Main polymer-functionalized mixed reticular materials for carbon dioxide capture

Abstract

Compositions comprising a polymer-functionalized mixed reticular material such as a covalent organic framework (COF), as well as making and using such compositions are described herein.

Description

Main Polymer-functi.onaliz.ed Mixed Reticular Materials for Carbon Dioxide CaptureCross-Reference To Related Applications

[0001] Pursuant to 35 U.S.C. § 119(e), this application claims priority to the filing dates of United States Provisional Patent Application Serial Nos. 63 / 709,163 filed October 18, 2024, and 63 / 782,824 filed April 3, 2025, the disclosure of each of which is herein incorporated by reference in their entirety.Introduction

[0002] The unprecedented rise in atmospheric carbon dioxide (CO2) concentrations, largely attributed to anthropogenic activities such as fossil fuel combustion and deforestation, has become an urgent global issue because of its key role in driving climate change. The unprecedented accumulation of CO2 in the atmosphere has exacerbated the greenhouse effect, leading to increased temperatures, altered precipitation patterns, and other negative environmental impacts.

[0003] In response, a significant number of materials have been investigated. Polymers, such as polyethylenimine and polylysine, have demonstrated significant promise in addressing the CO2 problem. However, it is challenging to meet all the demanding application requirements, which include high capacity, low regeneration energy, quick kinetics, and long cycling lifetime. The applicability of the current desiccants, namely porous carbon, zeolites, hydroxides, amine liquids, and grafted amines, is limited by low carbon dioxide capacity, high energy consumption, and low cycle stability.

[0004] In particular, porous carbon and zeolites display low carbon dioxide capacity under low pressure or diluted conditions because of the physisorption mechanism, which limits their applicability in direct air capture and post combustion capture from natural gas flue gas. For hydroxides, the binding between carbon dioxide and adsorbent is too strong, thus requiring very high energy to regenerate the material. Amine liquids have suitable basicity and show high carbon dioxide uptake, but face the problems of amine loss, corrosion, and amine oxidation during application. Physically grafted amines in solidified resins and silica increase the uptake and decrease the desorption temperature compared to amine liquids, but still have stability and amine loss issues under cycling. By covalently linking amines to resins or silica supports, the cycle stability would increase; however, most resins and silica contain only hydroxyl functionalities inside the pore, which limits the possibility of post-modification reactions of the material. Meanwhile, the hydrophilic backbones of those materials also adsorb water underhumid conditions, thus raising their regeneration temperature and costing more energy to regenerate.Summary of the Invention

[0005] The invention provides methods, systems and compositions comprising reticular materials, including covalent organic frameworks (COFs), that can be employed as carbon dioxide adsorbents because of their highly stable pores which can be functionalized with desired functional groups.

[0006] The invention provides innovative post-synthetic modifications to functionalize reticular materials with polymers, which enables the sorbent to have strong chemisorption of carbon dioxide, and addresses the volatility of polymers, increasing the stability of the sorbent.

[0007] Reticular materials (including metal-organic frameworks and covalent organic frameworks) are composed of rigid molecular building blocks linked together through strong bonds to generate two- and three-dimensional extended structures. They can be employed as carbon dioxide adsorbents because of their highly stable and ordered pores which can be functionalized with desired functional groups. In this disclosure, the synthesis of polymer- functionalized reticular materials formed by in situ polymerization or chemical reactions between the functional groups of the polymer and the functional groups within or on the surface of the reticular material is described. The polymer-functionalized reticular materials show high carbon dioxide uptake and cycling stability sufficient to be useful for carbon dioxide capture and separation from air and flue gas.

[0008] In an aspect the invention provides a composition comprising a polymer-functionalized reticular material (e.g. COF) configured for carbon dioxide capture. In certain embodiments, the composition is a COF described herein.

[0009] In an aspect the invention provides polymer-functionalized reticular materials configured for carbon dioxide capture and separation, including direct air capture from ambient air and post-combustion capture from natural gas or flue gas.

[0010] In an aspect the invention provides a composition comprising a polymer-functionalized reticular material, formed by in situ polymerization or chemical reactions between the functional groups of the polymer and the functional groups within or on the surface of the reticular material, wherein the polymer-functionalized reticular material provides carbon dioxide uptake and cycling stability sufficient for carbon dioxide capture and separation from air or flue gas.

[0011] In an aspect the invention provides a composition herein, wherein the functionalization of the reticular materials with polymers is accomplished (i) through in situ polymerization reactions within or on the surface of the reticular material; or (ii) through chemical reactions between the functional groups of the polymer and the functional groups within or on the surface of the reticular material.

[0012] In an aspect the invention provides a composition herein, wherein (i) the in situ polymerization is achieved by mixing metal-organic frameworks or covalent organic frameworks with the monomer of polymers, followed by polymerization reactions.

[0013] In an aspect the invention provides a composition herein, wherein (ii) the chemical reactions occur between the functional groups of the polymer and the functional groups within or on the surface of the reticular materials, wherein reticular materials can be functionalized through chemical reactions with polymers to form covalent bonds.

[0014] In an aspect the invention provides methods of using the subject compositions for carbon dioxide capture and / or separation, especially from air or flue gas.

[0015] The invention encompasses all combinations of the particular embodiments recited herein, as if each combination had been laboriously recited.Description of Particular Embodiments of the Invention

[0016] Unless contraindicated or noted otherwise, in these descriptions and throughout this specification, the terms “a” and “an” mean one or more, the term “or” means and / or. It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims. All publications, patents, and patent applications cited herein, including citations therein, are hereby incorporated by reference in their entirety for all purposes.

[0017] The symbol , whether utilized as a bond or displayed perpendicular to a bond, indicates the point at which the displayed moiety is attached to the remainder of the composition. In certain instances, such as a Formula described herein, the symbol indicates the point at which the core is attached to another repeating core.

[0018] The invention provides polymer-functionalized reticular materials configured as carbon dioxide adsorbents. The various functionalities of reticular materials provide alternative chemical reactions for post-synthetic modifications with polymers. At the same time, benefitingfrom the adjustable pore environment and pore size, the material can be design-configured for specific applications under different pressures and relative humidities.

[0019] Polymer functionalized reticular materials synthesized as disclosed herein can be utilized as CO2 adsorbents in ambient air or post-combustion capture from natural gas or flue gas. In embodiments, the CO2 concentration in the feed gas is 400 ppm to 16%, and the temperature of the feed gas is 293 K to 373 K.I. COFs

[0020] Covalent organic frameworks are a class of compounds that are synthesized through reactions between organic linkers resulting in two- or three-dimensional structures. In an exemplary embodiment, the invention provides a COF of the invention. In an exemplary embodiment, the invention provides a COF described herein. In an exemplary embodiment, the invention provides a COF described herein, or a salt thereof. In an exemplary embodiment, the invention provides a COF described herein, wherein the COF is not a salt.

[0021] In one aspect, termed Option A, the invention provides a covalent organic framework(COF) comprising a structure according to Formula (I):, wherein each n is an integer independently selected from 0 to 12; and when n is an integer from 1 to 12, each W is independently selected from H, halogen, ethylene glycol, poly(ethylene glycol), methyl, C2-C6 linear alkyl, C3-C6NHo I — C=CH, OH branched alkyl, « ,H / , -NH(CH2)2NH2, poly(ethylenimine), -NHCH2N(CH3)H, poly(l-ethylenimine), -NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NII(CIl2)3NIl2, poly(propyleneimine), -NII(CII2)2N(CIl3)II, poly(isopropyleneimine), -NH(CH(CH3))3NH2, poly(methyl(propyleneimine)), -NH(C(CH3)2)3NH2, poly(dimethyl(propyleneimine)), -NH(CH2)4NH2, poly(butyleneimine), - NH(CH2)3N(CH3)H, poly(isobutyleneimine), -NHCH(CH3)(CH2)2NH2, poly(secbutyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l-amine), 4-aminostyrene, and poly(4-aminostyrene), or a combination thereof, and when n is 0, each W is independently selected from H, halogen, ethylene glycol, poly(ethylene glycol), methyl, C2-C6 linear alkyl, C3-C5 branched alkyl, -(CJhhNBh, poly(ethylenimine), -(CH(CH3))2NH2, poly(methyl(ethylenimine)), -(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -(CEh^NEh, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l -amine), 4-aminostyrene, and poly(4-aminostyrene), wherein at least one and not more than (X- 1 ) of the W is H, halogen, ethylene glycol, polyethylene glycol), methyl, C2-C6 linear alkyl, or C3-C6 branched alkyl, and q is 1, 2, 3, or 4, or a salt thereof. In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), poly(dimethyl(propyleneimine)), poly(butyleneimine), poly(isobutyleneimine), poly(secbutyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l- amine), or poly(4-aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly-lysine, poly(allylamine), poly(but-3- en-l-amine), or poly(4-aminostyrene). In an exemplary embodiment, according to Option A, thethen ql + q2 = q, and wherein whenthen ql + q2+ q3 = q; each X is independently selected fromwherein each n is an integer independently selected from 0 to 12; and when n is an integer from 1 to 12, each W is independently selected from H, halogen, ethylene glycol, poly(ethylene glycol), methyl, C2-C6 linear alkyl, C3-C6 branched alkyl,poly(ethylenimine), -NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l-amine, poly(but-3-en-l -amine), 4-aminostyrene, and poly(4-aminostyrene); and when n is 0, each W is independently selected from ethylene glycol, poly(ethylene glycol), methyl, C2-C6 linear alkyl, C3-C6 branched alkyl, -(Ckh^NFF, poly(ethylenimine), -(CH(CH3))2NH2, poly(methyl(ethylenimine)), -(CXCHshhNFF, poly(dimethyl(ethylenimine)), -(CH2)3NH2, poly (propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l-amine), 4-aminostyrene, and poly(4- aminostyrene), wherein, for at least one X in Formula (I) and not more than the number of Xs in Formula (I) minus one, W is independently selected from H, halogen, ethylene glycol, poly(ethylene glycol), methyl, C2-C6 linear alkyl, or C3-C6 branched alkyl; and q is 1, 2, 3, or 4, or a salt thereof.

[0022] In one aspect, termed Option B, the invention provides a covalent organic framework(COF) comprising a structure according to Formula (I):wherein, wherein each n is an integer independently selected from 0 to 12; and when n is an integer from 1 to 12, each W is independently selected fromNHJ HCM0H, -NH(CH2)2NH2, poly(ethylenimine), -NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l -amine), 4- aminostyrene, and poly(4-aminostyrene), and when n is 0, each W is independently selected from -(CH2)2NH2, poly(ethylenimine), -(CH(CH3))2NH2, poly(methyl(ethylenimine)), -(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -(CH2)3NH2, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l -amine), 4-aminostyrene, and poly(4-aminostyrene), and q is 1, 2, 3, or 4, or a salt thereof. In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l -amine), or poly(4- aminostyrene).

[0023] In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, and q are as described herein,each X is independently selected from, and Y isIn an exemplary embodiment, according to Option A or Option B, theCOF comprises a structure according to Formula (I), or a salt thereof, wherein Y, Z, and q are as described herein, each X is independently selected fromandIn an exemplary embodiment, according to Option A orOption B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein VIn an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V and Y are as described herein, each X is independently selected from, Z isexemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, whereinV and Y are as described herein, each X is independently selected fromT j UlX, and Z is , and q is 2. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, and Y are as described herein, each X is independently selected from, and q is l. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, and Y arc as described herein, each X is independently selected from, and q is 2. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, and Y are as described herein, each X is independently selected from, and q is 3. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, and Y are as described herein, each X is independently selected from, and q is 4. In an exemplary embodiment, for any of the embodiments in the paragraph, the Option is Option A. In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), poly(dimethyl(propyleneimine)), poly(butyleneimine), poly(isobutyleneimine), poly(secbutyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l -amine), or poly(4- aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), or poly(dimethyl(propyleneimine)). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l-amine), or poly(4- aminostyrene).

[0024] In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V and Y are as described herein, each X is independently selected from, Z isexemplary embodiment, according to Option A or OptionB, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V and Y are as described herein, each X is independently selected fromand1; or ql is 2 and q2 is 0; or ql is 2 and q2 is 1; or ql is 2 and q2 is 2; or ql is 1 and q2 is 2; or ql is 0 and q2 is 2; or ql is 3 and q2 is 0; or ql is 3 and q2 is 1; or ql is 1 and q2 is 3; or ql is 0 and q2 is 3; or ql is 4 and q2 is 0; or ql is 0 and q2 is 4. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof,O"('CH2^ — w wherein V and Y are as described herein, each X is independently selected from5' 'n,ql is 1 and q2 is 1; or ql is 2 and q2 is 0; or ql is 2 and q2 is 1; or ql is 2 and q2 is 2; or ql is 1 and q2 is 2; or ql is 0 and q2 is 2; or ql is 3 and q2 is 0; or ql is 3 and q2 is 1; or ql is 1 and q2 is 3; or ql is 0 and q2 is 3; or ql is 4 and q2 is 0; or ql is 0 and q2 is 4. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V and Y are as described herein, each X is independentlyselected fromis 0 and q3 is 1 ; or ql is 0 and q2 is 1 and q3 is 0; or ql is 1 and q2 is 0 and q3 is 0; or ql is 1 and q2 is 0 and q3 is 1; or ql is 1 and q2 is 1 and q3 is 1; or ql is 2 and q2 is 0 and q3 is 0; or ql is 2 and q2 is 1 and q3 is 0; or ql is 2 and q2 is 0 and q3 is 1; or ql is 2 and q2 is 1 and q3 is 1; or ql is 1 and q2 is 2 and q3 is 1 ; or ql is 3 and q2 is 0 and q3 is 1 ; or ql is 0 and q2 is 1 and q3 is 3; or ql is 0 and q2 is 3 and q3 is 1; or ql is 4 and q2 is 0 and q3 is 0; or ql is 0 and q2 is 4 and q3 is 0; or ql is 0 and q2 is 0 and q3 is 4. In an exemplary embodiment, for any of the embodiments in the paragraph, the Option is Option A. In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l- ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), poly (di methyl(propyleneimine)) , poly (butyleneimine) , poly(i sobutyleneimine) , poly(secbutyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l -amine), or poly(4- aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), or poly(dimethyl(propyleneimine)). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l -amine), or poly(4- aminostyrene).

[0025] In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, each X is independently, each W is as described herein, and each n is independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, each X is independently, each W is as described herein, and n is 2, 3, 4, 5, 6, 7, 8, 9, 10,11, or 12. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, each X is independently, each W is as described herein, and each n is independently from 2 to 8, from 2 to 6, from 3 to 6, from 5 to 6, from 5 to 7, or from 4 to 8. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as O-^CH2^ — w described herein, X is 'n, each W is as described herein, and each n is independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In an exemplary embodiment, according to Option A or Option B, the COF comprises a slruclure according to Formula (I), or a salt thereof, wherein V, 07^CH2d — wZ, Y, and q are as described herein, X is 'n, each W is as described herein, and each n is independently 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, I- O-fcH24- W wherein V, Z, Y, and q are as described herein, X is?' / n, each W is as described herein, and each n is independently from 2 to 8, from 2 to 6, from 3 to 6, from 5 to 6, from 5 to 7, or from 4 to 8. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as ^-O-fcH24-W described herein, X iss v / n, each W is as described herein, and each n is independently from 2 to 8. In an exemplary embodiment, for any of the embodiments in the paragraph, the Option is Option A. In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), poly(dimethyl(propyleneimine)), poly(butyleneimine), poly(isobutyleneimine), poly(secbutyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l- amine), or poly(4-aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), or poly(dimethyl(propyleneimine)). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l-amine), or poly(4- aminostyrene).

[0026] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, each— N-(CH2)-W NH2X is independently '7n or, each W is independently H, * -NH(CH2)2NH2, poly(ethylenimine), -NHCH2N(CH3)H, poly(l-ethylenimine), - NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), -NH(CH2)2N(CH3)H, poly(isopropyleneimine), -NH(CH(CH3))3NH2, poly(methyl(propyleneimine)), - NH(C(CH3)2)3NH2, poly(dimethyl(propyleneimine)), -NH(CH2)4NH2, poly(butyleneimine), - NH(CH2)3N(CH3)H, poly(isobutyleneimine), -NHCH(CH3)(CH2)2NH2, poly(secbutyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l-amine), 4- aminostyrene, and poly(4-aminostyrene), and each n is independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , or 12. In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, eachX is independently, each W is independently H,-NH(CH2)2NH2, poly(ethylenimine), -NHCH2N(CH3)H, poly(l-ethylenimine), - NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), -NH(CH2)2N(CH3)H, poly(isopropylcnciminc), -NH(CH(CH3))3NH2, poly(mcthyl(propylcnciminc)), - NH(C(CH3)2)3NH2, poly(dimethyl(propyleneimine)), -NH(CH2)4NH2, poly(butyleneimine), - NH(CH2)3N(CH3)H, poly(isobutyleneimine), -NHCH(CH3)(CH2)2NH2, poly(secbutyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l-amine), 4- aminostyrene, and poly(4-aminostyrene), and n is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, each X is— N-(CH2)-W i — S-(CH2)-VV I — NH2independentlyv 7n or '7n , each W is independently H,5, -NH(CH2)2NH2, poly(ethylenimine), -NHCH2N(CH3)H, poly(l-ethylenimine), - NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), -NH(CH2)2N(CH3)H, poly(isopropyleneimine), -NH(CH(CH3))3NH2, poly(methyl(propyleneimine)), - NH(C(CH3)2)3NH2, poly(dimethyl(propyleneimine)), -NH(CH2)4NH2, poly(butyleneimine), - NH(CH2)3N(CH3)H, poly(isobutyleneimine), -NHCH(CH3)(CH2)2NH2, poly(secbutyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l -amine), 4- aminostyrene, and poly(4-aminostyrene), but-3-en-l-amine, poly(but-3-en-l-amine), 4-aminostyrene, and poly(4-aminostyrene), and each n is independently from 2 to 8, from 2 to 6, from 3 to 6, from 5 to 6, from 5 to 7, or from 4 to 8. In an exemplary embodiment, according to Option A, the OOF comprises a stmcture according to Formula (I), or a salt thereof, wherein V, O4"CH2^ — W — NH2Z, Y, and q are as described herein, X is ' / n, each W is independently H,5, -NH(CH2)2NH2, poly(ethylenimine), -NHCH2N(CH3)H, poly(l-ethylenimine), - NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), -NH(CH2)2N(CH3)H, poly(isopropyleneimine), -NH(CH(CH3))3NH2, poly(methyl(propyleneimine)), - NH(C(CH3)2)3NH2, poly(dimethyl(propyleneimine)), -NH(CH2)4NH2, poly(butyleneimine), - NH(CH2)3N(CH3)H, poly(isobutyleneimine), -NHCH(CH3)(CH2)2NH2, poly(secbutyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l -amine), 4- aminostyrene, and poly(4-aminostyrene), and each n is independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , or 12. In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, X isO-f- — W — NHO5' , each W is independently H, < , -NH(CH2)2NH2, poly(ethylenimine), -NHCH2N(CH3)H, poly(l-cthylcniminc), -NH(CH(CH3))2NH2, poly(mcthyl(cthylcniminc)), - NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), - NH(CH2)2N(CH3)H, poly(isopropyleneimine), -NH(CH(CH3))3NH2, poly(methyl(propyleneimine)), -NH(C(CH3)2)3NH2, poly(dimethyl(propyleneimine)), - NH(CH2)4NH2, poly(butyleneimine), -NH(CH2)3N(CH3)H, poly(isobutyleneimine), - NHCH(CH3)(CH2)2NH2, poly(secbutyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l-amine), 4-aminostyrene, and poly(4- aminostyrene), and each n is independently 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or ^-O-^CH2^-W a salt thereof, wherein V, Z, Y, and q are as described herein, X isv, each W is independently H,NH2, -NH(CH2)2NH2, poly(ethylenimine), -NHCH2N(CH3)H, poly(l- ethylenimine), -NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), -NH(CH2)2N(CH3)H, poly(isopropyleneimine), -NH(CH(CH3))3NH2, poly(methyl(propyleneimine)), - NH(C(CH3)2)3NH2, poly(dimethyl(propyleneimine)), -NH(CH2)4NH2, poly(butyleneimine), - NH(CH2)3N(CH3)H, poly(isobutyleneimine), -NHCH(CH3)(CH2)2NH2, poly(secbutyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l-amine), 4- aminostyrene, and poly(4-aminostyrene), and each n is independently from 2 to 8, from 2 to 6,from 3 to 6, from 5 to 6, from 5 to 7, or from 4 to 8. In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, U O-ACH2-)— W I— NHoZ, Y, and q are as described herein, X is ' / n, each W is independently H, < , -NH(CH2)2NH2, poly(ethylenimine), -NHCH2N(CH3)H, poly(l-ethylenimine), - NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), -NH(CH2)2N(CH3)H, poly(isopropyleneimine), -NH(CH(CH3))3NH2, poly(methyl(propyleneimine)), - NH(C(CH3)2)3NH2, poly(dimethyl(propyleneimine)), -NH(CH2)4NH2, poly(butyleneimine), - NH(CH2)3N(CH3)H, poly(isobutyleneimine), -NHCH(CH3)(CH2)2NH2, poly(secbutyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l-amine), 4- aminostyrene, and poly(4-aminostyrene), and each n is independently from 2 to 8. In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly ( 1 -ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), poly(dimethyl(propyleneimine)), poly(butyleneimine), poly(isobutyleneimine), poly(secbutyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l- amine), or poly(4-aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly (1 -ethylenimine), poly(propyleneimine), or poly (isopropyleneimine). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l -amine), or poly(4-aminostyrene).

[0027] In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described s H s_ herein, each n is 0, and each X is independently ?N wor *W, each W is independently selected from H, halogen, ethylene glycol, poly(ethylene glycol), methyl, C2-Ce linear alkyl, C3- Ce branched alkyl, -(CH2)2NH2, poly(ethylenimine), -(CH(CH3))2NH2, poly(methyl(ethylenirnine)), -(C(CH3)2)2NH2, poly(dimethyl(ethylenirnine)), -(CH2)3NH2, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l -amine), 4-aminostyrene, and poly(4-aminostyrene). In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, each n is 0, and each X is0 W, each W is independently selected from H, halogen, ethylene glycol,poly(ethylene glycol), methyl, C2-C6 linear alkyl, C3-C6 branched alkyl, -(CFh^NFh. poly(ethylenimine), -(CH(CHa))2NH2, poly(methyl(ethylenimine)), -(C(CH3>2)2NH2, poly(dimethyl(ethylenimine)), -(CEhhNFh, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l- amine), 4-aminostyrene, and poly(4-aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, the Option is Option A. In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropylcnciminc), poly(mcthyl(propylcnciminc)), poly(dimcthyl(propylcnciminc)), poly(butyleneimine), poly(isobutyleneimine), poly(secbutyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l -amine), or poly(4-aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l -ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), or poly(dimethyl(propyleneimine)).

[0028] In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, each X is independently selected fromeach n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12, and each W is independently selected from H,, -NHCCFFhNFF, and poly(ethylenimine). In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, eachX is independently selected fromeach n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12, and each W is independently selected from H,, -NH(CH(CH3))2NH2, and poly(methyl(ethylenimine)).In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, each X is independently selected fromeach n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12, and each W is independently selected from H, , -NHCCCCFbhhNFh, and poly(dimethyl(ethylenimine)). In an exemplary embodiment, according to Option A or OptionB, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, o-fcH2-) — w and q are as described herein, each X is independently selected fromx n,each n is an integer independently selected from 2, 3, 4, 5, 6, 7,5 _ Ml— I8, 9, 10, 11, and 12, and each W is independently selected from H, <2, -NHfCFfohNFh, and poly(propyleneimine). In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, each X is independently selected fromand I— S-(CH2)-W?'zn , each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and12, and each W is independently selected from 11 Y, lysine, and polylysine. In an exemplary embodiment, for any of the embodiments in the paragraph, the Option is Option A. In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimcthyl(cthylcniminc)), poly(propylcnciminc), poly(isopropylcnciminc), poly(methyl(propyleneimine)), poly(dimethyl(propyleneimine)), poly(butyleneimine), poly(isobutyleneimine), poly(secbutyleneimine), poly-lysine, poly( allylamine), poly(but-3-en-l- amine), or poly(4-aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly (propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), or poly(dimethyl(propyleneimine)). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propylcnciminc), poly-lysinc, poly(allylaminc), poly(but-3-cn-l -amine), or poly(4- aminostyrene).

[0029] In certain embodiments of the invention, W is a polymer which is generated in situ and thus each core in the COF may have one or more W which are a polymer with a different number of subunits than another W. In an exemplary embodiment, poly(ethylenimine), as described herein, has from 2 to 30 subunits, from 2 to 25 subunits, from 2 to 20 subunits, from 2 to 15 subunits, from 2 to 12 subunits, from 2 to 10 subunits, from 2 to 9 subunits, from 2 to 8 subunits, from 2 to 7 subunits, from 2 to 6 subunits, or from 2 to 5 subunits. In an exemplary embodiment, poly(methyl(ethylenimine)), as described herein, has from 2 to 30 subunits, from 2 to 25 subunits, from 2 to 20 subunits, from 2 to 15 subunits, from 2 to 12 subunits, from 2 to 10subunits, from 2 to 9 subunits, from 2 to 8 subunits, from 2 to 7 subunits, from 2 to 6 subunits, or from 2 to 5 subunits. In an exemplary embodiment, poly(dimethyl(ethylenimine)), as described herein, has from 2 to 30 subunits, from 2 to 25 subunits, from 2 to 20 subunits, from 2 to 15 subunits, from 2 to 12 subunits, from 2 to 10 subunits, from 2 to 9 subunits, from 2 to 8 subunits, from 2 to 7 subunits, from 2 to 6 subunits, or from 2 to 5 subunits. In an exemplary embodiment, poly(propylenimine), as described herein, has from 2 to 30 subunits, from 2 to 25 subunits, from 2 to 20 subunits, from 2 to 15 subunits, from 2 to 12 subunits, from 2 to 10 subunits, from 2 to 9 subunits, from 2 to 8 subunits, from 2 to 7 subunits, from 2 to 6 subunits, or from 2 to 5 subunits. In an exemplary embodiment, polylysinc, as described herein, has from 2 to 20 subunits, from 2 to 15 subunits, from 2 to 12 subunits, from 2 to 10 subunits, from 2 to 9 subunits, from 2 to 8 subunits, from 2 to 7 subunits, from 2 to 6 subunits, from 2 to 5 subunits, from 2 to 4 subunits, or from 2 to 3 subunits.

[0030] In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein; each X is independently selected from; each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; and each W is KJ I— I independently selected from H, <2, -NH(CH2)2NH2, and poly(ethylenimine) having a subunit range described herein. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein; each X is independently selected from,each n is 0; and each W is independently H, -(CH2)2NH2or poly(ethylenimine) having a subunit range described herein. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein; each X is independently selected fromeach n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; and each W is independently selected from H, , -NH(CH(CH3))2NH2, and poly(methyl(ethylenimine)) having a subunit range described herein. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein; each X is independently selected from;each n is 0; and each W is independently H, -(CI KCI htpNI b. and poly(methyl(ethylenimine)) having a subunit range described herein. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein ko-fcH24-WV, Z, Y, and q are as described herein; each X is independently selected from ' Aeach n is an integer independently selected from 2, 3, 4, 5, 6,7, 8, 9, 10, 11, or 12; and each W is independently selected from H,NH2, -NH(C(CH3)2)2NH2, and poly(dimethyl(ethylenimine)) having a subunit range described herein. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein; each X is independently selected from; each n is 0; and each W is independently H, -(CfCFBhhNFh or poly(dimethyl(ethylenimine)) having a subunit range described herein. In an exemplary embodiment, according to Option A or Option B, theCOF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are O4-CH2^ — w — N-^CH2)—w as described herein; each X is independently selected from ' ' / n, ' C , and; n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; and each W is independently selected? _ KI I— I from H, 52, -NH(CH2)JNH2, and poly (propyleneimine) having a subunit range described herein. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein; each X is independently selected from; each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; and each W is independently H, -(CFh^NFb or poly(propyleneimine) having a subunit range described herein. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein; each X is independently selected from; each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; and each W is independently selected from H,, lysine, and polylysine having a subunit range described herein. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as describedherein; each X is independently selected from; each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; and each W is independently selected from H,, lysine, and polylysinc having a subunit range described herein. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein; each X is independently selected fromeach n is 0; and each W is independently H, lysine or polylysine having a subunit range described herein. In an exemplary embodiment, for any of the embodiments in the paragraph, the Option is Option A. In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), poly(dimethyl(propyleneimine)), poly(butyleneimine), poly(isobutyleneimine), poly(secbutyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l -amine), or poly(4-aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly( 1 -ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), or poly(dimethyl(propyleneimine)). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly-lysine, poly (allylamine), poly(but-3-en-l -amine), or poly(4- aminostyrene).

[0031] In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, each X is independently selected fromNH each n is an integer from 1 to 12, and each W is independently selected from H,52, -NH(CH2)2NH2, and poly(ethyleneimine). In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein ko-^CH24-WV, Z, Y, and q are as described herein, each X is independently selected from * ' / n,I— N-(CH2)-W I— S-(CH2VW v , andxm , each n is 0, and each W is independently H, -(CH2)2NH2orpoly(ethyleneimine). In an exemplary embodiment, In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, each X is independently selected fromexemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, eachX is independently selected from' A A , and A , and m is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, or 12. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V,O"(‘CH2^ — wZ, Y, and q are as described herein, each X is independently selected from 'n, a linear or branched polymerderived from AA . [n anexemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, each X is independently selected fromand I— NH2— C=CH2I— OH, and each W is independently selected from H,5? H J , a linear orH N branched polymer derived from a monomer which is AX;an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, eachX is independently selected from, each W is| — NH? i — C=CH2?— OH independently selected from H, < ,5H t , a linear or branched polymer derived from a monomer selected fromIn an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein V, Z, Y, and q are as described herein, each X is independently selected from, and each W is independently selected fromexemplary embodiment, for any of the embodiments in the paragraph, the Option is Option A. In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l -ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), poly(dimethyl(propyleneimine)), poly(butyleneimine), poly(isobutyleneimine), poly(secbutyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l- amine), or poly(4-aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l -ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), or poly(dimethyl(propyleneimine)). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l -amine), or poly(4- aminostyrene).

[0032] In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein W, Z and q are as described herein,each X is independently selected from, Y isexemplary embodiment, according to Option A orOption B, the OOF comprises a structure according to Formula (1), or a salt thereof, wherein W and V is as described herein, each X is independently selected from,exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein W and Y is as described herein, each X is independently selected fromis 2,In an exemplary embodiment, according to Option A or Option B, theCOF comprises a structure according to Formula (I), or a salt thereof, wherein W, n, and V are as described herein,each X is. In an exemplary embodiment, for any of the embodiments in the paragraph, the Option is Option A. In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(cthylcniminc), poly(l-cthylcniminc), poly(mcthyl(cthylcniminc)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), poly(dimethyl(propyleneimine)), poly(butyleneimine), poly(isobutyleneimine), poly(secbutyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l- amine), or poly(4-aminostyrene). In an exemplary embodiment, for any of the embodiments inthe paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), or poly(dimethyl(propyleneimine)). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l-amine), or poly(4- aminostyrene).

[0033] In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, and Z are as described herein,Uo-fCH24-W 1— N-fcH2)-W Ys-(cH2^W each X is independently selected from5 vY , and ' 'n , n is 6NH and each W is independently selected from H,52, -NH(CH2)2NH2, and polyethyleneimine.In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof,wherein each n is an integer independently selected from 2 to 8; each W is independently selected from H,, -NH(CH2)2NH2, poly(ethylenimine), -NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CHa)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), lysine, and poly-lysine, and q is 1, 2, 3, or 4. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, Z and q arc as described herein; each X is independentlywherein each W is as described herein. In an exemplary embodiment, according to Option A or Option B, theCOF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, Z and q areas described herein; each X is, wherein each W is as described herein. In an exemplary embodiment, according to Option A or Option B, the COF comprises a structure according to Formula (I), or a salt thereof, whereinXJQx ko-^CH2^- w I—NH; each X is6: and each W is independently selected from: a) H,5, -NH(CH2)2NH2, or poly(ethyleneimine);p _ [\l I— I poly(methyl(ethylenimine)); c) H, <2, -NH(C(CH3)2)2NH2, or poly(dimethyl(ethylenimine));| — NH2I — NH d) H, < , -NH(CH2)3NH2, or poly(propyleneimine); and e) H, <2, lysine, or polylysine.In an exemplary embodiment, the COF comprises a structure according to Formula (I), or a salt^-O{CH2-)-W §_NH6 ; and each W is independently selected from H, < , -NH(CH2)2NH2, and poly(ethyleneimine). In an exemplary embodiment, for any of the embodiments in the paragraph, the Option is Option A. In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly (1 -ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), poly(dimethyl(propyleneimine)), poly(butyleneimine), poly(isobutyleneimine), poly(secbutyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l -amine), or poly(4-aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l -ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), or poly(dimethyl(propyleneimine)). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W ispoly(ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l-amine), or poly(4- aminostyrene).

[0034] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, Z, and q are as described herein, eachX is independentlywherein each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12, and each W is independently selected from , -NH(CH2)2NH2, poly(ethylenimine), -NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l-amine, poly(but-3-en-l -amine), 4- aminostyrene, and poly(4-aminostyrene). In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, Z, and qN-fcH2^ — H N-fa-U — W are as described herein, each X is independently ' orv / r, wherein each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12, and each W is independently selected from, -NH(CH2)2NH2, poly(ethylenimine), -NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), - NH(CH2)3NH2, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3- en-l-amine, poly(but-3-en-l -amine), 4-aminostyrene, and poly(4-aminostyrene). In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, Z, and q are as described herein, each X is independently■nor •n, wherein each n is an integer independently selected from 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12, and each W is independently selected from , -NH(CH2)2NH2, poly(ethylenimine), -NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l-amine, poly(but-3-en-l -amine), 4- aminostyrene, and poly(4-aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l- ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), poly(dimethyl(propyleneimine)), poly(butyleneimine), poly(isobutyleneimine), poly(secbutyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l -amine), or poly(4-aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), or poly(dimethyl(propyleneimine)).

[0035] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, Z, and q are as described herein, eachX is independently, -O-(CH2)2NH2, and -O-poly(ethylenimine), wherein n is an integer selected from 1 , 2, 3, 4, 5, 6, 7, and 8. In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, Z, § H ! x S-N+CH24— H and q are as described herein, each X is independently?' / n, -NH-(CH2)2NH2, and -NH-poly(ethylenimine), wherein n is an integer selected from 1, 2, 3, 4, 5, 6, 7, and 8. In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, and Z are as described herein, each X isS_f'CH2-) — H independently5 v, -S-(CH2)2NH2, and -S-poly(ethylenimine), wherein n is an integer selected from 1, 2, 3, 4, 5, 6, 7, and 8. In an exemplary embodiment, for any of the embodiments in this paragraph, n is 4, 5, 6, 7, or 8. In an exemplary embodiment, for any of the embodiments in this paragraph, n is 6.

[0036] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, Z, and q are as described herein, each^O^CH2^ — HX is independentlys' / n, -O-(CH2)2NH2, and -O-poly(ethylenimine), wherein n is an integer selected from 1, 2, 3, 4, 5, 6, 7, and 8. In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, Z, and q are as described herein, each X is independently-NH-(CH2)2NH2, and - NH-poly(ethylenimine), wherein n is an integer selected from 1, 2, 3, 4, 5, 6, 7, and 8. In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, Z, and q are as described herein, each X is S4-CH2-) — H independentlyv, -S-(CH2)2NH2, and -S-poly(ethylenimine), wherein n is an integer selected from 1, 2, 3, 4, 5, 6, 7, and 8. In an exemplary embodiment, for any of the embodiments in this paragraph, n is 4, 5, 6, 7, or 8. In an exemplary embodiment, for any of the embodiments in this paragraph, n is 6.

[0037] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, and Z are as described herein, q is 1, each X is independentlywherein each W is independently as5 _ Nl_l described herein, such as selected from *2, -NH(CH2)2NH2, poly(ethylenimine), -NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NHCCFkhNFF, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l-amine), 4-aminostyrene, and poly(4-aminostyrene), wherein each n is an integer independently selected from 2, 3, 4, 5, 6, 7,O_ACH2^ — H O-^CH2^ — W and 8, and when: a) 1 of the X iss, 5 of the X are *v; b) 2 of the X areX OTCHJT — W are, 1 of the X is * ' . In an exemplary embodiment, for any of the embodiments in this paragraph,exemplary embodiment, for anyCN of the embodiments in this paragraph, V isIn an exemplary embodiment, for any of the embodiments in this paragraph,whereinwherein ql + q2 + q3 is 1. In an exemplary embodiment, for any of the embodiments in this paragraph, when X isn is 6. In an exemplaryembodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly( 1 -ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl (propyleneimine)), poly(dimethyl (propyleneimine)) , poly(butyleneimine), poly(isobutyleneimine), poly(secbutyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l- amine), or poly(4-aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l -ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropylcnciminc), poly(mcthyl(propylcnciminc)), or poly(dimcthyl(propylcnciminc)).

[0038] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, and Z are as described herein, q is 2, each X is independently, wherein each W is independently as described herein, such as selected from, -NFKCFhhNFfc, poly(ethylenimine), -NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l-amine, poly(but-3-en-l -amine), 4-aminostyrene, and poly(4-aminostyrene), wherein each n is an integer independently selected from 2, 3, 4, 5, 6, 7,O-^CH2^ — H O-f'CHo'} — W and 8, and when: a) 1 of the X iss, 11 of the X are * ' 'n ; b) 2 of the XO-(-CH2") — H O"^CH2^ — W O-fci-U — H arez'n, 10 of the X are5' ; c) 3 of the X are5' , 9 of the X aref the X are^?-O-fcH24— H O+CH24- W |-O+CH24— H ' 'n 7 of the X are5' 'n ; f) 6 of the X are5' 'n , 6 of the X arethe X aref the X aref the Xthe X is. In an exemplary embodiment, for any of the embodiments in this paragraph,exemplary embodiment, for anyCN<— Q=C — ? of the embodiments in this paragraph, V is§H \ In an exemplary embodiment, for any of the embodiments in this paragraph,whereinwherein . In an exemplary embodiment, for any of the embodiments in this paragraph,n an exemplary embodiment, for anyO"^CH2^ — H of the embodiments in this paragraph, when X is ' / fln is 6. In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), poly(dimethyl(propyleneimine)), poly(butyleneimine), poly(isobutyleneimine), poly(secbutyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l- amine), or poly(4-aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(mcthyl(cthylcniminc)), poly(dimcthyl(cthylcniminc)), poly(propylcnciminc), poly(isopropyleneimine), poly(methyl(propyleneimine)), or poly(dimethyl(propyleneimine)).

[0039] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, and Z are as described herein, q is 3, each X is independentlywherein each W is independently as described herein, such as selected from , -NH(CH2)2NH2, poly(ethylenimine), -NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NI KCXCHihFNI b,poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l-amine, poly(but-3-en-l -amine), 4-aminostyrene, and poly(4-aminostyrene), wherein each n is an integer independently selected from 2, 3, 4, 5, 6, 7, ^-C4CH24— H ^-O-^CH2^-W and 8, and when: a) 1 of the X is5' , 17 of the X are 'n ; b) 2 of the X^-O-fcH74— H ^-O-^CH24-W O-fcH24— H are ’ ' 'n, 16 of the X are ’ ' 'n ; c) 3 of the X are5' 'n, 15 of the X|-OfCH24-W i-O+CH24— H i- O+CH2+~ W are ’ ' ; d) 4 of the X are ' , 14 of the X are5' 'n; e) 5 of the X^-o-fcH24— H S>-O7-CH2-)— W UO-(-CH24— H are ’ ' 'n, 13 of the X are ’ ' ; f) 6 of the X are ' 'n, 12 of the X are^-O4CH24— H -O^CH24-W are 'n, 1 of the X is ' In an exemplary embodiment, for any of the embodiments in this paragraph,exemplary embodiment, for anyCN of the embodiments in this paragraph, V is k ’ c=c H-^ \ In an exemplary embodiment, for any of the embodiments in this paragraph,whereinwherein ql + q2 + q3 is 3. In an exemplary embodiment, for any of the embodiments in this paragraph, when X isn is 6. In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), poly(dimethyl (propyleneimine)), poly(butyleneimine), poly(isobutyleneimine), poly(secbutyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l- aminc), or poly(4-aminostyrcnc). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), or poly(dimethyl(propyleneimine)). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), poly(dimethyl (propyleneimine)), poly(butyleneimine), poly(isobutyleneimine), poly(secbutyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l- amine), or poly (4- aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l-ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), or poly(dimethyl(propyleneimine)).

[0040] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, and Z are as described herein, q is 4, each X is independentlywherein each W is independently as? _ KI I— I described herein, such as selected from «2, -NH(CH2)2NH2, poly(ethylenimine), -NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l-amine, poly(but-3-en-l- amine), 4-aminostyrene, and poly(4-aminostyrene), wherein each n is an integer independently selected from 2, 3, 4, 5, 6, 7,>— OTCH2~) — H and 8, and X is selected from: a) 1 of the X is * 'zn and 23 of the X areO-^CHo^ — H o4cH24 — W b) 2 of the X are5' 'n and 22 of the X are5' '<> ; c) 3 of the X are ho-fcH24— H ^-O-^CHo^-W ^-O-ACH24— H5'zn and 21 of the X are * ' 'n; d) 4 of the X are5' 'n and 20 of the^-O4CH24-W ^-O4CH24— H ^-O4CH24-WX are5' 'n; e) 5 of the X are5'zn and 19 of the X are5' 'n ; f) 6 ofO"ACH2^ — H O4‘CH2^ — w O"ACH2^ — H the X are5' 'nand 18 of the X are5' 'n; g) 7 of the X are * ' 'nandUO4CH24-W ko4cH24— H17 of the X are * 'zn ; h) 8 of the X are5' 'n and 16 of the X are|-O+CH24-W -O+CH24— H i-ofCH24-w5; i) 9 of the X are 'nand 15 of the X are * ' 'n; j) 10 of the X^-O4-CH2^— H ^-C4CH24-W ^-O4CH24— H are 'zn and 14 of the X are ' ; k) 1 1 of the X are5' and 13 of^-O^CH24-W UO4CH24— H ^-O^CH24-W the X are ' 'n; 1) 12 of the X are ' 'nand 12 of the X are ' 'n; m)H ^-O-("CH2-)— W 'n and 11 of the X are ' 'n ; n) 14 of the X are5—O4CH23 — W O-fCH2“) — Hthe X are * ' 'n; o) 15 of the X are * ' 'nand 9 of the^-O-fcH24-W hc4cH24— H ^-o4-CH24-WX are1'zn : p) 16 of the X are5' 'n and 8 of the X are5 kY ; q) 17 ofO"TCH2T — H O"fCH2~T — H the X are?'zn and 7 of the X aref the X are; vand 6 k O-^CH2^- W ^-O4CH2^— H of the X are 'zn ; s) 19 of the X are ' 'n and 5 of the X areO"rCH2“i — H 5—O“TCH2“T — W 5—O-rCFO-) — H20 of the X arc5'Znand 4 of the X are * 'z" ; u) 21 of the X are * ' 'n ko^CH24-W ^-O-ACH2^— H and 3 of the X aren; v) 22 of the X are * ' 'n and 2 of the X areO4"CH2“) — W O4"CH2") — H ^OfCH2^ W5\ 4 ; or w) 23 of the X are5' 'nand 1 of the X is . In an exemplary embodiment, for any of the embodiments in this paragraph,CN 5 i s f-C=C-|In an exemplary embodiment, for any of the embodiments in this paragraph, V is H . Inan exemplary embodiment, for any of the embodiments in this paragraph, Z iswherein ql + q2 + q3 is 4. In an exemplary embodiment, for any of the embodiments in this paragraph, when X isn is 6. In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly(l -ethylenimine), poly(mcthyl(cthylcniminc)), poly(dimcthyl(cthylcniminc)), poly(propylcnciminc), poly(isopropyleneimine), poly(methyl(propyleneimine)), poly(dimethyl(propyleneimine)), poly(butyleneimine), poly(isobutyleneimine), poly( secbutyleneimine), poly-lysine, poly(allylamine), poly(but-3-en-l -amine), or poly(4-aminostyrene). In an exemplary embodiment, for any of the embodiments in the paragraph, at least one of the W is poly(ethylenimine), poly ( 1 -ethylenimine), poly(methyl(ethylenimine)), poly(dimethyl(ethylenimine)), poly(propyleneimine), poly(isopropyleneimine), poly(methyl(propyleneimine)), or poly(dimethyl(propyleneimine)).

[0041] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, and Z are as described herein, q is 1, each X is independently selected from, -O-(CH2)2NH2, and -O- poly(ethylenimine), each n is an integer independently selected from 2, 3, 4, 5, 6, 7, and 8, andO-^CF^ — H when: a) 1 of the X is5 v'n , 5 of the X are independently -O-(CH2)2NH2or -O- poly(ethylenimine); b) 2 of the X are, 4 of the X are independently -O-(CH2)2NH2O4-CH2-) — H or -O-poly(ethylenimine); c) 3 of the X are 'zn , 3 of the X are independently -O-(CH2)2NH2 or -O-poly(ethylenimine); d) 4 of the X are, 2 of the X are independently -O-(CH2)2NH2 or -O-poly(ethylenimine); or e) 5 of the X are, 1 of the X is -O-(CH2)2NH2or -O-poly(ethylenimine). In an exemplary embodiment, for any of theembodiments in this paragraph,exemplary embodiment, for anyCN of the embodiments in this paragraph, V isIn an exemplary embodiment, for any of the embodiments in this paragraph,whereinwherein ql + q2 + q3 is 1. In an exemplary embodiment, for any of the embodiments in this paragraph, when X isn is 6.

[0042] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, and Z are as described herein, q is 2, each X is independently selected from, -O-(CH2)2NH2, and -O- poly(ethylenimine), each n is an integer independently selected from 2, 3, 4, 5, 6, 7, and 8, andO-^CF^ — H when: a) 1 of the X is5 v / n, 11 of the X are independently -O-(CH2)2NH2 or -O- poly(ethylenimine); b) 2 of the X is, 10 of the X are independently -O-(CH2)2NH2 or -O-poly(ethylenimine); c) 3 of the X is, 9 of the X are independently -O-^-O4CH24— H(CH2)2NH2 or -O-poly(ethylenimine); d) 4 of the X is5 v'n , 8 of the X areO4-CH2") — H independently -O-(CH2)2NH2 or -O-poly(ethylenimine); e) 5 of the X is?' / n, 7 of theX are independently -O-(CIl2)2NIl2 or -O-poly(ethylenimine); f) 6 of the X is, 6 of the X are independently -O-CCFkhNFfc or -O-poly(ethylenimine); g) 7 of the X isare independently -O-(CH2)2NH2 or -O-poly(ethylenimine); h) 8 of the the X are independently -O-(CH2)2NH2 or -O-poly(ethylenimine); i) 9, 3 of the X are independently -O-(CH2)2NH2 or -O-poly(ethylenimine): j) 10 of the X is, 2 of the X are independently -O-(CH2)2NH2 or -O- poly(ethylenirnine); or k) 11 of the X is, 1 of the X is -O-(CH2)2NH2 or -O- poly(ethylenimine). In an exemplary embodiment, for any of the embodiments in this paragraph,exemplary embodiment, for any of the embodiments in thisCN i— c=c— paragraph, V is5H \ In an exemplary embodiment, for any of the embodiments in thisparagraph, when

[0043] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, and Z are as described herein, q is 3,^-O^-CH2-J— H each X is independently selected from -O-(CH2)2NH2, and -O-poly(ethylenimine), each n is an integer independently selected from 2, 3, 4, 5, 6, 7, and 8, and when: a) 1 of the XI— O4-CH2") — H is ' , 17 of the X are independently -O-(CH2)2NH2or -O-poly(ethylenimine); b) 2O ( CH2— H of the X are5' 'n, 16 of the X are independently -O-(CH2)2NH2or -O- o-fci-U — H poly(ethylenimine); c) 3 of the X are ' / n, 15 of the X are independently -O-OT"CH2“) — H(CH2)2NH2or -O-poly(ethylenimine); d) 4 of the X are5' / n, 14 of the X areO“^CH2^ — H independently -O-(CH2)2NH2or -O-poly(ethylenimine); e) 5 of the X are ' Y , 13 of the X are independently -O-(CH2)2NH2or -O-poly(ethylenimine); f) 6 of the X are^-O-fcH24— H5' 7 , 12 of the X are independently -O-(CH2)2NH2or -O-poly(ethylenimine); g) 7 of the X are, 11 of the X are independently -O-(CH2)2NH2or -O-poly(ethylenimine): h) 8 of the X are, 10 of the X are independently -O-(CH2)2NH2or -O- poly(ethylenimine); i) 9 of the X are, 9 of the X are independently -O-(CH2)2NH2or -O-poly(ethylenimine); j) 10 of the X are, 8 of the X are independently -O-O"PcH2^ — H(CH2)2NH2or -O-poly(ethylenimine); k) 11 ol the X are ’ 'zn , 7 of the X areO"AcH2^ — H independently -O-(CH2)2NH2or -O-poly(ethylenimine); 1) 12 of the X arez v, 6 of the X are independently -O-(CH2)2NH2or -O-poly(ethylenimine); m) 13 of the X are, 5 of the X are independently -O-(CH2)2NH2or -O-poly(ethylenimine); n) 14 ofO4"CH2^ — H the X arez'zn , 4 of the X are independently -O-(CH2)2NH2or -O-poly(ethylenimine);^-O-ACH2A— H o) 15 of the X are 'zn , 3 of the X are independently -O-(CH2)2NH2or -O-O-(-CH2-) — H poly(ethylenimine); p) 16 of the X aref v / n, 2 of the X are independently -O-^-O4CH24— H(CH2)2NH2or -O-poly(ethylenimine); or q) 17 of the X are ’ ' 'n , 1 of the X is -O-(CH2)2NH2or -O-poly(ethylenimine). In an exemplary embodiment, for any of theembodiments in this paragraph,exemplary embodiment, for anyCN of the embodiments in this paragraph, V isIn an exemplary embodiment, for any of the embodiments in this paragraph,whereinwherein ql + q2 + q3 is 3. In an exemplary embodiment, for any of the embodiments in this paragraph, when X isn is 6.

[0044] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, and Z are as described herein, q is 4, each X is independently selected fromand -O-poly(ethylenimine), each n is an integer independently selected from 2, 3, 4, 5, 6, 7, and 8, and when: a) 1 of the XO“^CH2-) — H is?' / n, 23 of the X are independently -O-CCIhhNFh or -O-poly(ethylenimine); b) 2 ko-fcH24— H of the X are ' 'n , 22 of the X are independently -O-(CH2)2NH2 or -O- poly(ethylenimine); c) 3 of the X are, 21 of the X are independently -O-Fo-fcH24— H(CH2)2NH2or -O-poly(ethylenimine); d) 4 of the X are5, 20 of the X are independently -O-(CH2)2NH2 or -O-poly(ethylenimine); e) 5 of the X are, 19 of the X are independently -O-CCFFhNFF or -O-poly(ethylenimine); f) 6 of the X areFO“^CH2^ — H4 v, 18 of the X are independently -O-CCFFhNFF or -O-poly(ethylenimine): g) 7 ofthe X are, 17 of the X are independently -O-(CH2)2NH2 or -O-poly(ethylenimine): h) 8 of the X are, 16 of the X are independently -O-(CH2)2NH2or -O- poly(ethylenimine); i) 9 of the X are,15 of the X are independently -O-(CH2)2NH2O“f-CH2^ — H or -O-poly(ethylenimine); j) 10 of the X are5' / n, 14 of the X are independently -O-(CH2)2NH2or -O-poly(ethylenimine); k) 11 of the X are, 13 of the X areindependently -O-(CH2)2NH2or -O-poly(ethylenimine); 1) 12 of the X are?'zn , 12 of the X are independently -O-(CH2)2NH2or -O-poly(ethylenimine); m) 13 of the X are e X are independently -O-(CH2)2NH2or -O-poly(ethylenimine): n) 14 of, 10 of the X are independently -O-(CH2)2NH2or -O-poly(ethylenimine);O"ACH2^ — H o) 15 of the X are 'zn , 9 of the X are independently -O-(CH2)2NH2or -O- poly(ethylenimine); p) 16 of the X are, 8 of the X are independently -O-(CII2)2NII2or -O-poly(ethylenimine); q) 17 of the X are, 7 of the X are independently -O-(CH2)2NH2 or -O-poly(ethylenimine); r) 18 of the X arc, 6 of the X are independently -O-(CH2)2NH2or -O-poly(ethylenimine); s) 19 of the X are, 5 of the X are independently -O-(CH2)2NH2or -O-poly(ethylenimine); t) 20 ofO-f-CH2') — H the X arcz'zn , 4 of the X are independently -O-(CH2)2NH2or -O-poly(ethylenimine);O"ACH2^ — H u) 21 of the X are ' 'n, 3 of the X are independently -O-(CH2)2NH2or -O-O"f'CH2^ — H poly(ethylenimine); v) 22 of the X are 'zn , 2 of the X are independently -O-(CH2)2NH2or -O-poly(ethylenimine); or w) 23 of the X are, 1 of the X is -O-(CH2)2NH2or -O-poly(ethyleniinine). In an exemplary embodiment, for any of the embodimentsexemplary embodiment, for any of theCN embodiments in this paragraph, V isIn an exemplary embodiment, for any of the embodiments in this paragraph,whereinwhereinwherein q 1 + q2 + q3 is 4. In an exemplary embodiment, for any of the embodiments in this paragraph, when X isn is 6.

[0045] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, and Z are as described herein, q is 1, each X is independently selected from, -O-(CH2)aNH2 or -O- poly(propyleneimine), each n is an integer independently selected from 2, 3, 4, 5, 6, 7, and 8, and when: a) 1 of the X is, 5 of the X are independently -O-(CH2)3NH2 or -O- poly (propyleneimine); b) 2 of the X are, 4 of the X are independently -O-(CH2)3NH2 or -O-poly(propyleneimine); c) 3 of the X are, 3 of the X are independently -O-(CH2)3NH2 or -O-poly(propyleneimine); d) 4 of the X are, 2 of the X are independently -O-(CH2)3NH2or -O-poly(propyleneimine); or e) 5 of the X are, 1 of the X is -O-(CH2)3NH2or -O-poly(propyleneimine). In an exemplary embodiment, for any of the embodiments in this paragraph,exemplary embodiment, for any of the embodiments in this paragraph, V isIn anexemplary embodiment, for any of the embodiments in this paragraph,whereinwhereinwherein ql + q2 + q3 is 1. In an exemplary embodiment, for any of the embodiments in this paragraph, when X is

[0046] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, and Z are as described herein, q is 1, each X is independently selected fromor -O- poly(propyleneimine), each n is an integer independently selected from 2, 3, 4, 5, 6, 7, and 8,O“f-CH2^ — H and when: a) 1 of the X is5 v'n , 5 of the X are independently -O-(CH2)3NH2 or -O-poly (propyleneimine); b) 2 of the X are5' 'n , 4 of the X are independently -O- o-f CH2^ — H(CH2)3NH2 or -O-poly(propyleneimine); c) 3 of the X are ' 'n, 3 of the X areO-f-CH2-) — H independently -O-(CH2)3NH2 or -O-poly(propyleneimine); d) 4 of the X are ' 'n , 2 of the X are independently -O-CCEhhNFh or -O-poly(propyleneimine); or e) 5 of the X are1 of the X is -O-(CH2)3NH2or -O-poIy(propyleneimine). In an exemplary embodiment, for any of the embodiments in this paragraph,CNI— c=c— exemplary embodiment, for any of the embodiments in this paragraph, V is5H . In anexemplary embodiment, for any of the embodiments in this paragraph,whereinwhereinwherein ql + q2 + q3 is 1. In an exemplary embodiment, for any of the embodiments in this paragraph, when X is

[0047] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, and Z are as described herein, q is 2, each X is independently selected from-O- poly(propyleneimine), each n is an integer independently selected from 2, 3, 4, 5, 6, 7, and 8,and when: a) 1 of the X is5n , 11of the X are independently -O-(CH2)3NH2 or -O- poly(propyleneimine); b) 2 of the X is, 10 of the X are independently -O-O"^CH2^ — H(CFFhNFF or -O-poly(propyleneimine); c) 3 of the X is 'Zn, 9 of the X are independently -O-lCFFhNFF or -O-poly(propyleneimine); d) 4 of the X is, 8 of the X are independently -O-CCEhhNFh or -O-poly(propyleneimine); e) 5 of the X is, 7 of the X are independently -O-(CH2)3NH2 or -O-poly(propyleneimine); f) 6 of0“rCH2“i — H the X is5, 6 of the X are independently -O-(CH2)3NH2 or -O-poly(propyleneimine); g) 7 of the X is, 5 of the X are independently -O-(CH2)JNH2 or -O- o-f CH2^ — H poly(propyleneimine); h) 8 of the X is 'zn , 4 of the X are independently -O-(CH2)3NH2 or -O-poly(propylcnciminc); i) 9 of the X is, 3 of the X arcO"ACH2^ — H independently -O-CCFFFNFh or -O-poly(propyleneimine); j) 10 of the X iss'zn , 2 ofthe X are independently -O-(CH2)3NH2 or -O-poly(propyleneimine); or k) 11 of the X is, 1 of the X is -O-(CH2)3NH2or -O-poly(propyleneimine). In an exemplary embodiment, for any of the embodiments in this paragraph,CN^-c=c-^ exemplary embodiment, for any of the embodiments in this paragraph, V is H . In an exemplary embodiment, for any of the embodiments in this paragraph, Z iswherein ql + q2 + y embodiment, for any of the embodiments in this paragraph, Z is plary embodiment, for any of the embodiments in this paragraph, when X

[0048] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, and Z arc as described herein, q is 3, each X is independently selected from, -O-(CH2)3NH2 or -O- poly(propyleneimine), each n is an integer independently selected from 2, 3, 4, 5, 6, 7, and 8, and when: a) 1 of the X is, 17 of the X are independently -O-(CH2)3NH2 or -O-O-f-CH2") — H poly(propyleneimine); b) 2 of the X are * ' / n, 16 of the X are independently -O-(CH2)3NH2or -O-poly(propylcnciminc); c) 3 of the X arc, 15 of the X arc-of CH24 — H independently -O-(CH2)3NH2or -O-poly(propyleneimine); d) 4 of the X arc ' 'n, 14 of the X are independently -O-(CH2)3NH2or -O-poly(propyleneimine); e) 5 of the X are e X are independently -O-(CII2)3NII2or -O-poly(propyleneimine); f) 6 of, 12 of the X are independently -O-lCffefNfh or -O- poly(propyleneimine); g) 7 of the X are, 11 of the X are independently -O-(CH2)3NH2or -O-poly(propyleneimine): h) 8 of the X are, 10 of the X are independently -O-(CH2)3NH2or -O-poly(propyleneimine); i) 9 of the X are, 9 of the X are independently -O-(CII2)3NII2or -O-poly(propyleneimine); j) 10 of the X areO“f-CH2^ — H* ' / n, 8 of the X are independently -O-(CH2)3NH2or -O-poly(propyleneimine); k) 1 1 of the X are, 7 of the X are independently -O-(CH2)3NH2or -O- poly(propyleneimine); 1) 12 of the X are, 6 of the X are independently -O-I-O-ACH24— H(CH2)3NH2or -O-poly(propyleneimine); m) 13 of the X are5' 'n , 5 of the X areO-fcH2^ — H independently -O-(CH2)3NH2or -O-poly(propyleneimine); n) 14 of the X arev, 4 of the X are independently -O-CCffefNfh or -O-poly(propyleneimine); o) 15 of the X are^-O~fcH24— H5' Y , 3 of the X are independently -O-(CH2)3NH2or -O-poly(propyleneimine); p) 16 ofO^CH2^ — H the X are5' / n, 2 of the X are independently -O-(CH2)3NH2or -O-^-O-fcH2-)— H poly(propyleneimine); or q) 17 of the X are5 v'n , 1 of the X is -O-(CH2)3NH2or -O- poly(propyleneimine). In an exemplary embodiment, for any of the embodiments in this paragraph,exemplary embodiment, for any of the embodimentsCN in this paragraph, V is. In an exemplary embodiment, for any of the embodiments inthis paragraph,wherein ql + q2 is 3, orwherein ql + q2 + q3 is 3. In an exemplary embodiment, for any of the embodiments in-OfCH2j— H this paragraph, when X is 'zn n is 6.

[0049] In an exemplary embodiment, according to Option A, the COF comprises a structure according to Formula (I), or a salt thereof, wherein Y, V, and Z are as described herein, q is 4, O-AcH2-) — H each X is independently selected from4'n, -O-(CH2)3NH2, and -O- poly(propyleneimine), each n is an integer independently selected from 2, 3, 4, 5, 6, 7, and 8, and when: a) 1 of the X is, 23 of the X are independently -O-(CH2)3NH2or -O- poly(propyleneimine); b) 2 of the X are, 22 of the X are independently -O-(CH2)3NH2or -O-poly(propyleneimine); c) 3 of the X are, 21 of the X are independently -O-(CH2)3NH2or -O-poly(propyleneimine); d) 4 of the X are, 20 of the X are independently -O-(CH2)3NH2 or -O-poly(propyleneimine); e) 5 of the X are e X are independently -O-(CH2)3NH2or -O-poly(propyleneimine); f) 6 of, 18 of the X are independently -O-(CIl2)3NII2or -O-O"^CH2^ — H poly(propyleneimine); g) 7 of the X are5'zn , 17 of the X are independently -O-(CH2)3NH2or -O-poly(propyleneimine); h) 8 of the X are, 16 of the X areO-f-CH2-) — H independently -O-(CH2)3NH2or -O-poly(propyleneimine); i) 9 of the X are 'zn ,15 of the X are independently -O-(CH2)3NH2or -O-poly(propyleneimine); j) 10 of the X are, 14 of the X are independently -O-(CH2)3NH2 or -O-poly(propyleneimine); k) 11^-o4cH24— H of the X are5' 'n , 13 of the X are independently -O-(CH2)3NH2 or -O-O-fcH2^ — H poly(propyleneimine); 1) 12 of the X arev / n, 12 of the X are independently -O-(CH2)3NH2or -O-poly(propyleneimine); m) 13 of the X are, l l of the X are independently -O-(CH2)3NH2 or -O-poly(propyleneimine); n) 14 of the X are, 10 of the X are independently -O-(CH2)3NH2 or -O-poly (propyleneimine): o) 15 of the X are X are independently -O-(CH2)3NH2or -O-poly(propyleneimine); p) 16 of t, 8 of the X are independently -O-(CH2)3NH2 or -O- poly(propyleneimine); q) 17 of the X are, 7 of the X are independently -O-(CH2)3NH2or -O-poly(propyleneimine): r) 18 of the X are, 6 of the X are independently -O-(CH2)3NH2or -O-poly(propyleneimine); s) 19 of the X are, 5 of the X are independently -O-(CH2)3NH2or -O-poly(propyleneimine); t) 20 of the X are, 4 of the X are independently -O-(CH2)3NH2 or -O-poly(propyleneimine); u) 21 of O4CH24— H the X are5' 'n , 3 of the X are independently -O-(CH2)3NH2or -O-F o-f CH2^ — H poly(propyleneimine); v) 22 of the X are 'A|, 2 of the X are independently -O-(CH2)3NH2or -O-poly(propyleneimine); or w) 23 of the X are5X , 1 of the X is -O-(CH2)3NH2or -O-poly(propyleneimine). In an exemplary embodiment, for any of the embodiments in this paragraph,exemplary embodiment, for any of the embodiments in this paragraph, V isIn an exemplary embodiment, for any ofthe embodiments in this paragraph,whereinwherein ql + q2 + q3 is 4. In an exemplary embodiment, for any of the embodiments in this paragraph, when X isn is 6.

[0050] In an exemplary embodiment, the COF comprises a structure according to Formula (I), or a salt thereof, whereinly selected from 0 to 12; and when n is an integer from 1 to 12, each W is H.

[0051] In an exemplary embodiment, the COF comprises a structure according to Formula (I), or a salt thereof, whereinselected fromwherein each n is an integer independently selected from 0 to 12; and W is H or -OH or -SH or -NH2.

[0052] In an exemplary embodiment, the COF comprises a structure according to Formula (I), or a salt thereof, whereinis an integer independently selected from 0 to 12; and W is H or -OH or -SH or -NH2.

[0053] In an exemplary embodiment, the COF is mCOF-999-lNH2, or a salt thereof. In an exemplary embodiment, the COF is mC0F-999-10H, or a salt thereof. In an exemplary embodiment, the COF is mCOF-999-2OH, or a salt thereof. In an exemplary embodiment, the COF is mCOF-999-3OH, or a salt thereof.

[0054] In an exemplary embodiment, the COF is mCOF-999-lN-PEI, or a salt thereof. In an exemplary embodiment, the COF is mCOF-999-lN-PEIl, mCOF-999-lN-PEI2, mCOF-999- 1N-PEI3, mCOF-999-lN-PEI4, mCOF-999-lN-PEI5, or mCOF-999-lN-PEI6. In an exemplary embodiment, the COF is a salt of mCOF-999-lN-PEIl, mCOF-999-lN-PEI2, mCOF-999-lN- PEI3, mCOF-999-lN-PEI4, mCOF-999-lN-PEI5, or mCOF-999-lN-PEI6. In an exemplary embodiment, the COF is mCOF-999-lN-PEI3, or a salt thereof.

[0055] In an exemplary embodiment, the COF is mCOF-999-lN-PPI, or a salt thereof. In an exemplary embodiment, the COF is mCOF-999-lN-PPIl, mCOF-999-lN-PPI2, mCOF-999-lN- PPI3, mCOF-999-lN-PPI4, mCOF-999-lN-PPI5, or mCOF-999-lN-PPI6. In an exemplary embodiment, the COF is a salt of mCOF-999-lN-PPIl, mCOF-999-lN-PPI2, mCOF-999-lN- PPI3, mCOF-999-lN-PPI4, mCOF-999-lN-PPI5, or mCOF-999-lN-PPI6.

[0056] In an exemplary embodiment, the COF is mC0F-999-10-PEI, or a salt thereof. In an exemplary embodiment, the COF is mC0F-999-10-PEIl, mC0F-999-10-PEI2, mCOF-999- 1O-PEI3, mC0F-999-10-PEI4, mC0F-999-10-PEI5, or mC0F-999-10-PEI6. In an exemplary embodiment, the COF is a salt of mC0F-999-10-PEIl, mC0F-999-10-PEI2, mC0F-999-10- PEI3, mC0F-999-10-PEI4, mC0F-999-10-PEI5, or mC0F-999-10-PEI6. In an exemplary embodiment, the COF is mC0F-999-10-PEIl, or a salt thereof.

[0057] In an exemplary embodiment, the COF is mC0F-999-10-PPI, or a salt thereof. In an exemplary embodiment, the COF is mC0F-999-10-PPIl, mC0F-999-10-PPI2, mC0F-999-10- PPI3, mC0F-999-10-PPI4, mC0F-999-10-PPI5, or mC0F-999-10-PPI6. In an exemplaryembodiment, the COF is a salt of mC0F-999-10-PPIl, mC0F-999-10-PPI2, mC0F-999-10- PPI3, mC0F-999-10-PPI4, mC0F-999-10-PPI5, or mC0F-999-10-PPI6. In an exemplary embodiment, the COF is mC0F-999-10-PPI3, or a salt thereof.

[0058] In an exemplary embodiment, the COF is mCOF-999-2O-PEI, or a salt thereof. In an exemplary embodiment, the COF is mCOF-999-2O-PEIl, mCOF-999-2O-PEI2, mCOF-999- 2O-PEI3, mCOF-999-2O-PEI4, mCOF-999-2O-PEI5, or mCOF-999-2O-PEI6. In an exemplary embodiment, the COF is a salt of mCOF-999-2O-PEIl, mCOF-999-2O-PEI2, mCOF-999-2O- PEI3, mCOF-999-2O-PEI4, mCOF-999-2O-PEI5, or mCOF-999-2O-PEI6. In an exemplary embodiment, the COF is mCOF-999-2O-PEI3, or a salt thereof.

[0059] In an exemplary embodiment, the COF is mCOF-999-2O-PPI, or a salt thereof. In an exemplary embodiment, the COF is mCOF-999-2O-PPIl, mCOF-999-2O-PPI2, mCOF-999-2O- PPI3, mCOF-999-2O-PPI4, mCOF-999-2O-PPI5, or mCOF-999-2O-PPI6. In an exemplary embodiment, the COF is a salt of mCOF-999-2O-PPIl, mCOF-999-2O-PPI2, mCOF-999-2O- PPI3, mCOF-999-2O-PPI4, mCOF-999-2O-PPI5, or mCOF-999-2O-PPI6. In an exemplary embodiment, the COF is mCOF-999-2O-PPI3, or a salt thereof.

[0060] In an exemplary embodiment, the COF is mCOF-999-3O-PEl, or a salt thereof. In an exemplary embodiment, the COF is mCOF-999-3O-PEIl, mCOF-999-3O-PEI2, mCOF-999- 3O-PEI3, mCOF-999-3O-PEI4, mCOF-999-3O-PEI5, or mCOF-999-3O-PEI6. In an exemplary embodiment, the COF is a salt of mCOF-999-3O-PEIl, mCOF-999-3O-PEI2, mCOF-999-3O- PEI3, mCOF-999-3O-PEI4, mCOF-999-3O-PEI5, or mCOF-999-3O-PEI6. In an exemplary embodiment, the COF is mCOF-999-3O-PEIl, or a salt thereof.

[0061] In an exemplary embodiment, the COF is mCOF-999-3O-PPl, or a salt thereof. In an exemplary embodiment, the COF is mCOF-999-3O-PPIl, mCOF-999-3O-PPI2, mCOF-999-3O- PPI3, mCOF-999-3O-PPI4, mCOF-999-3O-PPI5, or mCOF-999-3O-PPI6. In an exemplary embodiment, the COF is a salt of mCOF-999-3O-PPIl, mCOF-999-3O-PPI2, mCOF-999-3O- PPI3, mCOF-999-3O-PPI4, mCOF-999-3O-PPI5, or mCOF-999-3O-PPI6.

[0062] In an exemplary embodiment, according to Option A or Option B, the COF comprises a repeating core, wherein a core is according to a Formula described herein. In an exemplary embodiment, according to Option A or Option B, the COF comprises a core (such as according to a Formula described herein). In an exemplary embodiment, according to Option A or Option B, a core described herein (such as according to a Formula described herein) forms part of an adjacent core which is part of the repeating core. In an exemplary embodiment, according to Option A or Option B, the COF according to a Formula described herein is crystalline. In anexemplary embodiment, according to Option A or Option B, the structure according to a Formula described herein is crystalline. In an exemplary embodiment, according to Option A or Option B, the COF according to a Formula described herein is porous. In an exemplary embodiment, according to Option A or Option B, the structure according to a Formula described herein is porous. In an exemplary embodiment, according to Option A or Option B, the structure according to a Formula described herein is stable. In an exemplary embodiment, according to Option A or Option B, the COF according to a Formula described herein is stable. In an exemplary embodiment, according to Option A or Option B, the structure according to a Formula described herein is hydrolytically stable. In an exemplary embodiment, according to Option A or Option B, the COF according to a Formula described herein is hydrolytically stable. In an exemplary embodiment, according to Option A or Option B, the structure according to a Formula described herein is two-dimensional. In an exemplary embodiment, according to Option A or Option B, the repeating core described herein is two-dimensional. In an exemplary embodiment, according to Option A or Option B, the structure according to a Formula described herein has a hcb topology. In an exemplary embodiment, according to Option A or Option B, the COF described herein has a hcb topology. In an exemplary embodiment, for any of the embodiments in the paragraph, the Option is Option A.

[0063] In exemplary embodiments, COFs according to Option A are different than those COFs according to Option B. Those of Option A possess at least one and not more than (X-l) of the Ws as H, halogen, ethylene glycol, poly(ethylene glycol), methyl. C2-C6 linear alkyl, or C3-C6 branched alkyl. The presence of these moieties confer beneficial properties on COFs according to Option A over those COFs according to Option B.

[0064] In an exemplary embodiment, according to Option A, the COF comprises a plurality of two-dimensional structures according to a Formula described herein. In an exemplary embodiment, according to Option A, the COF comprises a first two-dimensional slruclure according to a Formula described herein, and a second two-dimensional structure according to a Formula described herein, and the first two-dimensional structure and the second two- dimensional structure have a staggered, eclipsed, serrated, or inclined configuration with respect to each other. In an exemplary embodiment, the COF according to Option A the two- dimensional structures arc in a configuration that increases passage of CO2 through the COF as compared to the COF according to Option B. The increased CO2 passage through the COF of Option A over the COF of Option B is a beneficial property.

[0065] In an exemplary embodiment, a COF according to Option A has a greater capacity / cost efficiency than those known in the art. In an exemplary embodiment, a COF according to Option A has a greater capacity / cost efficiency than a COF according to Option B.

[0066] The term “salt” means a salt which is acceptable for use in a COF. Such salts can be derived from inorganic or organic bases and from inorganic or organic acids. Such salts can be derived from inorganic or organic acids and from inorganic or organic bases. The salts can be derived from a variety of organic and inorganic counter ions well known in the art and include, by way of example only, sodium, potassium, calcium, magnesium, ammonium, tetraalkylammonium, aluminum, and the like; and when the molecule contains a basic functionality, salts of organic or inorganic acids, such as hydrochloride, hydrobromide, hydroiodide, trifluoroacetate, formate, tartrate, besylate, mesylate, acetate, maleate, oxalate, sulfate, phosphate, citrate, nitrate, gluconate, and the like.IL Improved Methods of COF SynthesisIL a) Azide-free synthesis of pre-polymerized COFs

[0067] Compounds that contain the azide group (-Ns) are generally considered to be explosive and unstable, especially under heat, shock, friction, or exposure to certain chemicals. The instability arises from the azide group’s tendency to rapidly decompose into nitrogen gas (N2), releasing a large amount of energy in a short time.

[0068] A common reactant in the synthesis of azide-containing compounds is sodium azide. Sodium azide is highly toxic if ingested, inhaled, or absorbed through the skin. Even small amounts can lead to severe poisoning. In rats, the LD50 (oral) is 27 mg / kg, which is extremely toxic. In addition, sodium azide is explosive when heated or subjected to shock or friction, especially in a solid form. It can also be explosive when in contact with metals such as lead or copper, forming highly sensitive metal azides.

[0069] Pre-polymerized compositions according to Option A or Option B are currently synthesized using azide-containing precursors and / or reactants. An example of the previously known azide-involved synthetic method is described below for COF-999-NH2:The production of these COF compositions are thus dangerous to humans. The dangers of toxicity and explosivity increase as the amount of the COF composition produced also increases. An essentially azide-free synthesis of COF compositions would thus be an improvement in the art. Surprisingly, the inventors have created such a synthesis.IL a) i) Azide-free synthesis of pre-polymerized COFs

[0070] In an exemplary embodiment, the invention provides a COF synthesized by a method described in Section II. a) i) and / or herein (such as in the Examples). In an exemplary embodiment, the invention provides a composition described herein according to Option B in which its synthesis is essentially free of azide. In an exemplary embodiment, the invention provides a composition described herein according to Option B in which its synthesis does not comprise an azide.

[0071] In an exemplary embodiment, the invention provides a method of synthesizing a COF according to Option B, comprising contacting a compound according to this structurewherein Xi is independently selected fromHN4CH2)-OH , i— S4CH2VOH , . . . . . .' 'n, and ' 'yn , each D is a first reactive moiety, and each E is a second reactive moiety, wherein the reaction of the D and the E produces V which is selected from\ In an exemplary embodiment, the method of synthesis is essentially free of azide.

[0072] In an exemplary embodiment, the invention provides a method of synthesizing COF-999, comprising a) contacting a compound according to this structureEO{CH2^ — OH compound independently selected from E , wherein Xi is ' , each D is a first reactive moiety, and each E is a second reactive moiety, wherein the reaction of the D and the ECN J f-C=C-| produces V which is H . In an exemplary embodiment, the method of synthesis is essentially free of azide. In an exemplary embodiment, the method of synthesizing COF-999 further comprises: b) converting the hydroxyl group on Xi to a hydroxyl leaving group (such as Cl, Br, tosyl or mesyl): c) converting the hydroxyl leaving group on Xi to NH2; and d) converting the NH2 on Xi to poly(ethylenimine). In an exemplary embodiment, the method of synthesis is essentially free of azide. In an exemplary embodiment, the method of synthesis is essentially free of aziridine.

[0073] General azide-free of COF-999: BPDA-OH can react with a halogenated alkanol (such as 6-chloro-l -hexanol shown below) to give a product with alkanol (such as hexanol) groups. This product can react with TCPB to form a COF material with free OH groups. This COF canbe activated with a group such as TsCl, and then reacted with an ammonia solution to give COF- 999-NH2.IL a) ii) Azide-free synthesis of pre-polymerized mCOF-999-O

[0074] In an exemplary embodiment, the invention provides a COF synthesized by a method described in Section II. a) ii) and / or herein (such as in the Examples). In an exemplary embodiment, the invention provides a method of synthesizing a COF according to Option A, comprising contacting a compound according to this structurefirst linker independently selected from, whereinE? _ OH ? _ 3HXi is * or ? , and with a second linker independently selected from E, , , g , y g y , poly(ethylene glycol), methyl, C2-C6 linear alkyl, C3-C6 branched alkyl, each D is a first reactive moiety, and each E is a second reactive moiety, wherein the reaction of the D and the Eproduces V which is selected fromIn an exemplary embodiment, when the first linker ithen the second linker iexemplary embodiment, when the first linker ithen the second linker is lary embodiment, when the first linkerthen the secondexemplary embodiment, when the first linkerthen the second linkerexemplary embodiment, the method of synthesis is essentially free of azide.

[0075] In an exemplary embodiment, the invention provides a method of synthesizing an mCOF-999-*O, comprising contacting a compound according to this structureand with a second linkerE, wherein X2 is '&, each D is a first reactive moiety, and each E is a second reactive moiety, wherein the reaction of the D and the E produces V which is selected fromIn an exemplary embodiment, the method of synthesis is essentially free of azide.

[0076] General azide-free syntheses of mCOF-999-*O: TCPB (about 1 eq), BPDA-OH (** eq), and BPDA-OC6 (*** eq, **+*** = about 1.5) are added to a pressure vessel, followed by 1,2-dichlorobenzene (about 30 mL per gram of TCPB) and n-butanol (about 30 mL per gram of TCPB). The vessel is capped and heated at about 80 °C until all solid dissolved. CS2CO3 (about 2 eq) is added, and the resultant mixture is sonicated at ambient temperature for about 1 hour. After this time, the vessel is heated at about 120 °C for about 4 hours. After cooling to room temperature, the mixture is filtered and washed thoroughly with H2O, methanol, ethyl acetate, and hexanes to give the desired product as a yellow powder. In an exemplary embodiment, about 0.75 eq BPDA-OH and about 0.75 eq BPDA-OC6 are used in the above synthesis to produce mCOF-999-OH with 6 alkanes to 6 OH (mCOF-999-3O). In an exemplary embodiment, about 1.0 eq BPDA-OH and about 0.5 eq BPDA-OC6 are used in the above synthesis to produce mCOF-999-OH with 4 alkanes to 8 OH (mCOF-999-4O). In an exemplary embodiment, about 1.25 eq BPDA-OH and about 0.25 eq BPDA-OC6 are used in the above synthesis to produce mCOF-999-OH with 2 alkanes to 10 OH (mCOF-999-5O).IL a) iii) Azide-free synthesis of pre-polymerized mCOF-999-N

[0077] In an exemplary embodiment, the invention provides a COF synthesized by a method described in Section II. a) iii) and / or herein (such as in the Examples). In an exemplary embodiment, the invention provides a method of synthesizing a COF according to Option A,Xi is independently selected from, Wi is independently selected from NHBoc, NHFmoc, NHC(O)O-benzyl, NHC(O)O-benzyl,NHC(O)CH3, NHC(O)CF3, -phthalimide, -NH-benzyl, -NHC(Ph)3, N=R (Schiff base), and -ENHS(O)2-(p-toluene) and with a second linker independently selected from E, wherein n as described herein, and W is FI, halogen, ethylene glycol, poly(ethylene glycol), methyl, C2-C6 linear alkyl, C3-C6 branched alkyl, each D is a first reactive moiety, and each E is a second reactive moiety, wherein the reaction of the D and the ECN produces V which isIn an exemplary embodiment, when the first linker ithen the second linker iexemplary embodiment, when the first linker isexemplary embodiment, when the first linker ithen the second linker iexemplary embodiment, when the first linker iexemplary embodiment, the method of synthesis is essentially free of azide.

[0078] In an exemplary embodiment, the invention provides a method of synthesizing an mCOF-999-*N, comprising contacting a compound according to this structureEsecond linkerEwherein X2 is, each D is a first reactive moiety, and eachE is a second reactive moiety, wherein the reaction of the D and the E produces V which isCN l-c=c-|H . In an exemplary embodiment, the method of synthesis is essentially free of azide.

[0079] General azide-free syntheses of mCOF-999-*N: TCPB (about 1 eq), BPDA-NBoc (** eq), and BPDA-OC6 (*** eq, **+”* = about 1.5) are added to a pressure vessel, followed by 1,2-dichlorobenzene (about 30 mL per gram of TCPB) and n-butanol (about 30 mL per gram of TCPB). The vessel is capped and heated at 80 °C until all solid dissolved. CS2CO3 (about 2 eq) is added, and the resultant mixture is sonicated at ambient temperature for about 1 hour. After this time, the vessel is heated at about 120 °C for about 4 hours. After cooling to room temperature, the mixture is filtered and washed thoroughly with H2O, methanol, ethyl acetate, and hexanes to give the desired product as a yellow powder. In an exemplary embodiment, about 0.5 eq BPDA-NBoc and about 1.0 eq BPDA-OC6 arc used in the above synthesis to produce mCOF-999-NBoc with 8 alkanes to 4 NBoc (mCOF-999-2NBoc). In an exemplary embodiment, about 0.75 eq BPDA-NBoc and about 0.75 eq BPDA-OC6 are used in the above synthesis to produce mCOF-999-NBoc with 6 alkanes to 6 NBoc (mCOF-999-3NBoc). In an exemplary embodiment, about 1 .0 eq BPDA-NBoc and about 0.5 eq BPDA-OC6 are used in the above synthesis to produce mCOF-999-NBoc with 4 alkanes to 8 NBoc (mCOF-999-4NBoc). In an exemplary embodiment, about 1.25 eq BPDA-NBoc and about 0.25 eq BPDA-OC6 are used in the above synthesis to produce mCOF-999-NBoc with 2 alkanes to 10 NBoc (mCOF-999- 5NBoc).IL b) Aziridine-free synthesis of COFs comprising poly(ethylenimine)

[0080] The known syntheses of COFs comprising poly(ethylenimine) involve aziridine. Using aziridine in these syntheses is undesirable for at least the following reasons. First, aziridine is a potent irritant to the skin, eyes, and respiratory system and can cause respiratory distress and skin bums. Second, aziridine can form DNA adducts and is thus thought to be carcinogenic. Third, aziridine is highly reactive, polymerizing and undergoing other reactions that lead to hazardous situations, such as explosions, if not handled properly. Fourth, aziridine is flammable, which poses risks of fire or explosion in an industrial environment. Fifth, aziridine poses environmental concerns as it can harm aquatic and plant life and potentially enter the food chain.

[0081] Because of these issues, the use and storage of aziridine is not feasible, particularly for large-scale processes. Thus, we found chemical substitutes that can yield the same or similar result as using aziridine. An essentially aziridine-free synthesis of COF compositions would thus be an improvement in the art. Surprisingly, the inventors have created such a synthesis.

[0082] An example of the previously known aziridine-involved synthetic method is described below for COF-999:wherein each W is independently selected from -NH2, -NH(CH2)2NH2, and poly (ethyleneimine).In certain embodiments, the poly(ethyleneimine) in this paragraph has from 2 to 30 subunits, or from 2 to 25 subunits, or from 2 to 20 subunits, or from 2 to 15 subunits, or from 2 to 12 subunits, or from 2 to 10 subunits, or from 2 to 9 subunits, or from 2 to 8 subunits, or from 2 to 7 subunits, or from 2 to 6 subunits, or from 2 to 5 subunits.

[0083] In an exemplary embodiment, the invention provides a composition described herein according to Option A or Option B wherein at least one W is poly(ethyleneimine) in which its synthesis is essentially free of aziridine. In an exemplary embodiment, the invention provides a composition described herein according to Option A or Option B wherein at least one W is poly(ethyleneimine) in which its synthesis does not comprise aziridine.IL b) i) Aziridine-free synthesis of COFs comprising poly(ethylenimine)

[0084] In an exemplary embodiment, the invention provides a OOF synthesized by a method described in Section II. b) i) and / or herein (such as in the Examples). In an exemplary embodiment, the invention provides a composition described herein according to Option B comprising poly(ethylenimine) in which its synthesis is essentially free of aziridine. In an exemplary embodiment, the invention provides a composition described herein according to Option B comprising poly(ethylenimine) in which its synthesis is essentially free of aziridine.

[0085] In an exemplary embodiment, the invention provides a method of synthesizing a covalent organic framework (COF) comprising a structure according to Formula (I), or a salt thereof,m k O-fcH24- W v 'n, wherein each W is independently selected from -NI I(CI FhNl F or poly(ethyleneimine) each n is an integer independently selected from 2 to 12; and q is 1, 2, 3, or 4, the method comprising contacting a reactant selected from 2-chloroethylamine, 2- bromoethylamine, ethanolamine, tert-butyl (2-bromoethyl)carbamate, ethyl (2- bromoethyl)carbamate, benzyl (2-bromoethyl)carbamate, and tert-butyl (2-iodoethyl)carbamate, and a covalent organic framework (COF) comprising a structure according to Formula (I), or amO^CH2-^-NH2, wherein each n is an integer independently selected from 2 to 12; and q is 1, 2,3, or 4. In an exemplary embodiment, the method of synthesis is essentially free of aziridine.

[0086] In an exemplary embodiment, the invention provides a method of synthesizing COF-999, the method comprising contacting a reactant selected from 2-chloroethylamine, 2- bromoethylamine, ethanolamine, tert-butyl (2-bromoethyl)carbamate, ethyl (2- bromoethyl)carbamate, benzyl (2-bromoethyl)carbamate, and tert-butyl (2-iodoethyl)carbamate,and a covalent organic framework (COF) comprising a structure according to the following formula:

[0087] General aziridine-free syntheses of a COF-999: COF-999-NH2 can then be reacted with a compound such as 2-chloroethylamine hydrochloride (or 2-bromoethylamine, ethanolamine, tert-butyl (2-bromoethyl)carbamate, ethyl (2-bromoethyl)carbamate, benzyl (2- bromoethyl)carbamate, and tert-butyl (2-iodoethyl)carbamate) to provide COF-999.IL b) ii) Aziridine-free synthesis of mCOF-999-*O-PEI****

[0088] In an exemplary embodiment, the invention provides a COF synthesized by a method described in Section II. b) ii) and / or herein (such as in the Examples). In an exemplary embodiment, the invention provides a method of synthesizing a covalent organic framework(COF) comprising a structure according to Formula (I), or a salt thereof, wherein Y is- w, wherein each n is an integer independently selected from 0 to12; and when n is an integer from 1 to 12, each W is independently selected from H, halogen, ethylene glycol, poly(ethylene glycol), methyl, C2-C6 linear alkyl, C3-C6 branched alkyl, - NH(CH2)2NH2, poly(ethylenimine), and when n is 0, each W is independently selected from H, halogen, ethylene glycol, polyethylene glycol), methyl, C2-Ce linear alkyl, C3-C6 branched alkyl, -(CIl2)2NIl2, and poly(ethylenimine), wherein at least one and not more than (X-l) of the W is H, halogen, ethylene glycol, poly(ethylene glycol), methyl, C2-C6 linear alkyl, or C3-C6 branched alkyl, and q is 1, 2, 3, or 4, the method comprising contacting a reactant selected from 2-chloroethylamine, 2-bromoethylamine, ethanolamine, tert-butyl (2-bromoethyl)carbamate, ethyl (2-bromoethyl)carbamate, benzyl (2-bromoethyl)carbamate, and tert-butyl (2- iodoethyl)carbamate, and a covalent organic framework (COF) comprising a structure accordingI- O4-CH23 — w ? — N4CH2T- W q2 + q3 = q; each X is independently selected from4'zn ' 'n , andI— S-(CH2)-W' 'n, wherein each n is an integer independently selected from 0 to 12; and when n is an integer from 1 to 12, each W is independently selected from H, halogen, ethylene glycol, polyethylene glycol), methyl, C2-C6 linear alkyl, C3-G5 branched alkyl, and -NH2. and when n is 0, each W is independently selected from H, halogen, ethylene glycol, poly(ethylene glycol), methyl, C2-C6 linear alkyl, C3-C6 branched alkyl, -NH2, wherein at least one and not more than (X-l) of the W is H, halogen, ethylene glycol, poly( ethylene glycol), methyl, C2-C6 linear alkyl, or C3-C6 branched alkyl, and q is 1, 2, 3, or 4.

[0089] In an exemplary embodiment, the invention provides a method of synthesizing mCOF- 999-*O-PEI****, the method comprising contacting a reactant selected from 2- chloroethylamine, 2-bromoethylamine, ethanolamine, tert-butyl (2-bromoethyl)carbamate, ethyl (2-bromoethyl)carbamate, benzyl (2-bromoethyl)carbamate, and tert-butyl (2- iodoethyl)carbamate, and a covalent organic framework (COF) comprising a structure according to the following formula:wherein each X is independently selected fromor -OH, wherein at least one X is-O-(CH2)2NH2and at least one X is -OH.

[0090] General aziridine-free syntheses of mCOF-999-*O-PEI****: The attachment of PEI to the mCOF-999-*O sample can be done by taking mCOF-999-*O (800 mg), 2- chloroethylamine hydrochloride (10 g, 86 mmol), and H2O (10 mL) and putting them a 100 mL pressure vessel, followed by NaOH (6.88 g, 172 mmol) in H2O (10 mL). The pressure vessel can be capped, and the resultant mixture can be stirred at 100 °C for 4 hours. After cooling to room temperature, the mixture can be filtered and washed thoroughly with H2O until the filtrate does not change color after adding 5% Q1SO4 solution. The filtrate cake can be further washed with methanol, ethyl acetate, and hexanes, and dried under reduced pressure to give the mCOF-999- *O-PEI1. Using mCOF-999-*O-PEH instead of mCOF-999-*O, the PEI attachment reaction can be repeated to give mCOF-999-*O-PEI2. Using mCOF-999-*O-PEI(t) instead of mCOF- 999-*O, the PEI attachment reaction can be repeated to give mCOF-999-*O-PEI(t+l).IL b) iii) Aziridine-free synthesis of mCOF-999-*N-PEI****

[0091] In an exemplary embodiment, the invention provides a COF synthesized by a method described in Section II. b) iii) and / or herein (such as in the Examples). In an exemplary embodiment, the invention provides a method of synthesizing a covalent organic framework(COF) comprising a structure according to Formula (I), or a salt thereof, wherein Y is,O-(-CH2^ — H' / <3, -O-(CH2)2NH2, and -O-poly(ethylenimine), and wherein at least one X is -O-(CH2)2NH2or -O-poly(ethylenimine), the method comprising contacting a reactant selected from 2-chloroethylamine, 2-bromoethylamine, ethanolamine, tert-butyl (2-bromoethyl)carbamate, ethyl (2-bromoethyl)carbamate, benzyl (2-bromoethyl)carbamate, and tert-butyl (2- iodoethyl)carbamate, and a covalent organic framework (COF) comprising a structure accordingUo-fCH2-)— H ko-fcH24-W2q2 + q3 = q; each X is independently selected from 'zn , 'z2, wherein n is an integer selected from 2 to 12; W2 is independently selected from H, halogen, ethylene glycol, polyethylene glycol), methyl, C2-C6 linear alkyl, C3-C6 branched alkyl, NHBoc, NHFmoc, NHC(O)O-benzyl, NHC(O)O-benzyl, NHC(O)CH3, NHC(O)CF3, -phthalimide, -NH-benzyl, -NHC(Ph)3, N=R (Schiff base), and - NHS (O)2-(p-toluene) .

[0092] In an exemplary embodiment, the invention provides a method of synthesizing mCOF- 999-*N-PEI****, the method comprising contacting a reactant selected from 2- chloroethylamine, 2-bromoethylamine, ethanolamine, tert-butyl (2-bromoethyl)carbamate, ethyl (2-bromoethyl)carbamate, benzyl (2-bromoethyl)carbamate, and tert-butyl (2- iodoethyl)carbamate, and a covalent organic framework (COF) comprising a structure according to the following formula:wherein each X is independently selected froinor -O-(CH2)2WI, wherein Wi is independently selected from NHBoc, NHFmoc, NHC(O)O-benzyl, NHC(O)O-benzyl, NHC(O)CH3, NHC(O)CF3, -phthalimide, -NH-benzyl, -NHC(Ph)3, N=R (Schiff base), and - NHS(O)2-(p-toluene), wherein at least one X is -O-(CH2)2WI and at least one X is

[0093] General aziridine-free syntheses of mCOF-999-*N-PEI****: The attachment of PEI to the mCOF-999-*N sample can be done by taking mCOF-999-*N (approx 800 mg), 2- chloroethylamine hydrochloride (approx 10 g, 86 mmol), and FEO (approx 10 mL) and putting them into a 100 mL pressure vessel, followed by NaOH (approx 6.88 g, 172 mmol) in H2O (approx 10 mL). The pressure vessel can be capped, and the resultant mixture can be stirred at 100 °C for 4 hours. After cooling to room temperature, the mixture can be filtered and washed thoroughly with H2O until the filtrate does not change color after adding 5% CuSCU solution. The filtrate cake can be further washed with methanol, ethyl acetate, and hexanes, and dried under reduced pressure to give mCOF-999-*N-PEIl. Using mCOF-999-*N-PEIl instead of mCOF-999-*N, the PEI attachment reaction can be repeated to give mCOF-999-*N-PEI2. Using mCOF-999-*N-PEI(t) instead of mCOF-999-*N, the PEI attachment reaction can be repeated to give mCOF-999-*N-PEI(t+l).IL c) Non-Aziridine polymer introductions into COFs

[0094] In an exemplary embodiment, the invention provides a COF synthesized by a method described in Section II. c) and / or herein (such as in the Examples). Poly(propyleneimine) can be introduced into a pre -polymerized COF described herein by replacing 2-chloroethylamine in a synthesis described herein with 3 -chloropropylamine hydrochloride, 3 -bromopropylamine hydrobromide, azetidine hydrochloride or azetidine.

[0095] Synthesis of mCOF-999-2O-PPI3: The attachment of poly(propyleneimine) to the mCOF-999-2O sample can be done by taking mCOF-999-2O (approx 800 mg), 3- chloropropylamine hydrochloride (approx 11.2 g, 86 mmol), and I CO (approx 10 mL) and putting them into an approx 100 mL pressure vessel, followed by NaOH (approx 6.88 g, 172 mmol) in H2O (approx 10 mL). The pressure vessel can be capped, and the resultant mixture can be stirred at approx 100 °C for approx 4 hours. After cooling to room temperature, the mixture can be filtered and washed thoroughly with H2O. The filtrate cake can be reacted with 3- chloropropyl amine hydrochloride again using the previous condition to give mCOF-999-2O- PPI2. mCOF-999-2O-PPI2 can be reacted with 2-chloropropylamine hydrochloride again using the previous condition. After cooling to room temperature, the mixture can be filtered and washed thoroughly with H2O, MeOH, ethyl acetate, and hexanes to give the desired product (mCOF-999-2O-PPI3).III. Methods of Use and SystemsUtilization of COFs for Carbon Capture Processes Post-combustion capture (PCC)

[0096] In specific embodiments, a COF described herein is used as a solid adsorbent in the postcombustion capture of CO2 from natural gas or coal flue gas. In some variations, the CO2 concentration in the feed flue gas is from 4% to 16%, and the temperature of the feed flue gas is below 40 °C. In certain variations, the CO2 concentration in the feed flue gas is from 4% to 16%, and the temperature of the feed flue gas is below 90 °C.

[0097] In some variations, a COF described herein is used in pure form, homogeneously mixed with other materials, or supported on other materials in the form factor of powders. In some variations, a COF described herein is used in pure form, homogeneously mixed with other materials, or supported on other materials in the form factor of shape bodies. In these scenarios, the powder or shape bodies are used in packed bed, cartridge exchanger, fluidized bed, etc.

[0098] In these scenarios, removal of CO2 from a COF described herein involves heating, change of pressure, gas sweeping, washing, etc., or the combination of some or all of them.

[0099] In these scenarios, a COF described herein exhibiting such properties are used:

[0100] High working capacity difference toward CO2 from the combination of chemisorption (if present) and physisorption depending on the adsorption condition and regeneration condition;

[0101] For chemisorption, bearing reactive functional groups such as those in the W variable described herein;

[0102] For the dynamic capacity measurement of COFs described herein, breakthrough experiments are configured with feed gas mixture of 4%-50% (or from 4%-16%), corresponding humidity and temperature.

[0103] Adequate affinity to CO2 such that enough working capacity is retained in the presence of H2O.

[0104] Robustness: chemical stability to H2O, O2, CO2, and impurities in both adsorption condition and regeneration condition, including the retention of chemical composition, crystallinity, sorption capacities and porosity. Thermal stability toward the range of operation temperature.

[0105] Open framework structure with permanent porosity to ensure efficient mass transfer.

[0106] In some variations where heating is used for regeneration, low heat capacity. In some variations where the COF is in shape body or supported by other materials, tight binding for mechanical stability.

[0107] In some variations, COFs are used in pure form, homogeneously mixed with other materials, or supported on other materials in the form factor of membranes. In these scenarios, the powder or shape bodies are used in membrane filtration, membrane exchanger, or cartridge exchanger, etc.

[0108] High, selective affinity toward CO2 that increases the solubility of the membrane, through both chemisorption (if present) and physisorption at the separation condition.

[0109] -For chemisorption, reactive functional groups such as -NIfc or -NIIR are part of the COF.

[0110] For the dynamic capacity measurement of such COFs, breakthrough experiments or membrane-specific continuous tests are configured with feed gas mixture of 4%-50% (or from 4%-16%), corresponding humidity and temperature.

[0111] Adequate affinity to CO2 such that enough working capacity is retained in the presence of H2O.

[0112] Robustness: chemical stability to H2O, O2, CO2, and impurities in both adsorption condition and regeneration condition, including the retention of chemical composition, crystallinity, sorption capacities and porosity. Thermal stability toward the range of operation temperature.

[0113] In some variations where the COF is supported by other materials in the membrane, tight binding with the support for mechanical stability.

[0114] In some variations where heating is used for regeneration, low heat capacity.Direct air capture (DAC)

[0115] In a specific embodiment, COFs are used as solid adsorbent in the direct capture of CO2 from ambient air. In most variations, the CO2 concentration in the feed flue gas is atmospheric concentration (-400 ppm, 1 atm. In some variations, CO2 concentration > 400 ppm when compressed air is used) or slightly higher through compression or in a closed, non-ambient chamber, and the temperature of the feed gas is ambient temperature.

[0116] In some variations, COFs are used in pure form, homogeneously mixed with other materials, or supported on other materials in the form factor of powders. In some variations, COFs are used in pure form, homogeneously mixed with other materials, or supported on other materials in the form factor of shape bodies. In these scenarios, the powder or shape bodies are used in packed bed, cartridge exchanger, fluidized bed, etc.

[0117] In these scenarios, removal of CO2 from COFs involves heating, change of pressure, gas sweeping, washing, etc., or the combination of some or all of them.

[0118] In these scenarios, COFs exhibiting such properties are used:

[0119] High working capacity difference toward CO2 from chemisorption depending on the adsorption condition and regeneration condition.

[0120] -For chemisorption, high gravimetric or volumetric density of reactive functional groups such as -NH2 or -NHR.

[0121] For the dynamic capacity measurement of such COFs, breakthrough experiments are configured with feed gas mixture of -400 ppm, corresponding humidity and temperature.

[0122] Adequate affinity to CO2 such that enough working capacity is retained in the presence of H2O.

[0123] Robustness: chemical stability to H2O, O2, CO2, and impurities in both adsorption condition and regeneration condition, including the retention of chemical composition,crystallinity, sorption capacities and porosity. Thermal stability toward the range of operation temperature.

[0124] Open framework structure with permanent porosity to ensure efficient mass transfer.

[0125] In some variations where heating is used for regeneration, low heat capacity.

[0126] In some variations where the COF is in shape body or supported by other materials, tight binding for mechanical stability.

[0127] In an exemplary embodiment, the COF described herein is configured for carbon dioxide capture. In an exemplary embodiment, the COF described herein is configured for carbon dioxide capture and separation, including direct air capture from ambient air and postcombustion capture from natural gas or flue gas. In an exemplary embodiment, the COF described herein is contained in a matrix configured as a sorption bed, fluidized bed, coated heat exchanger, or membrane. In an exemplary embodiment, the COF described herein is contained in a matrix configured as a sorption bed, fluidized bed, coated heat exchanger, or membrane, in a fluid flow path configured to pass the air or mixture over, around and / or through the matrix. In an exemplary embodiment, the COF described herein comprises an air or post-combustion exhaust gas mixture, wherein water is present in the air or mixture, and the material is configured and is operative to harvest the water from the air or mixture. In an exemplary embodiment, the COF described herein is configured for carbon dioxide capture in a matrix which further comprising an air or post-combustion exhaust gas mixture, wherein water is present in the air or mixture, and the material is configured and is operative to harvest the water from the air or mixture, and provides facile collection of water as a second value-delivering function.

[0128] In another aspect, the invention provides a system for capturing carbon dioxide from air or a post-combustion exhaust gas mixture comprising a matrix, such as a sorption bed containing the COF described herein, configured as a solid adsorbent for capturing the carbon dioxide, and optionally water, from the air or mixture.

[0129] In another aspect, the invention provides a method comprising using the COF described herein as a solid adsorbent for capturing carbon dioxide, and optionally water, from air or a postcombustion exhaust gas mixture. In an exemplary embodiment, the method of using the COF described herein for carbon dioxide capture and / or separation, especially from air or flue gas.Parallel Water Harvesting

[0130] In some variations, the COF adsorbent exhibit high uptake of both CO2 and H2O at the same time of PCC or DAC. The CO2 and H2O can be therefore removed in the same step, or in different steps through different conditions. Through facile further purification, such COF adsorbent can produce high-purity water as a side-product of CO2 capture from air or from flue gas.

[0131] In these scenarios, COFs exhibiting such properties are used:

[0132] High working capacity difference toward H2O from physisorption depending on the adsorption condition and regeneration condition.

[0133] For the dynamic capacity measurement of such COFs, breakthrough experiments are configured with feed gas mixture at the desired humidity and temperature.

[0134] Adequate affinity to H2O such that enough working capacity is retained in the presence of CO2.

[0135] Robustness: chemical stability to H2O, O2. CO2, and impurities in both adsorption condition and regeneration condition, including the retention of chemical composition, crystallinity, sorption capacities and porosity. Thermal stability toward the range of operation temperature.

[0136] Open framework structure with permanent porosity to ensure efficient mass transfer.

[0137] In some variations where heating is used for regeneration, low heat capacity.

[0138] In some variations where the COF described herein is in shape body or supported by other materials, tight binding for mechanical stability.

[0139] In an exemplary embodiment, the COF described herein is configured for carbon dioxide capture. In an exemplary embodiment, the COF described herein is configured for carbon dioxide capture and separation, including direct air capture from ambient air and postcombustion capture from natural gas or flue gas. In an exemplary embodiment, the COF described herein is contained in a matrix configured as a sorption bed, fluidized bed, coated heat exchanger, or membrane. In an exemplary embodiment, the COF described herein is contained in a matrix configured as a sorption bed, fluidized bed, coated heat exchanger, or membrane, in a fluid flow path configured to pass the air or mixture over, around and / or through the matrix. In an exemplary embodiment, the matrix described herein is comprising an air or postcombustion exhaust gas mixture, wherein water is present in the air or mixture, and the material is configured and is operative to harvest the water from the air or mixture, and provides facilecollection of water as a second value-delivering function. In another aspect, the invention provides a system for capturing carbon dioxide from air or a post-combustion exhaust gas mixture comprising a matrix, such as a sorption bed containing the COF described herein, configured as a solid adsorbent for capturing the carbon dioxide, and optionally water, from the air or mixture. In another aspect, the invention provides a method comprising using the COF described herein as a solid adsorbent for capturing carbon dioxide, and optionally water, from air or a post-combustion exhaust gas mixture. In another aspect, the invention provides a method of using the COF described herein for carbon dioxide capture and / or separation, especially from air or flue gas.

[0140] In an exemplary embodiment, the invention is a COF described herein, configured for carbon dioxide capture. In an exemplary embodiment, the invention is a COF described herein configured for carbon dioxide capture and separation, including direct air capture from ambient air and post-combustion capture from natural gas or flue gas. In an exemplary embodiment, the invention is a COF described herein, contained in a matrix configured as a sorption bed, fluidized bed, coated heat exchanger, or membrane. In an exemplary embodiment, the invention is a COF described herein, contained in a matrix configured as a sorption bed, fluidized bed, coated heat exchanger, or membrane, in a fluid flow path configured to pass the air or mixture over, around and / or through the matrix. In an exemplary embodiment, the invention is a COF described herein, comprising an air or post-combustion exhaust gas mixture, wherein water is present in the air or mixture, and the material is configured and is operative to harvest the water from the air or mixture. In an exemplary embodiment, the invention is a system for capturing carbon dioxide from air or a post-combustion exhaust gas mixture comprising a matrix, such as a sorption bed containing the COF described herein, configured as a solid adsorbent for capturing the carbon dioxide, and optionally water, from the air or mixture. In an exemplary embodiment, the invention is a method comprising using the COF described herein as a solid adsorbent for capturing carbon dioxide, and optionally water, from air or a post-combustion exhaust gas mixture. In an exemplary embodiment, the invention is a method of using the COF described herein for carbon dioxide capture and / or separation, especially from air or flue gas.

[0141] All publications and patent applications mentioned in this disclosure are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.

[0142] No admission is made that any reference cited herein constitutes prior art. The discussion of the references states what their authors assert, and the Applicant reserves the right to challenge the accuracy and pertinence of the cited documents. It will be clearly understood that,although a number of information sources, including scientific journal articles, patent documents, and textbooks, are referred to herein; this reference does not constitute an admission that any of these documents forms part of the common general knowledge in the art.

[0143] The discussion of the general methods given herein is intended for illustrative purposes only. Other alternative methods and alternatives will be apparent to those of skill in the art upon review of this disclosure, and are to be included within the spirit and purview of this application.

[0144] Additional embodiments are disclosed in further detail in the following examples, which are provided by way of illustration and are not in any way intended to limit the scope of this disclosure or the claims.EXAMPLESExample 1: Synthesis of COF-999 with aziridine

[0145] Synthesis of COF-999 -Ns. A borosilicate glass tube measuring 8 x 10 mm (i.d. x o.d.) was charged with TCPB (16.9 mg, 0.04 mmol), BPDA-N3 (29.6 mg, 0.06 mmol) and CS2CO3 (39.1 mg, 0.12 mmol) were mixed in 0.5 mb 1,2-dichlorobenzene and 0.5 mL 1 -butanol. The mixture was flash frozen at 77 K in a liquid nitrogen bath, evacuated to an internal pressure below 0.2 mbar, and flame sealed. The length of the tube was reduced to around 10 cm upon sealing. After warming to room temperature, the mixture was heated at 120 °C for 3 days in an oven to yield a yellow solid. The solid was filtered, washed with methanol (30 mL), and was used directly for the next step without further treatment. To characterize COF-999-N3, the yellow solid described above was transferred into a Kimwipe bag and further washed with methanol for 16 h in a Soxhlet extractor, dried with supercritical CO2, and degassed at 30 °C for 3 h under vacuum to yield COF-999-N3 as a yellow-colored solid (yield 81 %). Elemental analysis for C23H21N4O: Calcd. C 74.77%, H 5.73%, N 15.17%; Found C 74.08%, H 5.79%, N 14.01%.

[0146] Synthesis of COF-999-NH2. To a 100 mL round bottom flask, COF-999-N3 (100 mg), PPhs (200 mg), and 30 mL methanol were added under 25 °C. After 24 h, the suspension was filtered and washed with methanol to remove excess PPh3. The yellow residue was transferred to another 100 mL round bottom flask, and 24 mL methanol and 6 mL water were added under 25 °C. After 24 h, the suspension was filtered in a Kimwipe bag, washed in methanol for 16 h in a Soxhlet extractor, dried with supercritical CO2, and degassed at 30 °C for 3 h under vacuum to yield COF-999-NH2 as a yellow-colored solid (yield 98%). Elemental analysis for C23H23N2O: Calcd. C 80.44%, H 6.75%, N 8.16%; Found C 78.51%, H 6.38%, N 8.10%.

[0147] Synthesis of COF-999. COF-999-NH2(30 mg), toluene (2 mL), acetic acid (5 pL), and aziridine (100 pL) were added to a borosilicate glass tube measuring 8 x 10 mm (i.d. x o.d. The mixture was flash frozen at 77 K in a liquid nitrogen bath, evacuated to an internal pressure below 0.3 mbar, and flame sealed. The length of the tube was reduced to around 10 cm upon sealing. After warming to room temperature, the reaction was heated at 100 °C for 24 h. After cooling down to 25 °C, the solid was filtered in a Kimwipe bag, washed with 50 mL 1 M NaOH in methanol, then washed with methanol for 16 h in a Soxhlet extractor, and dried at 120 °C for 12 h under vacuum to yield COF-999 as a yellow-colored solid (yield 86%). Elemental analysis for C23H23N2O (C2H5N)3.I: Calcd. C 73.53%, H 8.14%, N 14.98%; Found C 70.19%, H 7.24%, N 14.35%.Example 2: Aziridine-free synthesis of COF-999Synthesis of 3,3'-bis[(6-azidohexyl)oxy]-4,4'-biphenyldicarbaldehyde (BPDA-N3).

[0148] 3,3'-Dihydroxy-4,4'-biphenyldicarboxaldehyde (1.0 g, 4.1 mmol, 1.0 equiv.), K2CO3 (1.7 g, 12 mmol, 3.0 equiv.) and 1 -hexanol, 6-azido-, 1 -(4-methylbenzenesulfonate) (2.7 g, 9.0 mmol, 2.2 equiv.) were added to 30 mL anhydrous DMF under N2atmosphere. The resulting suspension was heated to 80 °C and stirred for 16 h. After cooling down, DMF was evaporated under reduced pressure, and the remaining mixture was extracted by water (100 mL) and DCM (100 mL). The organic phase was collected, washed with water (100 mL) and brine (50 mL), and dried over sodium sulfate. The solution was filtered and concentrated, and the resulting solid was subjected to flash column chromatography using silica gel and with ethyl acetate / hexanes (1 / 5, v / v) as eluent to afford the product as a white solid (1.52 g, yield 74%).!H NMR (600 MHz, CDCI3): 5 (ppm) 10.53 (s, 2H), 7.92 (d, 7 = 8.0 Hz, 2H), 7.23 (d, 7 = 8.0 Hz, 2H), 7.14 (s, 2H), 4.18 (t, 7 = 6.3 Hz, 4H), 3.30 (t, 7 = 6.3 Hz, 4H), 1.91 (m, 4H), 1.65 (m, 4H), 1.57 (m, 4H), 1.50 (m, 4H).13C NMR (151 MHZ, CDCI3) 5 189.4, 161.8, 147.9, 129.1, 124.7, 120.0, 111.5, 68.7, 51.5, 29.1, 28.9, 26.6, 25.8. HR-ESI-MS: m / z: 515.2382 (|A7 + Na|+. calcd. for [C26H32N6O4Na]+515.2377).

[0149] Synthesis of COF-999-Ns. TCPB (169 mg, 0.400 mmol, 1 eq) and BPDA-N3 (295 mg, 0.600 mmol) were added to a 30 mL glass vial, followed by 1,2-dichlorobenzene (5 mL) and n- butanol (5 mL). The mixture was heated at 80 °C till all solid dissolved. CS2CO3 (391 mg, 1.20mmol) was added. The vial was capped and sonicated for 1 hour at ambient temperature. The cap was removed, and the vial was put into a 100 mL autoclave reactor. The reactor was heated in an oven at 120°C for 2 hours. After cooling to room temperature, the mixture was filtered and washed thoroughly with H2O, MeOH, ethyl acetate, and hexanes. The filtrate cake was dried under reduced pressure to give COF-999-Ns as a yellow solid.

[0150] The PXRD pattern showed COF-N3 is a crystalline material, with a prominent peak at 2theta = -2.4° indicating the presence of a hexagonal pore structure. The FTIR spectrum showed the presence of two signature function groups: cyano (-C=N) group at -2250cm1from TCPB and azido (-N3) group at -2090cm1from BPDA-N3. The absence of the aldehyde group at -1680cm1in the FTIR spectrum indicated successful polymerization.

[0151] Synthesis of COF-999-NH2. COF-999-N3 (880 mg), PPI13 (1.77 g, 6.7 mmol), and methanol (250 mL) were added to a 500 mL round-bottomed flask. The resultant mixture was stirred at room temperature for 16 hours. After this time, the suspension was filtered, and the filtrate cake was washed with methanol till the filtrate showed no UV absorbance at 254 nm. The filtrate cake and MeOH / FFO (4: 1 v / v, 200 mL) were added to a 500 mL round-bottomed flask and stirred at room temperature for 1 day. After this time, the mixture was filtered and washed thoroughly with ILO, MeOII, ethyl acetate, and hexanes. The filtrate cake was dried under reduced pressure to give COF-999-NH2 as a yellow solid.

[0152] The PXRD pattern showed COF-NH2 is a crystalline material, with a prominent peak at 2theta = -2.4° which indicated the presence of a hexagonal pore structure. The FTIR spectrum showed the absence of azido (-N3) group at -2090cm1which indicated the successful reduction of the azido group to an amino group.

[0153] Synthesis of COF-999. COF-999-NH2 (200 mg) was put into a 15 mL pressure vessel. 2-Chloroethylamine hydrochloride (2 g, 17.2 mmol), H2O (2 mL) and NaOH (1.38 g, 34.4 mmol) were added. The resultant mixture was stirred at room temperature for 24 h, and then stirred at 100 °C for 16 hours. After cooling to room temperature, the mixture was filtered and washed thoroughly with H2O until the filtrate does not change color after adding 5% CuSCU solution. The filtrate cake was put into a 15 mL pressure vessel again. 2-Chloroethylamine hydrochloride (2 g, 17.2 mmol), II2O (2 mL) and NaOII (1.38 g, 34.4 mmol) were added. The resultant mixture was stirred at room temperature for 24 h, and then stirred at 100°C for 16 hours. After cooling to room temperature, the mixture was filtered and washed thoroughly with H2O, MeOH, ethyl acetate, and hexanes. The filtrate cake was dried under reduced pressure to give COF-999 as a yellow solid (76% Yield).

[0154] The PXRD pattern showed that COF-999 remained semi-crystalline after the PEI polymerization. The FTIR spectrum showed the emergence of ethylene C-H stretch at -2820cm'1.Example 3: Alternate synthesis of BPDA-OH

[0155] 4-Bromo-2-methoxybenzaldehyde (64.5 g, 0.3 mol, 1.0 eq), (Bpinh (76.2 g, 0.3 mol, 1.0 eq), KOAc (89.2 g, 0.9 mol, 3 eq), Pd(dppf)Ch (550 mg, 0.75 mmol, 0.25% eq) and 1,4-dioxane (500 mL) were added to a 2 L flask equipped with a condenser under N2. The resultant mixture was stirred at 90 °C for 18 hours. After cooling down to room temperature, the solvent was evaporated and the residue was precipitate was filtered, and the remaining mixture was extracted by water (1 L) and ethyl acetate (1 L). The organic phase was collected, washed with water (500 mL) and brine (200 mL), and dried over sodium sulfate. The solvent was evaporated and the residue was recrystallized in ethyl acetate and hexane to give 2-methoxy-4-(4,4,5,5-tetramethyl- l,3,2-dioxaborolan-2-yl)benzaldehyde as a brown solid (75.0 g, 95% yield).

[0156] 2-methoxy-4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)benzaldehyde (75 g, 0.29 mol, 1.0 eq), 4-Bromo-2-methoxybenzaldehyde (61.5 g, 0.29 mol, 1 eq), Pd(PPh3)4 (867 mg, 0.75 mmol, 0.25% eq), K2CO3 (80.1 g, 0.58 mol, 2 eq), water (125 mL) and 1,4-dioxane (500 mL) were added to a 2 L flask equipped with a condenser under N2. The resultant mixture was stirred at 95 °C for 18 hours. After cooling down to room temperature, the mixture was filtered and the residue was washed with water (200 mL) and DCM (50 mL) to yield 3,3'- Dimethoxy[l,l'-biphenyl]-4,4'-dicarboxaldehyde as an off white sold (70.9 g, 91% yield).

[0157] Dimethoxyfl, l'-biphenyl]-4,4'-dicarboxaldehyde (70.9 g, 0.26 mol, 1 eq) and 500 mL DCM were added to a 2 L flask under N2. The flask was cooled to 0 °C and BBn (74.6 mL, 0.78 mol, 3 eq) was added dropwise into the flask. The mixture was then stirred under 25 °C for 18 h. Water (300 mL) was then slowly added to the mixture under 0 °C. The mixture was filtered and the residue was washed with water (100 mL) and DCM (100 mL) to yield 3,3'-Dihydroxy[l,l'- biphenyl]-4,4'-dicarboxaldehyde as an off white solid (52.7 g, 84% yield).Example 4: Synthesis of mCOF-999-lN-PEI3

[0158] mCOF-999-lN-PEI3 comprises a structure:wherein each R is -(Cl h lsCI h and each W is independently selected from,-NH(CH2)2NH2, and poly(ethylenimine). Synthesis of BPDA-OC6 was described herein. a) Synthesis of BPDA-NBoc

[0159] 3,3'-Dihydroxy-4,4'-biphenyldicarboxaldehyde (484 mg, 2.00 mmol, 1 eq), DMF (10 mL), and K2C(L (828 mg, 6.00 mmol, 3 eq) were added to a 50 mL round bottomed flask. The mixture was stirred at 80 °C for 10 min. tert-butyl M(2-bromoethyl)carbamate (986 mg, 0.440 mmol, 2.2 eq) in DMF (2 mL) was added at 80 °C portion wise in 1 hour. The resultant mixture was stirred at 80 °C for 16 hours. After cooling to room temperature, the mixture was poured into water (100 mL) and filtered. The filtrate cake was collected and dried under reduced pressure to give the crude product, which was further purified by recrystallization from ethyl acetate to afford the desired product as a pale-yellow powder (582 mg, 55% Yield). 'l l NMR (60 MHz, CDCL): 5 (ppm) 10.49 (m, 2 H), 7.91 (m, 2 H), 7.24 (m, 4 H), 4.80 (m, 2 H), 4.24 (m, 4H), 3.66 (m, 4 H), 1.43 (S, 18 H). The FTIR of BPDA-NBoc showed the expected peaks of secondary amine group (-3300cm1), aldehyde group (-1680cm1), and ester group (-1710cm1).b) Synthesis of mCOF-999-lNBoc

[0160] TCPB (169 mg, 0.400 mmol), BPDA-NBoc (53 mg, 0.10 mmol), and BPDA-OC6 (205 mg, 0.500 mmol) were added to a 20 mL glass vail, followed by 1,2-dichlorobenzene (5 mL) and n-butanol (5 mL). The mixture was heated at 80 °C till all solid dissolved. CS2CO3 (391 mg, 1.20 mmol) was added. The vial was capped and sonicated for 1 hour at ambient temperature. The cap was removed, and the vial was put into a 100 mL autoclave reactor. The reactor was heated in an oven at 120 °C for 4 hours. After cooling to room temperature, the mixture was filtered and washed thoroughly with H2O, MeOH, ethyl acetate, and hexanes. The filtrate cake was dried under reduced pressure to give mCOF-999-lNBoc as a yellow solid. The PXRD pattern showed mCOF-999-2NBoc was a crystalline material, with a prominent peak at 2theta = -2.4° which indicated the presence of a hexagonal pore structure. The FTIR spectrum showed the presence of a cyano group (at -2250cm’1), a hexyl group (from 2800-3000cm’1), a secondary amine group (-3300cm1), and an ester group (-1710cm1).c) Synthesis of mCOF-999-lNH2

[0161] The mCOF-999-lNBoc was then converted into mCOF-999-lNH2. mCOF-999-lNBoc (400 mg) was treated with TFA (5 mL) at room temperature for 24 hours. The mixture was filtered and washed thoroughly with 10 wt. % NaOH, H2O, MeOH, ethyl acetate, and hexanes. The filtrate cake was dried under reduced pressure to give mCOF-999-lNH2 as a yellow solid. The N2 sorption isotherm of mCOF-999-lNH2 was measured at 77 K, giving a Brunauer- Emmett- Teller (BET) surface area of 820 m2g ’. The PXRD pattern showed mCOF-999-lNH2 remained a crystalline material after the deprotection reaction. The FTIR spectrum showed the presence of a cyano group (at -2250cm1) and a hexyl group (from 2800-3000cm-1). d) Synthesis of mCOF-999 1N-PEI3

[0162] The next step for mCOF-999-lN-PEI3 is as follows:wherein each R is -(('I EhCI E and each W is independently selected from, -NH(CH2)2NH2, and poly(ethylenimine). The attachment of PEI to the mCOF-999-lNH2sample was done by taking mCOF-999-lNH2(289 mg), 2-chloroethylamine hydrochloride (3.00 g, 26.5 mmol), and H2O (3 mL) and putting them into a 48 mL pressure vessel, followed by NaOH (2.12 g, 53.1 mmol). The resultant mixture was stirred at room temperature for 24 h, and then stirred at 100 °C for 16 hours. After cooling to room temperature, the mixture was filtered and washed thoroughly with H2O till the filtrate doesn’t change color after adding 5% Q1SO4 solution. The filtrate cake reacted with 2-chloroethylamine hydrochloride again using the previous condition to give mCOF-999-lN-PEI2. mCOF-999-lN-PEI2 reacted with 2- chloroethylamine hydrochloride again using the previous condition. After cooling to room temperature, the mixture was filtered and washed thoroughly with H2O, MeOH, ethyl acetate, and hexanes to give the desired product as a yellow solid. The PXRD pattern showed that mCOF-999-lN-PEI3 remained a crystalline material after PEI polymerization. The FTIR spectrum showed the presence of a cyano group (at -2250cm1), a hexyl group (from 2800- 3000cm’1), and an ethylene group (~2820cm’1).Example 5: Synthesis of mCOF-999-lO-PEIl

[0163] mC0F-999-10-PEIl is synthesized as follows:wherein each R is -(CH2)sCH3 and each W is independently selected from *NH(CH2)2NH2, and poly(ethylenimine). The synthesis of mC0F-999-10H is described herein.The attachment of PEI to the mC0F-999-10H sample was done by taking mC0F-999-10H(1.00 g), 2-chloroethylamine hydrochloride (10.0 g, 86.2 mmol), and H2O (10 mL) and putting them into a 100 mL pressure vessel, followed by NaOH (6.88 g, 172 mmol) in H2O (10 mL). The pressure vessel was capped, and the resultant mixture was stirred at 100 °C for 10 hours. After cooling to room temperature, the mixture was filtered. The filter cake was washed with II2O (30 mL x 10) and methanol (30 mL x 3) and dried under reduced pressure to give mCOF- 999-1O-PEI1 as a yellow solid. The PXRD pattern showed mC0F-999-10-PEIl was a semicrystalline material after PEI polymerization. The FTIR spectrum showed the presence of a cyano group (at -2220cm’1), a hexyl group (from 2800-3000cm’1), and an ethylene group (-2820cm’1).

[0164] mC0F-999-10-PEIl demonstrated a CO2 DAC capacity of 0.5 mmol / g in open air (approximately 25 °C, 42% RII). It showed very fast CO2 adsorption kinetics. At 50% RII and 400 ppm CO2, mC0F-999-10-PEIl reached 80% of its working capacity in only 25 minutes.Example 6: Synthesis of mCOF-999-lO-PPI3 a) Synthesis of mCOF-999-lOH

[0165] TCPB (1.69 g, 4.00 mmol), BPDA-OH (242 mg, 1.00 mmol), and BPDA-C6 (2.05 g, 5.00 mmol) were added to a 200 mL PTFE pressure vessel, followed by 50 mL of 1,2- dichlorobenzene and / / .-butanol (50 mL). The vessel was capped and heated at 80 °C till all soliddissolved. CS2CO3 (7.82 g, 24 mmol, 2 eq) was added and the resultant mixture was sonicated at ambient temperature for 1 hour. After this time, the vessel was heated at 120 °C for 4 hours. After cooling to room temperature, the mixture was filtered and washed thoroughly with H2O, methanol, ethyl acetate, and hexanes to give the desired product as a yellow powder. The PXRD pattern showed mC0F-999-10II was a crystalline material, with a prominent peak at 2theta = -2.4° which indicated the presence of a hexagonal pore structure. The FTIR spectrum showed the presence of a cyano group (at -2220cm’1) and hexyl group (from 2800-3000cm'1). b) Synthesis of mCOF-999-lO-PPI3

[0166] The next step for mC0F-999-10-PPI3 is as follows:wherein each R is -(CHzhCH? and each W is independently selected from <NH(CH2)3NH2, and poly(propyleneimine). The attachment of PPI to the mC0F-999-10H sample was done by taking mC0F-999-10H (1.00 g), 3-chloropropylamine hydrochloride (10.0 g, 76.9 mmol), and H2O (10 mL) and putting them into a 100 mL pressure vessel, followed by (6. 15 g, 154 mmol) in H2O (10 mL). The pressure vessel was capped, and the resultant mixture was stirred at 100 °C for 10 hours. After cooling to room temperature, the mixture was filtered and washed thoroughly with H2O. The filtrate cake reacted with 3-chloropropylamine againusing the previous condition to give mC0F-999-10-PPI2. mC0F-999-10-PPI2 reacted with 3- chloropropylamine hydrochloride again using the previous condition. After cooling to room temperature, the mixture was filtered and washed thoroughly with H2O, MeOH, ethyl acetate, and hexanes to give the desired product (mC0F-999-10-PPI3) as a yellow solid. The PXRD pattern showed mC0F-999-10-PPI3 was a semi-crystalline material after PPI polymerization. The FTIR spectrum showed the presence of a cyano group (at -2220cm1), a hexyl group (from 2800-3000cm-1), and a propyl group (~2820cnr1).

[0167] mC0F-999-10-PPI3 demonstrated a CO2 DAC (direct air-capture) capacity of 1.4 mmol / g in open air (approximately 15 °C, 37% humidity). It was measured using the following procedure. The sample was first exposed to ambient outdoor air overnight to allow adsorption of atmospheric CO2 under natural conditions. After saturation, the sample was transferred to a sealed chamber equipped with a calibrated CO2 sensor and an integrated heating plate. The sample was heated at 100 °C for 5 minutes to desorb the captured CO2. The change in CO2 concentration within the sealed chamber was continuously monitored, and the total amount of CO2 released was quantified based on the measured concentration profile.

[0168] The thermal stability of mC0F-999-10-PPI3 was measured. A 0.5mm layer of 0.8g of mC0F-999-10-PPI3 was deposited on an aluminum plate and placed in a chamber. The film of mC0F-999-10-PPI3 was heated to 70°C for 5 minutes and then cooled to 10°C for 30 minutes and then the cycle repeated with 35 minutes for each cycle. The sample was cycled continuously for over 4 weeks for a total of 1170 cycles. The concentration of carbon dioxide (CO2) was measured inside the chamber to confirm the amount of CO2 adsorbed and released by the film during cycling. The ambient temperature was tracked and showed that the adsorption and desorption of CO2 depended slightly on the ambient temperature and tracked the day and night variation of the ambient temperature. The working capacity of the mCOF-999-IO-PPI3 sample, calculated by the amount of CO2 that was released into the chamber, was found to decrease by less than 10% after 1170 cycles.

[0169] mC0F-999-10-PPI3 showed better stability compared to mCOF-999-2O-PEI3. For mCOF-999-2O-PEI3, its CO2 DAC capacity decreased by more than 30% after being heated at 110 °C for 100 cycles. In contrast, the CO2 DAC capacity of mC0F-999-10-PPI3 had a marginal decrease of less than 5%. The cycle stability test was done using the following procedure. The sample was heated to 110 °C for 5 minutes in open air and then cooled to room temperature for 25 minutes, resulting in a total cycle time of 30 minutes. This process was repeated for 100 cycles. After completing the cycling test, the CO2 working capacity of thesample was measured. The percentage decrease in capacity was then calculated by comparing the post-cycling capacity with the initial value measured before cycling.

[0170] In long-term thermal stability tests, mC0F-999-10-PPI3 outperformed COF-999-PEI. Its To.oi / 10 h is 107.58 °C, compared to 102 °C for COF-999-PEI. Long term isothermal stability experiments were completed for 600 minutes at a constant temperature. For these experiments the sample was heated at 5 °C / min and held isothermally at for 600 mins from 90 °C to 110 °C in 10-degree increments and the subsequent degradation was then analyzed at each temperature and fit to generate zeroth order kinetics to give To.oi,iohr, where the subscript 0.01 indicates 1% of the mass and lOhr is designated 10 hours of isothermal exposure. The results showed that mC0F-999-10-153-PPI3 lost 1% of its mass when held at a temperature of 107.58 °C for 10 hours.

[0171] mC0F-999-10-PPI3 also exhibited faster adsorption kinetics than COF-999-PEI. At 50% RH and 400 ppm CO2, COF-999-PEI reached 80% of its working capacity in 61 minutes, whereas mC0F-999-10-PPI3 reached 80% of its working capacity in 42 minutes. A breakthrough system was constructed to examine CO2 / H2O mixed gas adsorption. The system was comprised of three feed streams, CO2, N2 and H2O. The relative humidity and temperature were detected using a Vaisala HMT310, while CO2 detection was completed using a Vaisala GMP251 detector. The sample was degassed at 80 °C for 120 hours under a N2 sweep, then passed through CO2, concentration of 400 ppm, a relative humidity of 50% or 75 %. The time to reach 50% and 80% CO2 adsorption equilibrium loadings were determined from the integrated data. At 50% RH mC0F-999-10-PPI3 required 18 minutes to reach 50% adsorption capacity and 42 minutes to reach 80% of the total capacity. When the relative humidity was switched to 75% RH the time required to reach 50% and 80% of the total CO2 capacity at 400ppm was reduced to 6 minutes and 22 minutes respectively.Example 7: Synthesis of mCOF-999-2O-PEI3

[0172] mCOF-999-2O-PEI3 comprises a structure:wherein each R is -(CH2)sCH3 and each W is independently selected fromNH(CH2)2NH2, and poly(ethylenimine). a) Synthesis of 3,3'-dihydroxy-4,4'-biphenyldicarboxaldehyde (BPDA-OH)

[0173] 4 -Bromo-2-hydroxybenzaldehyde (1.01 g, 5.0 mmol, 1.0 eq), (Bpin)2(1.27 g, 5.0 mmol, 1.0 eq), KOAc (1.47g, 15.0 mmol, 3.0 eq) and 1,4-dioxane (20 mL) were added to a 100 mL three-necked round bottomed flask equipped with a condenser. The flask was vacuumed and backfilled with Ar for 3 times. Pd(dppf)Cl2(109 mg, 0.15 mmol, 0.03 eq) was added. The flask was vacuumed and backfilled with Ar for 3 times. The resultant mixture was slirred at 80 °C for 16 hours. After this time, the mixture was cooled to room temperature. 4-Bromo-2-hydroxybenzaldehyde (1.01 g, 5.0 mmol, 1.0 eq), K2CO3 (1.38 g, 10 mmol, 2.0 eq), and H2O (4 mL) were added. The flask was vacuumed and backfilled with Ar for 3 times. Pd(dppf)C12 (109 mg, 0.15 mmol, 0.03 eq) was added. The flask was vacuumed and backfilled with Ar for 3 times. The resultant mixture was stirred at 80 °C for 16 hours. After cooled to room temperature, the mixture was concentrated by rotavapor to remove all volatile. The remaining mixture was added 10% NaOH to all solid dissolved and extracted with DCM (15 mL x 3). The aqueous phase was acidified with 37% HC1 to no new precipitate generated. The precipitate was collected by filtration to give the desired product as a pale yellow solid (1.15 g, 95% yield).JH NMR (60 MHz, CDCh): 5 (ppm) 11.06 (m, 2 H), 9.93 (m, 2 H), 7.58 (m, 4 H). The FTIR spectrum of BPDA-OH showed the expected peaks of phenol (-3300cm’1) and aldehyde (-1680cm’1). b) Synthesis of BPDA-OC6

[0174] 3,3’-Dihydroxy-4,4'-biphcnyldicarboxaldchydc (2.67 g, 11 mmol, 1 eq), 50 mL of DMF, and K2CO3 (4.56 g, 33 mmol, 3 eq) were added to a 250 mL round bottomed flask. The mixture was stirred at 80 °C for 10 min. 1-Bromohexane (3.40 mL, 24.2 mmol, 2.2 eq) in DMF (20 mL) was added dropwise at 80 °C in 1 hour. The resultant mixture was stirred at 80 °C for 16 hours. After cooling to room temperature, the mixture was poured into water (300 mL) and filtered. The filtrate cake was dissolved in ethyl acetate, dried with anhydrous Na2SC>4, filtered, and concentrated under reduced pressure to give the crude product, which was purified by column chromatography with hexanes / ethyl acetate (v / v from 10:1 to 3: 1) to give a still impure product as a yellow solid. This product was further purified by recrystallization from hexanes / ethyl acetate (10 / 1, v / v) to give the desired product as a white powder (3.0 g, 66% Yield). ’l l NMR (60 MHz, CDCL): 5 (ppm) 10.52 (m, 2 H), 7.83 (m, 2 H), 7.24 (m, 4 H), 4.15 (m, 4 H), 1.77 (m, 16 H), 1.52 (m, 6 H). The FTIR of BPDA-OCs showed the expected peaks of hexyl group (from 2800-3000cm’1) and aldehyde group (~1680cm’1).c) Synthesis of mCOF-999-2OH

[0175] This reaction produced an mCOF-999 with a mixture of linkers of BPDA-OH and BPDA-OC6. TCPB (338 mg, 0.800 mmol), BPDA-OH (96.8 mg, 0.400 mmol), and BPDA-OC6 (328 mg, 0.800 mmol) were added to a 30 mL glass vessel, followed by 10 mL of 1,2- dichlorobenzene and n-butanol (10 mL). The vessel was capped and heated at 80 °C until all solid was dissolved. CS2CO3 (1.56 g, 4.8 mmol, 2 eq) was added and the resultant mixture was sonicated at ambient temperature for 1 hour. After that time, the vessel was put into a 100 mL autoclave and heated at 120 °C for 4 hours. After cooling to room temperature, the mixture was filtered and washed thoroughly with H2O, methanol, ethyl acetate, and hexanes to give the desired product as a yellow powder. The N2 sorption isotherm of mCOF-999-2OH was measured at 77 K, giving a Brunaucr-Emmctt- Teller (BET) surface area of 920 m2g1. The PXRD pattern showed that mCOF-999-2OH was a crystalline material, with a prominent peak at 2theta = -2.4° which indicated the presence of the hexagonal pore structure. The FT1R spectrum showed the presence of cyano group (at -2250cm1) and hexyl group (from 2800-3000cm’1).d) Synthesis of mCOF-999-2O-PEI3

[0176] The attachment of PEI to the mCOF-999-2O sample was done by taking mCOF-999-2O (800 mg), 2-chloroethylamine hydrochloride (10 g, 86 mmol), and H2O (10 mL) and putting them into a 100 mL pressure vessel, followed by NaOII (6.88 g, 172 mmol) in II2O (10 mL). The pressure vessel was capped, and the resultant mixture was stirred at 100 °C for 4 hours. After cooling to room temperature, the mixture was filtered and washed thoroughly with H2O till the filtrate doesn’t change color after adding 5% CuSO4 solution. The filtrate cake reacted with 2-chloroethylamine hydrochloride again using the previous condition to give mCOF-999-2O- PEI2. mCOF-999-2O-PEI2 reacted with 2-chloroethylamine hydrochloride again using the previous condition. After cooling to room temperature, the mixture was filtered and washed thoroughly with H2O, MeOH, ethyl acetate, and hexanes to give the desired product (mCOF- 999-2O-PEI3) as a yellow solid. The PXRD pattern showed mCOF-999-2O-PEI3 was a semicrystalline material after PEI polymerization. The FTIR spectrum showed the presence of a cyano group (at -2250cm1), a hexyl group (from 2800-3000cm-1), and an ethylene group (~2820cm-1).

[0177] Under 400 ppm of CO2 without humidity, 25 °C, mCOF-999-2O-PEI3 exhibited a CO2 adsorption capacity of 0.7 mmol / g. It was measured through gas sorption isotherm measurement at 25 °C. From isotherm, we can get uptake for CO2 at 0.4 mbar (400 ppm, condition close to the CO2 partial pressure in air).Example 8: Synthesis of mCOF-999-2O-PPI3

[0178] mCOF-999-2O-PPI3 is synthesized as follows:wherein each R is -(CIDsCIL and each W is independently selected from <2, -NH(CH2)3NH2, and poly(propyleneimine). The synthesis of mCOF-999-2OH is described herein. The attachment of PPI to the mCOF-999-2OH sample was done by taking mCOF-999- 2OH (1.00 g), 3 -chloropropylamine hydrochloride (10.0 g, 76.9 mmol), and H2O (10 mL) and putting them into a 100 mL pressure vessel, followed by NaOH (6.15 g, 154 mmol) in H2O (10 mL). The pressure vessel was capped, and the resultant mixture was stirred at 100 °C for 10 hours. After cooling to room temperature, the mixture was filtered and washed thoroughly with H2O. The filtrate cake reacted with 3 -chloropropylamine hydrochloride again using the previous condition to give mCOF-999-2O-PPI2. mCOF-999-2O-PPI2 reacted with 3-chloropropylamine hydrochloride again using the previous condition. After cooling to room temperature, the mixture was filtered and washed thoroughly with H2O, MeOH, ethyl acetate, and hexanes to give the desired product (mCOF-999-2O-PPI3) as a yellow solid. The PXRD pattern showed mCOF-999-2O-PPI3 was a semi-crystalline material after PPI polymerization. The FTIR spectrum showed the presence of a cyano group (at -2220cm’1), a hexyl group (from 2800- 3000cm’1), and a propyl group (~2820cm’1).Example 9: Synthesis of mCOF-999-3O-PEIl a) Synthesis of mCOF-999-3OH

[0179] TCPB (339 mg, 0.800 mmol), BPDAH (145 mg, 0.600 mmol), and BPDA-C6 (246 mg, 0.600 mmol) were added to a 40 mL glass vial, followed by 10 mL of DCB and / / -butanol (10 mL). The vessel was capped and heated at 80 °C till all solid dissolved. CS2CO3 (1.56 g, 4.8 mmol, 2 eq) was added and the resultant mixture was sonicated at ambient temperature for 1 hour. After this time, the vessel was heated at 120 °C for 4 hours. After cooling to room temperature, the mixture was filtered and washed thoroughly with H2O, methanol, ethyl acetate, and hexanes to give the desired product as a yellow powder. The PXRD pattern showed mCOF- 999-3OH was a crystalline material, with a prominent peak at 2theta = -2.3° which indicated the presence of a hexagonal pore structure. The FTIR spectrum showed the presence of a cyano group (at ~2220cm-1) and hexyl group (from 2800-3000cm-1).b) Synthesis of mCOF-999-3O-PEIl

[0180] mCOF-999-3O-PEIl is synthesized as follows:wherein each R is -(CI LhCI L and each W is independently selected from, -NH(CH2)2NH2, and poly(ethylenimine). The attachment of PEI to the mCOF-999-3OH sample was done by taking mCOF-999-3OH (400 mg), 2-chloroethylamine hydrochloride (5.00 g, 43.1 mmol), and H2O (5 mL) and putting them into a 30 mL pressure vessel, followed by NaOH (3.5 g, 88 mmol) in H2O (5 mL). The pressure vessel was capped, and the resultant mixture was stirred at 100 °C for 10 hours. After cooling to room temperature, the mixture was filtered. The filter cake was washed with H2O ( 15 mL x 10) and methanol (15 mL x 3) and dried under reduced pressure to give mCOF-999-3O-PEIl as a yellow solid. The PXRD pattern showed mCOF-999-3O-PEIl was a semi-crystalline material after PEI polymerization. The FTIR spectrum showed the presence of a cyano group (at -2220cm1), a hexyl group (from 2800- 3000cm1), and an ethylene group (~2820cm-1).

[0181] The subject matter described herein was developed and the claimed invention was made by or on behalf of one or more parties to a joint research agreement, within the meaning of 35 U.S.C. 100(h) and § 1.9(e), that was in effect on or before the effective filing date of the claimed invention, and the claimed invention was made as a result of activities undertaken within the scope of the joint research agreement. The parties to the joint research agreement are Atoco, Inc. and The Regents of the University of California.

[0182] In at least some of the previously described embodiments, one or more elements used in an embodiment can interchangeably be used in another embodiment unless such a replacement is not technically feasible. It will be appreciated by those skilled in the art that various other omissions, additions and modifications may be made to the methods and structures described above without departing from the scope of the claimed subject matter. All such modifications and changes are intended to fall within the scope of the subject matter, as defined by the appended claims.

[0183] It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” etc.). It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases “at least one” and “one or more” to introduce claim recitations.However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles “a” or “an” limits any particular claim containing such introduced claim recitation to embodiments containing only one such recitation, even when the same claim includes the introductory phrases “one or more” or “at least one” and indefinite articles such as “a” or “an” (e.g., “a” and / or “an” should be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should be interpreted to mean at least the recited number (e.g., the bare recitation of “two recitations,” without other modifiers, means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to “at least one of A, B, and C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “a system having at least one of A, B, and C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). In those instances where a convention analogous to “at least one of A, B, or C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “ a system having at least one of A, B, or C” would include but not be limited to systems that have A alone, B alone, C alone, A andB together, A and C together, B and C together, and / or A, B, and C together, etc.). It will be further understood by those within the art that virtually any disjunctive word and / or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase “A or B” will be understood to include the possibilities of “A” or “B” or “A and B.”

[0184] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0185] As will be understood by one skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible sub-ranges and combinations of sub-ranges thereof. 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, tenths, etc. 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,” and the like include the number recited and refer to ranges which can be subsequently broken down into sub-ranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. Thus, for example, a group having 1-3 articles refers to groups having 1, 2, or 3 articles. Similarly, a group having 1-5 articles refers to groups having 1, 2, 3, 4, or 5 articles, and so forth.

[0186] Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it is readily apparent to those of ordinary skill in the art in light of the teachings of this invention that certain changes and modifications may be made thereto without departing from the spirit or scope of the appended claims.

[0187] Accordingly, the preceding merely illustrates the principles of the invention. It will be appreciated that those skilled in the art will be able to devise various arrangements which, although not explicitly described or shown herein, embody the principles of the invention and are included within its spirit and scope. Furthermore, all examples and conditional language recited herein are principally intended to aid the reader in understanding the principles of the invention and the concepts contributed by the inventors to furthering the art, and are to be construed as being without limitation to such specifically recited examples and conditions.Moreover, all statements herein reciting principles, aspects, and embodiments of the invention as well as specific examples thereof, are intended to encompass both structural and functional equivalents thereof. Additionally, it is intended that such equivalents include both currently known equivalents and equivalents developed in the future, i.e., any elements developed that perform the same function, regardless of structure. Moreover, nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims.

[0188] The scope of the present invention, therefore, is not intended to be limited to the exemplary embodiments shown and described herein. Rather, the scope and spirit of present invention is embodied by the appended claims. In the claims, 35 U.S.C. § 112(f) or 35 U.S.C. §112(6) is expressly defined as being invoked for a limitation in the claim only when the exact phrase "means for" or the exact phrase "step for" is recited at the beginning of such limitation in the claim; if such exact phrase is not used in a limitation in the claim, then 35 U.S.C. § 112 (f) or 35 U.S.C. §112(6) is not invoked.

Claims

CLAIMS:

1. A covalent organic framework (COF) comprising a structure according to Formula (I):each X is independently selected fromwherein each n is an integer independently selected from 0 to 12; and when n is an integer from 1 to 12, each W is independently selected from H, halogen, ethylene glycol, poly(ethylene glycol), methyl, C2-C6 linear alkyl, C3-C6 branched alkyl,NH2J HCH2J0H, -NH(CH2)2NH2, poly(ethylenimine), -NH(CH(CH3))2NH2, poly(methyl(ethylenimine)), -NH(C(CHJ)2)2NH2, poly(dimethyl(ethylenimine)), -NH(CH2)3NH2, poly(propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en-l -amine, poly(but-3-en-l- amine), 4-aminostyrene, and poly(4-aminostyrene); and when n is 0, each W is independently selected from ethylene glycol, polyethylene glycol), methyl, C2-C6 linear alkyl, C3-C6 branched alkyl, -(CH2)2NH2, poly(ethylenimine), -(CH(CH3))2NH2, poly(methyl(ethylenimine)), -(C(CH3)2)2NH2, poly(dimethyl(ethylenimine)), -(CFhhNHz, poly (propyleneimine), lysine, poly-lysine, allylamine, poly(allylamine), but-3-en- 1-amine, poly(but-3-en-l-amine), 4-aminostyrene, and poly(4-aminostyrene), wherein, for at least one X in Formula (I) and not more than the number of Xs inFormula (I) minus one, W is independently selected from H, halogen, ethylene glycol, poly(ethylene glycol), methyl, C2-C6 linear alkyl, or C3-C6 branched alkyl; and q is 1, 2, 3, or 4, or a salt thereof.

3. The COF of claim 1 or 2, wherein4. The COF of a preceding claim, wherein5. The COF of a preceding claim, wherein6. The COF of a preceding claim, wherein q is 1 or 2.

7. The COF of a preceding claim, wherein8. The COF of a preceding claim, wherein each X is9. The COF of a preceding claim, wherein each X is independently selected from-poly(ethylenimine).

10. The COF of claim 9, whereinthe 4 of the X are each independently -O-(CH2)2NH2or -O-poly(ethylenimine).

11. The COF of claim 9, whereinf the X are; and the2 of the X are each independently -O-(CH2)2NH2or -O-poly(ethylenimine).

12. The COF of claims 1-11, configured for carbon dioxide capture.

13. The COF of claims 1-11, configured for carbon dioxide capture and separation, including direct air capture from ambient air and post-combustion capture from natural gas or flue gas.

14. The COF of claims 1-11, contained in a matrix configured as a sorption bed, fluidized bed, coated heat exchanger, or membrane.

15. The COF of claims 1-11, contained in a matrix configured as a sorption bed, fluidized bed, coated heat exchanger, or membrane, in a fluid flow path configured to pass the air or mixture over, around and / or through the matrix.

16. The COF of claim 15, comprising an air or post-combustion exhaust gas mixture, wherein water is present in the air or mixture, and the material is configured and is operative to harvest the water from the air or mixture, and provides facile collection of water as a second valuedelivering function.

17. A system for capturing carbon dioxide from air or a post-combustion exhaust gas mixture comprising a matrix, such as a sorption bed containing the COF of claims 1-11, configured as a solid adsorbent for capturing the carbon dioxide, and optionally water, from the air or mixture.

18. A method comprising using the COF of claims 1-11 as a solid adsorbent for capturing carbon dioxide, and optionally water, from air or a post-combustion exhaust gas mixture.

19. A method of using the COF of claims 1-11 for carbon dioxide capture and / or separation, especially from air or flue gas.

20. A method of synthesizing the COF according to claims 9-11, wherein the method is essentially free of azide.

21. A method of synthesizing the COF according to claims 9-11, wherein the method is essentially free of aziridine.

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