0) were calculated using Clausius-Clapeyron equation82approach (Supporting Information) based on the pure component CO2 and CH4 adsorption isotherms at 288, 298, and 308 K obtained by GCMC simulation. Since the Tóth model showed the best characterization of CO2 and CH4 adsorption in MOFs, we have used the Tóth model parameters to generate pressure (p) / loading (n) pairs to estimate the Qst0 values. We have compared the isosteric heats of adsorption at infinite dilution (Qst0) values obtained by the Clausius-Clapeyron equation to the values acquired by MC simulation (using Widom insertion method) at different temperatures (Table 3). The results are comparable for CH4, while for CO2, the Qst0 values are higher for Clausius-Clapeyron method. It should be worth mentioning that our calculated Qst0 value for CO2 at 298 K in FMOF-1c (16.95 kJ / mol) using Clausius- PATENT 6343*161006PCT / Omary-M17 Clapeyron equation is comparable to the reported value (16.49 kJ / mol)69found in literature. Table 3. Qst0 (kJ / mol) for CO2 and CH4 adsorption of FMOF-1c and MeMOF-1c. Guest Adsorbent Qst0 Qst0 Qst0 Qst0 (Clausius- (MC / 288 K) (MC / 298 K) (MC / 308 K) Clapeyron) FMOF-1c 16.95 13.85 ± 2.56 13.71 ± 2.49 13.69 ± 2.41 CO2 MeMOF-1c 30.58 25.15 ± 2.67 24.51 ± 2.61 23.95 ± 2.50 FMOF-1c 11.28 11.60 ± 2.56 11.54 ± 2.48 11.48 ± 2.40 CH4 MeMOF-1c 18.24 17.28 ± 2.64 17.02 ± 2.57 16.82 ± 2.47 We also compared Henry’s constants of CO2 and CH4 obtained from the Widom particle insertion method62using RASPA2 (KH, RASPA) with the values (KH, Tóth) calculated from the slope of the isotherms generated by using the Tóth parameters in the low- pressure regime. Figures S70-S73 depict the pressure range used for KH calculations in MOFs and the results are summarized in Table S12, showing a satisfactory agreement between the two sets of values. 3.5 Interaction energies from DFT calculations Density Functional Theory- (DFT-) based calculations have also been used to obtain the interaction energy (IE) of the adsorbates (CO2 and CH4) with -CF3, in FMOF- 1c and -CH3, in MeMOF-1c (Table 4 and FIG.24A-D). The density functional B97D along with the CEP-31G basis set were used in this study using Gaussian16 code.66Only the triazole bearing the two -CF3 or two -CH3 substituents in the 3,5- positions was used in the molecular model for interaction with CO2 or CH4 (see FIG.24A-D), in order to render such high-accuracy DFT computations that account for dispersion (physisorption / van der Waals interactions) feasible. For the convergence of the optimized structures, we examined the "Maximum Force" and " Root Mean Square (RMS) Force" values within the optimization output, to make sure they fall below the predefined thresholds values. In Gaussian 16, the default threshold values for "Maximum Force" and "RMS Force" during a geometry optimization are typically set to 0.000450 Hartree / Bohr and 0.000300 Hartree / Bohr, respectively. The lower values of "Maximum Force" and PATENT 6343*161006PCT / Omary-M17 "RMS Force" than that of the threshold values ensured the convergence of the optimized structures, shown in FIG.24A-D. Table 4. DFT-based (B97D / CEP-31G) interaction energy of CO2 and CH4 in small molecular models for FMOF and MeMOF. Adsorbate Substituent Interaction Energy (kJ / mol) -CF3 (FMOF-1c) -18.20 CO2 -CH3 (MeMOF-1c) -22.46 -CF3 (FMOF-1c) -6.00 CH4 -CH3 (MeMOF-1c) -11.33 As per Table 4, the interaction energy of CO2 is higher than that of CH4 for both FMOF-1c and MeMOF-1c. It is also observed that, the -CH3 functionalization affords stronger interaction with CO2 and CH4, compared to the parent -CF3 functionalization. The results are very consistent with the Qst0 values, either obtained from MC simulation or via the Clausius-Clapeyron equation. The interaction energy between CO2 and the - CH3 groups is -22.46 kJ / mol, which is comparable to the interaction energy reported by the work of Gu et al.83The larger interaction energy of CO2 compared to CH4 can be, at least in part, ascribed to the quadrupole moment of CO2.84We observe a smaller distance between O_CO2 and H_CH3 in comparison with O_CO2 and F_CF3, which also supports the aforementioned contention of stronger interaction of CO2in MeMOFs than in FMOFs. The same analogy could also be made for CH4 interaction, as suggested upon comparing the distances between H_CH4 – F_CF3 vs H_CH4 – H_CH3 even after considering the covalent radius difference between F vs H. Given that the DFT calculations suggest that the interaction energy of CH4 is stronger with the -CH3 group in MeMOF-1 compared to the -CF3 group in FMOF-1c, one may ascribe that to stronger interactions of CH4 molecules with the -CF3 groups due to the presence of a partial negative charge on the rather electronegative F atoms. In contrast, the H atoms on the -CH3 group possess partial positive charges, and one might expect repulsive forces among H atoms of CH4 molecule and the -CH3 group. However, the calculations suggest an attractive C-H∙∙∙H-C interaction (even higher than C-F∙∙∙H-C interaction), which is not surprising. This could be explained by the dispersion PATENT 6343*161006PCT / Omary-M17 stabilization of CH4 molecules based on the valence bond (VB) model, as studied by Danovich et al.85The VB analysis revealed that the stabilization of C+-H-∙∙∙H+-C- interaction arises due to the alternation of atomic charges (i.e., C-H+∙∙∙H-C+and C-H∙∙∙H- C), hence bringing about an electrostatic interaction. This phenomenon is consistent with the classical mechanism of oscillating dipoles as the source of dispersion interactions. The existence of attractive C-H∙∙∙H-C interaction was further confirmed by other researchers based on theoretical calculations, using “Quantum Theory of Atoms in Molecules” (QTAIM) in planer aromatic system.86–90FIG.24A-D schematically illustrates DFT-optimized structures of the parent CF3- substituted linker with (FIG.24A) CO2 and (FIG.24B) CH4; and methyl-functionalized linker with (FIG.24C) CO2 and (FIG.24D) CH4. Color code (O: red, F: pink, N: blue, C: gray, and H: white). 3.6 Selectivity and Hydrophobicity of the MOFs We have investigated the MeMOFs vs FMOFs for their selective adsorption of CO2 or CH4 over water. As shown in Figure S74, the CO2 and CH4 adsorption selectivity values over H2O were comparable, obtained by two different methods (discussed in Section 2.3; vide supra) for FMOF-1c at 298 K. The selectivity of CO2 over water in FMOF-1c is 6.4, derived from GCMC, whereas the value is 6.5 acquired from Henry’s constant ratio. The selectivity of CH4 over water in FMOF-1c is 4.3 and 3.9 obtainedfrom GCMC simulations and Henry’s constant ratio, respectively. The CO2 / H2Oselectivity using GCMC simulations was examined from the binary mixture of CO2 and water (CO2: H2O = 7: 2 at 80% RH, corresponding to 3280 Pa) at 0.15 bar and 298 K. For CH4 / H2O selectivity, we modeled a binary mixture of CH4 and water at 95% RH at 1 bar and 298 K. The CO2 / H2O and CH4 / H2O selectivity for a set of MOFs were calculated by their Henry’s constant ratios, as shown in FIG.25A-B. We compared the results of different FMOF and MeMOF structures with those of a prototypical hydrophobic MOF, ZIF-8. The KH values of CO2, CH4, and H2O in ZIF-8 from our simulations are 2.01×10-5mmol / g / Pa, 1.09×10-5mmol / g / Pa and 2.61×10-6mmol / g / Pa, respectively. These values are comparable to those obtained by Moghadam et al.91-- namely 1.50×10-5mmol / g / Pa for CH4 and 2.60×10-6mmol / g / Pa for H2O -- suggesting a good validation for our methodology. Overall, the results suggest that ZIF-8 has the largest KH values for “dry” CO2 and CH4, as expected for such a high-surface-area standard hydrophobic framework. PATENT 6343*161006PCT / Omary-M17 The highest selectivity of CO2 over H2O was obtained for MeMOF-1c with a value of 11.9. ZIF-8 shows the largest KH for H2O among all the hydrophobic structures investigated. The higher CO2 / H2O selectivity of MeMOF-1c compared to ZIF-8 is due to the relatively lower KH value of H2O adsorption in MeMOF-1c vs that in ZIF-8. On the other hand, FMOF-1a shows the highest selectivity of CH4 over H2O -- likely due to its lowest H2O KH value. The CH4 / H2O selectivity was 5.7 for FMOF-1a, which is higher compared to ZIF-8, whereas all other structures showed similar lower values comparatively. FIG.25A-B graphically illustrate (FIG.25A) Henry’s constant (KH) for H2O, CO2, and CH4 at 298 K; (FIG.25B) adsorption selectivity of CO2 and CH4 over water for various MOFs at 298 K. The simulated pure component water adsorption isotherms are presented in Figure 12 for both the parent -CF3 and the -CH3 functionalized MOFs at 298 K. As water interaction is highly sensitive to the charges of framework atoms, we have used two different charge methods, CBAC56and EQeq,71to predict the water adsorption isotherm of the adsorbents. Type V water adsorption profile was observed for MeMOF-1c, indicating the presence of weak interactions between the adsorbate and the adsorbent, using the CBAC method. The water condensation pressure, Pc, for MeMOF-1c was found to be 4500 Pa, close to saturation. In contrast, these simulations do not predict any water condensation in MeMOF-1c based on the EQeq method. Likewise, no water condensation pressure was found for FMOF-1c. Figure S75 shows the number of water molecules adsorbed in FMOF-1c at 298 K and at 4500 Pa as a function of number of MC cycles. This graph confirms the water convergence in hydrophobic FMOF structures, and thus we determine that water adsorption isotherms showed in FIG.26, are reliable. FIG.26 graphically illustrates water uptake for FMOF-1c and MeMOF-1c at 298 degrees K. Lastly, we have used GCMC simulation to model a binary mixture of CH4 and water at 80% relative humidity to examine the influence of water / high humidity on CH4 uptake in FMOF-1c (FIG.27) and MeMOF-1c (FIG.28A-B). The isotherms show similar CH4uptake, under both dry and wet conditions, demonstrating negligible loss of CH4uptake at 80% relative humidity in FMOF-1c. The impact of humidity on CO2 and CH4 adsorption in MeMOF-1c was also considered to study the result of -CH3 functionalization on CO2 and CH4 uptake under humid condition (FIG.28A-B). Thus, GCMC simulations were performed to obtain excess adsorption isotherms for pure- PATENT 6343*161006PCT / Omary-M17 component CO2 and CH4 as well as binary mixtures of CO2 / H2O and CH4 / H2O at 80% RH at 298 K in MeMOF-1c (FIG.28A-B). MeMOF-1c exhibits a much higher uptake of CO2 and CH4 than H2O. Although the interaction of H2O with the methyl-functionalized MOF, MeMOF-1c, is higher than that of the parent MOF, FMOF-1c, this higher H2O interaction did not affect the CO2 and CH4 uptake significantly in MeMOF-1c at 80% RH (FIG.28A-B). We speculate this nominal influence on CO2 and CH4 uptake in MeMOF- 1c is due to the lower partial pressure of water (3280 Pa) than the observed water condensation pressure (4500 Pa). We simulated the 80% RH by fixing the partial pressure of water at 3280 Pa through the entire isotherm, based on the vapor pressure (4100 Pa) predicted by the TIP4P water model. As shown in Figure 12, water condensation occurs at 4500 Pa, which is higher than the partial pressure of water (3280 Pa) in the binary mixture. FIG.27 graphically illustrates adsorption isotherms of pure component CH4 and a binary mixture of CH4 and H2O at 80% relative humidity in FMOF-1c at 298 K. FIG.28A-B graphically illustrates adsorption isotherms of (FIG.28A) pure component CO2 and a binary mixture of CO2 and H2O at 80% relative humidity and (FIG. 28B) pure component CH4 and a binary mixture of CH4 and water at 80% relative humidity in MeMOF-1c at 298 K. 3.7 Experimental Validation of PXRD Pattern and Superhydrophobicity of MeMOFs The successful synthesis of a MeMOF-2 composition, corresponding to the same {Ag(3,5-(CH3)2-1,2,4-triazolate)} empirical formula of the simulated structures, was confirmed by powder X-ray diffraction (PXRD). The PXRD pattern for this synthesized material, however, corresponded to that of a different crystal structure pattern published by Zhai et al.67The two patterns show excellent agreement, as shown in FIG.29A. FIG.29A-B graphically illustrate: (FIG.29A) PXRD pattern of the synthesized MeMOF-2 herein (blue) overlaid with the published PXRD pattern by Zhai et al. (red)67and (FIG.29B) experimental PXRD pattern of the experimentally-prepared MeMOF-2 sample herein (blue) overlaid with the simulated PXRD patterns corresponding to the experimental crystal structure of FMOF-145(green) and the hypothetical MeMOF-1c analogue thereof (black). It should be noted that the structure from the simulated MeMOF-1 and the synthesized MeMOF-2 are dissimilar, as revealed by the PXRD pattern in Figure 15b, but more similar to the analogous FMOF-1 structure even after the CF3 CH3 replacement. PATENT 6343*161006PCT / Omary-M17 This underscores the complexity of prediction to synthesis. Despite this, the retention of the predicted hydrophobic property in the synthesized compound, based on contact angle measurements (FIG.30), suggests that the underlying design principles is still valuable. A crystal structure or PXRD pattern with the same Ag2[Ag4Tz6] unit cell formula and topology as those simulated hypothetical structures for MeMOF-1a / 1b / 1c that correspond to the analogous FMOF-1a / 1b / 1c experimental structures have not yet been isolated. Also, GCMC simulations of CH4 / CO2 / H2O adsorption for the experimental structure of MeMOF-2 that we have synthesized, which corresponds to that reported by Zhai et al.67are not feasible because of the very low porosity of this experimental structure compared to MeMOF-1a / 1b / 1c hypothetical structures. Nevertheless, the simulations for the hypothetical structures are still valuable not only in anticipation of culmination of our ongoing efforts to isolate those or other porous structures experimentally but also for the experimental and other possible low-porosity MeMOF-2 compositions corresponding to the same {Ag(3,5-(CH3)2-1,2,4-triazolate)} empirical formula. This is because the guest adsorption and water repulsion attributes are generally a function of the surface interaction energy of a given guest molecule with the surface functional group of the MOF, which is little-dependent on porosity. This is validated by the general agreement of the DFT simulations for CH4 / CO2 with the 3,5-(CH3)2-1,2,4-TzH ligand in Table 4 with the GCMC-derived Qst0 values in Tables 2-3 (and analogous comparisons for FMOF-137further validated by experimental Qst values). Furthermore, Galli et al.39 have reportedthat another water repulsion metric, low-^ (dielectric constant) at high humidity, was sustained and even slightly enhanced for FMOF-1 samples when pressed at very high pressure that rendered them amorphous instead of crystalline (hence greatly reducing their porosity). We have sought experimental validation of the GCMC-predicted hydrophobicity of the MeMOF-2 composition, [Ag(Me2Tz)]∞. As shown in Figure 16, the PET plastic substrate exhibits an increase in water-drop contact angle by an approximately 100°, from approximately 74° (mere hydrophobic) to approximately 172° (superhydrophobic) range. This contact angle for MeMOF-2@PET is similar to, indeed slightly higher than, that (approximately 160°) we had reported for a neat pellet of FMOF-1 formed spontaneously after the high-pressure CO2 adsorption experiment37and significantly higher than the FMOF-1@PET sample (approximately 131°) tested herein at the same conditions for comparison. PATENT 6343*161006PCT / Omary-M17 FIG.30 graphically, and in images, illustrates water-drop contact angle data for PET only, PET control (sanded), treated PET_1 (FMOF-1@PET), and treated PET_2 (MeMOF-2@PET) from left-to-right, respectively. Contact angle values are shown as average ± standard deviation for triplicate (n = 3) measurements. 4. Conclusions GCMC simulations were performed to study the CO2 and CH4 adsorption isotherms at three different temperatures (288, 298, and 308 K) in parent, FMOF-1, and analogous methyl-functionalized, MeMOF-1, structures, whereby CF3 groups in FMOF-1 were replaced by CH3, using a force field that has been validated. The thermodynamic parameters (Henry’s constants and isosteric heat of adsorption at infinite dilution) were obtained directly from MC simulations. The adsorption isotherms generated by molecular simulations were fitted to the Langmuir, Freundlich-Langmuir and Tóth models. The Tóth model showed the best fit for both CO2 and CH4 in FMOF-1 and MeMOF-1 at the three aforementioned temperatures indicated by the lower residual root mean square error and chi-square values. Our results of Henry’s constants (KH) and isosteric heat of adsorption at infinite dilution (Qst0), either obtained during the simulation or by using the Tóth isotherm model are very consistent and demonstrate that CO2 and CH4 have greater affinity to MeMOF-1 than FMOF-1 and for the same MOF the order is CO2 ˃ CH4 indicated by the higher KH and Qst0. The larger uptake of CO2 and CH4 in MeMOF-1predicted by GCMC simulations was found to be due to the effect of -CH3functionalization of FMOF-1. The selectivity and hydrophobicity were also investigated. The findings exhibited that water either does not condense at all, in one model, or condenses near saturation at 4500 Pa, in another model, in MeMOF-1, similar to the FMOF-1c behavior that exhibited no water condensation in either model. Most importantly, no loss of CO2 and CH4 uptake are found at 80% RH in the methyl- functionalized MOFs. Hence, MeMOF-1 is a promising candidate for CO2 and CH4 capture under humid conditions, suggesting that MeMOFs are potential fluorine-free superhydrophobic alternatives to FMOF, ZIF, Teflon, and PFAS materials. Finally, proof- of-concept experimental data have validated the superhydrophobic nature of the MeMOF- 2 composition, which increased the water-drop contact angle from approximately 74° to approximately 172° upon dry-coating a plastic substrate with MeMOF-2. References in the specification to "one embodiment", "an embodiment", etc., indicate that the embodiment described may include a particular aspect, feature, structure, PATENT 6343*161006PCT / Omary-M17 moiety, or characteristic, but not every embodiment necessarily includes that aspect, feature, structure, moiety, or characteristic. Moreover, such phrases may, but do not necessarily, refer to the same embodiment referred to in other portions of the specification. Further, when a particular aspect, feature, structure, moiety, or characteristic is described in connection with an embodiment, it is within the knowledge of one skilled in the art to affect or connect such aspect, feature, structure, moiety, or characteristic with other embodiments, whether or not explicitly described. The singular forms "a," "an," and "the" include plural reference unless the context clearly dictates otherwise. Thus, for example, a reference to "a compound" includes a plurality of such compounds, so that a compound X includes a plurality of compounds X. It is further noted that the claims may be drafted to exclude any optional element. As such, this statement is intended to serve as antecedent basis for the use of exclusive terminology, such as "solely," "only," and the like, in connection with any element described herein, and / or the recitation of claim elements or use of "negative" limitations. The term "and / or" means any one of the items, any combination of the items, or all of the items with which this term is associated. The phrases "one or more" and "at least one" are readily understood by one of skill in the art, particularly when read in context of its usage. For example, the phrase can mean one, two, three, four, five, six, ten, 100, or any upper limit approximately 10, 100, or 1000 times higher than a recited lower limit. For example, one or more substituents on a phenyl ring refers to one to five, or one to four, for example if the phenyl ring is disubstituted. As will be understood by the skilled artisan, all numbers, including those expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth, are approximations and are understood as being optionally modified in all instances by the term "about." These values can vary depending upon the desired properties sought to be obtained by those skilled in the art utilizing the teachings of the descriptions herein. It is also understood that such values inherently contain variability resulting from the standard deviations found in their respective testing measurements. When values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value without the modifier "about" also forms a further aspect. The terms "about" and "approximately" are used interchangeably. Both terms can refer to a variation of ± 5%, ± 10%, ± 20%, or ± 25% of the value specified. For example, "about 50" percent can in some embodiments carry a variation from 45 to 55 PATENT 6343*161006PCT / Omary-M17 percent, or as otherwise defined by a particular claim. For integer ranges, the term "about" can include one or two integers greater than and / or less than a recited integer at each end of the range. Unless indicated otherwise herein, the terms "about" and "approximately" are intended to include values, for example, weight percentages, proximate to the recited range that are equivalent in terms of the functionality of the individual ingredient, composition, or embodiment. The terms "about" and "approximately" can also modify the endpoints of a recited range as discussed above in this paragraph. As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges recited herein also encompass any and all possible sub-ranges and combinations of sub-ranges thereof, as well as the individual values making up the range, particularly integer values. It is therefore understood that each unit between two particular units are also disclosed. For example, if 10 to 15 is disclosed, then 11, 12, 13, and 14 are also disclosed, individually, and as part of a range. A recited range (for example, weight percentages or carbon groups) includes each specific value, integer, decimal, or identity within the range. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, or tenths. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art, all language such as "up to", "at least", "greater than", "less than", "more than", "or more", and the like, include the number recited and such terms refer to ranges that can be subsequently broken down into sub-ranges as discussed above. In the same manner, all ratios recited herein also include all sub-ratios falling within the broader ratio. Accordingly, specific values recited for radicals, substituents, and ranges, are for illustration only; they do not exclude other defined values or other values within defined ranges for radicals and substituents. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. This disclosure provides ranges, limits, and deviations to variables such as volume, mass, percentages, ratios, etc. It is understood by an ordinary person skilled in the art that a range, such as “number1” to “number2”, implies a continuous range of numbers that includes the whole numbers and fractional numbers. For example, 1 to 10 means 1, 2, 3, 4, 5, … 9, 10. It also means 1.0, 1.1, 1.2.1.3, …, 9.8, 9.9, 10.0, and also PATENT 6343*161006PCT / Omary-M17 means 1.01, 1.02, 1.03, and so on. If the variable disclosed is a number less than “number10”, it implies a continuous range that includes whole numbers and fractional numbers less than number10, as discussed above. Similarly, if the variable disclosed is a number greater than “number10”, it implies a continuous range that includes whole numbers and fractional numbers greater than number10. These ranges can be modified by the term “about”, whose meaning has been described above. The recitation of a), b), c), …or i), ii), iii), or the like in a list of components or steps do not confer any particular order unless explicitly stated. One skilled in the art will also readily recognize that where members are grouped together in a common manner, such as in a Markush group, the invention encompasses not only the entire group listed as a whole, but each member of the group individually and all possible subgroups of the main group. Additionally, for all purposes, the invention encompasses not only the main group, but also the main group absent one or more of the group members. The invention therefore envisages the explicit exclusion of any one or more of members of a recited group. Accordingly, provisos may apply to any of the disclosed categories or embodiments whereby any one or more of the recited elements, species, or embodiments, may be excluded from such categories or embodiments, for example, for use in an explicit negative limitation. Wherever the term “comprising” is used herein, options are contemplated wherein the terms “consisting of” or “consisting essentially of” are used instead. As used herein, “comprising” is synonymous with "including," "containing," or "characterized by," and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, "consisting of" excludes any element, step, or ingredient not specified in the aspect element. As used herein, "consisting essentially of" does not exclude materials or steps that do not materially affect the basic and novel characteristics of the aspect. In each instance herein any of the terms "comprising", "consisting essentially of" and "consisting of" may be replaced with either of the other two terms. The disclosure illustratively described herein may be suitably practiced in the absence of any element or elements, limitation or limitations which is not specifically disclosed herein. This disclosure provides methods of making the compounds and compositions of the invention. The compounds and compositions can be prepared by any of the applicable techniques described herein, optionally in combination with standard techniques of organic synthesis. Many techniques such as etherification and esterification are well PATENT 6343*161006PCT / Omary-M17 known in the art. However, many of these techniques are elaborated in Compendium of Organic Synthetic Methods (John Wiley & Sons, New York), Vol.1, Ian T. Harrison and Shuyen Harrison, 1971; Vol.2, Ian T. Harrison and Shuyen Harrison, 1974; Vol.3, Louis S. Hegedus and Leroy Wade, 1977; Vol.4, Leroy G. Wade, Jr., 1980; Vol.5, Leroy G. Wade, Jr., 1984; and Vol.6; as well as standard organic reference texts such as March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 5th Ed., by M. B. Smith and J. March (John Wiley & Sons, New York, 2001); Comprehensive Organic Synthesis. Selectivity, Strategy & Efficiency in Modern Organic Chemistry. In 9 Volumes, Barry M. Trost, Editor-in-Chief (Pergamon Press, New York, 1993 printing); Advanced Organic Chemistry, Part B: Reactions and Synthesis, Second Edition, Cary and Sundberg (1983); for heterocyclic synthesis see Hermanson, Greg T., Bioconjugate Techniques, Third Edition, Academic Press, 2013. The formulas and compounds described herein can be modified using protecting groups. Suitable amino and carboxy protecting groups are known to those skilled in the art (see for example, Protecting Groups in Organic Synthesis, Second Edition, Greene, T. W., and Wuts, P. G. M., John Wiley & Sons, New York, and references cited therein; Philip J. Kocienski; Protecting Groups (Georg Thieme Verlag Stuttgart, New York, 1994), and references cited therein); and Comprehensive Organic Transformations, Larock, R. C., Second Edition, John Wiley & Sons, New York (1999), and referenced cited therein. Stereochemical definitions and conventions used herein generally follow S.P. Parker, Ed., McGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, New York; and Eliel, E. and Wilen, S., “Stereochemistry of Organic Compounds”, John Wiley & Sons, Inc., New York, 1994. The compounds of the invention may contain asymmetric or chiral centers, and therefore exist in different stereoisomeric forms. It is intended that all stereoisomeric forms of the compounds of the invention, including but not limited to, diastereomers, enantiomers and atropisomers, as well as mixtures thereof, such as racemic mixtures, which form part of the present invention. Many organic compounds exist in optically active forms, i.e., they have the ability to rotate the plane of plane-polarized light. In describing an optically active compound, the prefixes D and L, or R and S. are used to denote the absolute configuration of the molecule about its chiral center(s). The prefixes d and l or (+) and (-) are employed to designate the sign of rotation of plane-polarized light by the compound, with (-) or l meaning that the compound is levorotatory. A compound prefixed with (+) or d is PATENT 6343*161006PCT / Omary-M17 dextrorotatory. For a given chemical structure, these stereoisomers are identical except that they are mirror images of one another. A specific stereoisomer may also be referred to as an enantiomer, and a mixture of such isomers is often called an enantiomeric mixture. A 50:50 mixture of enantiomers is referred to as a racemic mixture or a racemate (defined below), which may occur where there has been no stereoselection or stereospecificity in a chemical reaction or process. The phrase "one or more" is readily understood by one of skill in the art, particularly when read in context of its usage. For example, one or more substituents on a phenyl ring refers to one to five, or one to up to four, for example if the phenyl ring is disubstituted. One or more subunits (i.e., repeat units or blocks) of a polymer can refer to about 5 to about 100,000, or any number of subunits. Substituents of the compounds and polymers described herein may be present to a recursive degree. In this context, "recursive substituent" means that a substituent may recite another instance of itself. Because of the recursive nature of such substituents, theoretically, a large number may be present in any given claim. One of ordinary skill in the art of organic chemistry understands that the total number of such substituents is reasonably limited by the desired properties of the compound intended. Such properties include, by of example and not limitation, physical properties such as molecular weight, solubility or log P, application properties such as activity against the intended target, and practical properties such as ease of synthesis. Recursive substituents are an intended aspect of the invention. One of ordinary skill in the art of organic chemistry understands the versatility of such substituents. To the degree that recursive substituents are present in a claim of the invention, the total number in the repeating unit of a polymer example can be, for example, about 1-50, about 1-40, about 1-30, about 1-20, about 1-10, or about 1-5. References Example 1 (1) Upadhyay, et al., A Phosphorescent Trinuclear Gold(I) Pyrazolate Chemosensor for Silver Ion Detection and Remediation in Aqueous Media. Anal. Chem. 2018, 90, 4999–5006. DOI: https: / / doi.org / 10.1021 / acs.analchem.7b04334 (2) Moghadam, P. Z.; et al., Adsorption and Molecular Siting of CO2, Water, and Other Gases in the Superhydrophobic, Flexible Pores of FMOF-1 from Experiment and Simulation. Chem. Sci.2017, 8, 3989–4000. DOI: https: / / doi.org / 10.1039 / c7sc00278e PATENT 6343*161006PCT / Omary-M17 (3) Omary, M. A.; Marpu, S. Facile method for making non-toxic biomedical compositions comprising hybrid metal-polymer microparticles. U.S. Patent 9,872,916, issued January 23, 2018. 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All publications, patents, and patent documents cited herein are incorporated by reference as though individually incorporated by reference. No limitations inconsistent with this disclosure are to be understood therefrom. The invention has been described with reference to various specific and preferred embodiments and techniques. However, many variations and modifications may be made while remaining within the spirit and scope of the invention. While specific embodiments have been described above with reference to the disclosed embodiments and examples, such embodiments are only illustrative and do not limit the scope of the invention. Changes and modifications can be made in accordance with ordinary skill in the art without departing from the invention in its broader aspects as defined in the following claims.

Claims

PATENT 6343*161006PCT / Omary-M17 WHAT IS CLAIMED IS:

1. A polymer, wherein optionally the polymer comprises repeat unit coordination polymers, clusters and oligomers, comprising at least one metal coordination complex comprising a repeating unit of an alkylated azolate comprising nitrogen atoms, wherein the alkylated azolate comprises more than one alkyl group or a plurality of alkyl groups, and each nitrogen atom of each alkylated azolate is coordinated to a metal (M).

2. The polymer of claim 1, wherein the metal coordination complex is represented by or has a structure as set forth in Formula I or Formula II: I;Formula II, wherein, each J is J1, J2, N, or CRzwherein Rzis H or –(C1-C6)alkyl; each J1is:each J2is N---M, wherein N is the nitrogen atom of the triazole ring of Formula I; each M is independently a metal ion or each M is independently a metal(0); each Ar is an aromatic ring spacer or absent, or each Ar is a phenyl, optionally a phenyl substituted with substituents selected from the group consisting of –(C1-C6)alkyl and halo;PATENT 6343*161006PCT / Omary-M17 each R1and R2are independently –(C1-C6)alkyl, halo, or H; and each R3and R4are independently –(C1-C6)alkyl, halo, or H; wherein the alkylated azolate of Formula I or II is substituted with at least two – (C1-C6)alkyl groups; wherein the metal coordination complex is an oligomeric or polymeric metal coordination complex of Formula I when J is J1or J2; or the metal coordination complex is a cyclic trinuclear or cyclic tetranuclear metal coordination complex of Formula I when J is N or CRz.

3. The polymer of claim 1, 2, or 3, wherein the metal ion is a transition metal ion, or the metal ion is silver, copper, zinc, zirconium, iron, nickel, chromium, manganese, cobalt, or vanadium.

4. The polymer of any one of claims 1 to 3, wherein the metal coordination complex of Formula I is represented by or has a structure as set forth in Formula IA:Formula IA.

5. The polymer of any one of claims 1 to 3, wherein the metal coordination complex of Formula I is represented by or has a structure as set forth in Formula IB:Formula IB, wherein each Ra, Rb, Rc, and Rdare independently –(C1-C6)alkyl, halo, or H.

6. The polymer of claim 5, wherein two or more of R1, R2, R3, and R4are CH3, or two or more of Ra, Rb, Rc, and Rdare CH3.PATENT 6343*161006PCT / Omary-M17 7. The polymer of any one of claims 1 to 3, wherein the metal coordination complex of Formula I is represented by or has a structure as set forth in Formula IC:wherein each R1, R2, R3, and R4are independently –(C1-C6)alkyl, halo, or H.

8. The polymer of claim 7, wherein two or more of R1, R2, R3, and R4are CH3.

9. The polymer of any one of claims 1 to 3, wherein the metal coordination complex of Formula II is represented by or has a structure as set forth in Formula IIA:Formula IIA, wherein each Ra, Rb, Rc, and Rdare independently –(C1-C6)alkyl, halo, or H.

10. The polymer of claim 9, wherein two or more of Ra, Rb, Rc, and Rdare CH3.

11. The polymer of claim 1 or 2, wherein the metal coordination complex comprises: 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)-2,3,5,6-tetramethylbenzene coordinated to copper(II); 1,4-bis(4,4’-pyrazolato)-2,3,5,6-tetramethylbenzene coordinated to copper(II); 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)benzene coordinated to copper(II); bis(4,4’-[3,5-dimethyl]pyrazolate) coordinated to copper(II);PATENT 6343*161006PCT / Omary-M17 1,4-bis(4,4’-tetrazolato)-2,3,5,6-tetramethylbenzene coordinated to copper(II); or 3,5-dimethyl-1,2,4-triazolate coordinated to copper(II); or wherein the metal coordination complex comprises: 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)-2,3,5,6-tetramethylbenzene coordinated to silver(I); 1,4-bis(4,4’-pyrazolato)-2,3,5,6-tetramethylbenzene coordinated to silver(I); 1,4-bis(4,4’-[3,5-dimethyl]pyrazolato)benzene coordinated to silver(I); bis(4,4’-[3,5-dimethyl]pyrazolate) coordinated to silver(I); 1,4-bis(4,4’-tetrazolato)-2,3,5,6-tetramethylbenzene coordinated to silver(I); or 3,5-dimethyl-1,2,4-triazolate coordinated to silver(I).

12. The polymer of claim 1 or 2, wherein the metal coordination complex of Formula I is represented by or has a structure comprising a cyclic trinuclear metal coordination complex of Formula III or a cyclic tetranuclear metal coordination complex of IV:PATENT 6343*161006PCT / Omary-M17 wherein, each J is N or CRz; each Rzis H or –(C1-C6)alkyl; each R1and R2are independently –(C1-C6)alkyl, halo, or H; and each M is independently a metal(0).

13. The polymer of claim 12, wherein the cyclic trinuclear metal coordination complex of Formula III is:.

14. The polymer of claim 12, wherein the cyclic tetranuclear metal coordination complex of Formula IV is:.

15. A method for forming a superhydrophobic surface comprising: (a) coating a substrate with the polymer of any one of claims 1 to 14; or (b) mixing a substance with the metal coordination complex of any one of claims 1 to 15 to form a mixture, then coating a substrate with the mixture;PATENT 6343*161006PCT / Omary-M17 wherein the superhydrophobic surface is capable of forming a contact angle of at least 130 degrees with a water drop.

16. The method of claim 15, wherein the substrate or substance comprises polyethylene terephthalate, Nylon 6 / 6, poly(p-phenylene oxide) / polystyrene blend, activated carbon, carbon fiber, low carbon steel, aluminum, a metal ion or a transition metal, a glass, a plastic, a wood or a paper.

17. The method of claim 16, wherein the aluminum is an aluminum alloy, or the metal ion is iron, nickel, chromium, manganese, cobalt, vanadium or copper.

18. The method of claims 15 to 17, wherein the metal coordination complex is thermally stable at a process melt temperature of the substance.

19. The methods of any one of claims 1 to 18, wherein the superhydrophobic surface is corrosion resistant.

20. The methods of any one of claims 1 to 19, wherein the superhydrophobic surface is a barrier to or is impervious to moisture, air, ultraviolet light, or a combination thereof, or the superhydrophobic surface acts as a barrier that substantially blocks moisture, air, ultraviolet light, or a combination thereof.

21. The methods of any one of claims 1 to 20, wherein the superhydrophobic neat or additive in hybrid material or surface absorbs oil so as to decrease the oil content in fried food products, such as potato chips or French fries corn tortilla chips.

22. The methods of any one of claims 1 to 20, wherein the superhydrophobic neat or additive in hybrid material or surface absorbs oil so as to purify water, including lightly-contaminated drinking water or heavily-contaminated agricultural or industrial water, optionally the heavily-contaminated agricultural or industrial water comprises post-fracking produced water and / or oil spill-contaminated water.

23. A packaging surface, a container, a textile, a plastic, a paper, a metal, a wood, a glass, or a bioderived or synthetic polymer, comprising or having a coating applied thereon one, two or more surfaces of the packaging surface, container, textile,PATENT 6343*161006PCT / Omary-M17 plastic, paper, metal, wood, glass, or bioderived or synthetic polymer, or substantially most of or all surfaces of the packaging surface, container, textile, plastic, paper, metal, wood, glass, or bioderived or synthetic polymer, wherein the coating comprises a polymer of any one of claims 1 to 15.

24. The packaging surface, container, textile, plastic, paper, metal, wood, glass, or bioderived or synthetic polymer of claim 23, wherein the container is a food container, a beverage container, or a consumer product container.

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