Ordered and modifiable type graphitic materials based on covalent organic frameworks

Abstract

Embodiments of the present disclosure generally relate to covalent organic frameworks and to methods of forming covalent organic frameworks. In one embodiment, a composition includes a first two-dimensional covalent organic framework (COF) having an aromatic backbone defining at least one hexagonal pore with either a continuous aromatic ring comprising carbon and hydrogen or the pore defined by a ring of 6 subunits totaling more than 36 and less than 63 rings, and the first two-dimensional covalent organic framework is configured to be functionalized with a variety of functional groups.

Description

ORDERED AND MODIFIABLE TYPE GRAPHITIC MATERIALS BASED ON COVALENT ORGANIC FRAMEWORKSGOVERNMENT RIGHTS

[0001] This invention was made with government support under DMR-2118592 awarded by the National Science Foundation. The government has certain rights in the invention.FIELD

[0002] Embodiments of the present disclosure generally relate to covalent organic frameworks and to methods of forming covalent organic frameworks.BACKGROUND

[0003] The past decade has seen an explosion of interest in two-dimensional (2D) materials beginning with the demonstration of the properties of graphene, and has been extended to other 2D materials, such as transition metal dichalcogenides, nanoplatelets, and other elemental 2D phases (germanene, silicene, etc.). The promise of 2D materials is largely based on their unique single-layer electrical, optical, and magnetic properties. However, current 2D materials are not easily modified to suit a given application. That is, there is very little flexibility in adjusting the materials performance beyond their intrinsic properties. This rigidity and lack of adaptability presents significant barriers to technological implementation and broad use. Attempts have been made to achieve this goal by modifying graphene. For example, a top down approach using ion bombardment, etching, or oxidation, produces graphene oxide (GO) with pores containing a high degree of poly dispersity in both size and density. These randomly- produced pores start to overlap when produced at high density producing both larger openings and weakening the material. In fact, variations in the degree of oxidation caused by differences in starting materials (principally the graphite source) or oxidation protocol can cause substantial variation in the structure and properties of the material. As a result, permeation (flux) through GO membranes remains insufficient to technically compete with current commercial pressure-driven membranes. Thischallenging task of creating atomically precise nanopores, without destroying the material itself, has thus remained elusive. More recently, a bottom-up synthesis of a nanoporous “graphene” was reported, providing a material with ordered nanopores while maintaining the integrity of the graphene. Although this bottom-up strategy proved to be successful in the monolayer regime, the nine-step synthesis provides only nanogram quantities and failed to produce a material capable of pore functionalization. Metal organic framework (MOF) materials have also been investigated for membrane production. However, MOF materials suffer from their 3D structures where membranes have to be fabricated with grains of the MOF materials and species can diffuse in the spaces between grains rather than through the porous structure. A 2D material can naturally produce a membrane without this possibility via the natural stacking of the 2D grains as in GO where the size selection has been attributed to the tortuous diffusion path between the layers. These ordered and completely engineered pores might have great efficacy across multiple applications, including high performance separations.

[0004] Covalent organic frameworks (COFs) produced to-date have a high degree of crystallinity and order within the plane associated with covalent bonds therethrough, yet the interlayer forces have often relied on lower energy attractions. As a result, stacks of such layers can begin to have variable properties in use environments that disrupt these lower energy attractions.

[0005] Therefore, there is a need for covalent organic frameworks and to methods of forming covalent organic frameworks that have, for example, interlayer covalent bonds. There is also a need for devices inclusive of such materials to provide synthetically adjustable electronic conductivity, gas transport ability, catalyst binding, or ion transport properties.SUMMARY

[0006] Embodiments of the present disclosure generally relate to covalent organic frameworks (COFs) and to methods of forming COFs. Unlike conventional technologies, COFs described herein can have a highly ordered nanopore structure and can have the ability to selectively incorporate functionality within those pores. Embodiments described herein can, for example, be amenable to interlayer crosslinking to provide superimposed pores. COF materials described herein can be synthesized using targeted organic synthesis to produce a range of new functional, two- dimensional (2D) graphitic type materials with a unique combination of properties, such as electronic conductivity, filtration properties, gas transport abilities, catalyst binding properties, ion transport properties, or combinations thereof, among other properties.

[0007] In an embodiment, a composition is provided. The composition includes a first two-dimensional covalent organic framework (COF) having an aromatic backbone defining at least one hexagonal pore with either a continuous aromatic ring composed only of carbon and hydrogen or the pore defined by a ring of 6 subunits totaling more than 36 and less than 63 rings, and the first two-dimensional covalent organic framework is configured to be functionalized with a variety of functional groups.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

[0009] So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only exemplary embodiments and are therefore not to be considered limiting of its scope, may admit to other equally effective embodiments.

[0010] FIG. 1 A is an example reaction scheme in which a triamine is reacted with a benzaldehyde derivative to produce triazacoronenes (Type 1) according to at least one embodiment of the present disclosure.

[0011] FIG. IB is an example reaction scheme in which a triamine is reacted with ortho-hydroxy benzaldehydes, to produce pyrano derivatives by displacement of a methoxy group by the hydroxy unit of the benzaldehyde (Type 2) according to at least one embodiment of the present disclosure.

[0012] FIG. 2 is an example reaction scheme in which a dialdehyde is utilized to form COFs via the Type 1 protocol according to at least one embodiment of the present disclosure.

[0013] FIGS. 3A-3B is an example reaction scheme in which 2,5- dihydroxyterephthaldehyde is converted into a pyrano compound via the Type 2 protocol followed by a condensation to yield an exemplary five-pore COF according to at least one embodiment of the present disclosure.

[0014] FIG. 3C is a space filling model of an example Type 2 COF that is similar to graphene oxide in that the backbone is aromatic carbon-rich complete rings yet has a highly ordered nanopore structure and the ability to selectively incorporate functionality within those pores according to at least one embodiment of the present disclosure.

[0015] FIG. 4A is an example reaction scheme illustrating the use of a substituted triamine to form a COF according to at least one embodiment of the present disclosure.

[0016] FIG. 4B is an example reaction scheme in which a substituted COF can be utilized to form a variety of differently functionalized COFs according to at least one embodiment of the present disclosure.

[0017] FIG. 5A is an example reaction scheme illustrating the use of a substituted aromatic aldehyde to form a COF according to at least one embodiment of the present disclosure.

[0018] FIG. 5B is an example reaction scheme in which a substituted COF can be utilized to form a variety of differently functionalized COFs according to at least one embodiment of the present disclosure.

[0019] FIG. 6 is an example reaction scheme that use alternate between hydroxy and substituted amines where P is various functional groups to produce a COF with the formation of two different functional groups within the pore: the OR group and the second being the variable moiety P (not phosphorus atom) according to at least one embodiment of the present disclosure.

[0020] FIG. 7 is an example reaction scheme in which Type 1 COFs of FIG. 1 A are cross-linked using monomers such as 2,5-allyloxydihydroxyterephthalaldehde to incorporate allyl groups into the COF layer that can subsequently be cross-metathesizedto produce cross-linked COFs between superimposed layers according to at least one embodiment of the present disclosure.

[0021] FIG. 8 is an example reaction scheme in which 2,2'-bipyridine (BIPY) dialdehydes and 1,4,8,9-tetra-aza-triphenylene (TATP)-type compounds are incorporated into a COF and that will coordinate metals according to at least one embodiment of the present disclosure. The resulting COF can also be used to crosslink superimposed layers of COFs according to at least one embodiment of the present disclosure.

[0022] FIG. 9 shows an illustration of cross-linked superimposed layers of COFs formed from the COF of FIG. 8 according to at least one embodiment of the present disclosure.

[0023] FIG. 10 is a selected area electron diffraction (SAED) pattern of the COF produced in Example 1 collected using a transmission electron microscope.

[0024] FIG. 11 A shows a proton nuclear magnetic resonance (JH NMR) spectrum of 2,5-diformylterephthalic acid tautomers in dimethyl sulfoxide-de (DMSO-de).

[0025] FIG. 11B shows aJH NMR spectrum of 2,5-diformylterephthalic acid monoaldehyde monomer in chloroform-d (CDCh).

[0026] FIG. 12A shows an infrared (IR) spectrum of 2,5-diformylterephthalic acid.

[0027] FIG. 13 A shows aJH NMR spectrum of 2-nitroterephthaldehyde.

[0028] FIG. 13B shows an expanded region of the1H NMR spectrum of FIG. 13 A.

[0029] FIG. 14A shows a Carbon- 13 nuclear magnetic resonance (13C NMR) spectrum of 2-nitroterephthaldehyde in CDCh.

[0030] FIG. 14B shows an IR spectrum of 2-nitroterephthaldehyde.

[0031] Figures included herein illustrate various embodiments of the disclosure. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.DETAILED DESCRIPTION

[0032] Embodiments of the present disclosure generally relate to covalent organic frameworks and to methods of forming covalent organic frameworks. Embodiments of the present disclosure provide novel covalent organic frameworks (COFs) that are similar to graphene (or graphene oxide) but with highly ordered nanopores. Here, thebackbone of the COFs is almost entirely composed of carbon like graphene or graphene oxide. In contrast to graphene or graphene oxide, the COFs described herein can have a highly ordered nanopore structure and can have the ability to selectively incorporate functionality within those pores. Embodiments described herein also provide methods for the formation of the COFs.

[0033] The use of headings is for purposes of convenience only and does not limit the scope of the present disclosure. Embodiments described herein can be combined with other embodiments.

[0034] As used herein, a “composition” can include component(s) of the composition, reaction product(s) of two or more components of the composition, a remainder balance of remaining starting component(s), or combinations thereof. Compositions of the present disclosure can be prepared by any suitable mixing process.

[0035] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to make and use embodiments of the present disclosure, and are not intended to limit the scope of embodiments of the present disclosure. Efforts have been made to ensure accuracy with respect to numbers used but some experimental errors and deviations should be accounted for.Examples

[0036] According to the present disclosure, a polycyclic aromatic triamine 101 can be reacted with, for example, a benzaldehyde or an ortho-hydroxybenzaldehyde as shown in FIGS. 1A (reaction scheme 100) and IB (reaction scheme 150), respectively. While the polycyclic aromatic triamine operative herein as shown in FIGS. 1A and IB based on a triphenylene core that includes an amine adjacent to a bay region of the core, other polycyclic aromatic triamines operative herein are based on a core that includes an amine adjacent to a bay region. As used herein, a bay region is defined as an indent between the aromatic rings of the core. Examples of bay regions are shown in FIG. 1A. Illustrative, but non-limiting, examples of polycyclic aromatic triamines can include triamines based on (or having a core of) triphenylene, picene, dibenzo[a,e]pyrene, 9,10- diphenylanthrenece, benzo[b]fluoranthene, or combinations thereof, among others.

[0037] The polycyclic aromatic triamine core can be further functionalized such that at least one hydrogen atom of the core is substituted with an unsubstituted hydrocarbyl, a substituted hydrocarbyl, or a functional group comprising at least one element from Group 13-17 of the periodic table of the elements. As shown in FIG. 1 A, the polycyclic aromatic amine is functionalized with a methoxy (-OMe) group. However, other alkoxy groups and other functional groups used instead of, or in addition to, alkoxy groups are contemplated.

[0038] For example, and as shown in FIG. 2, each R of Formula (I) can be, independently, hydrogen, an unsubstituted hydrocarbyl, a substituted hydrocarbyl, or a functional group comprising at least one element from Group 13-17 of the periodic table of the elements. Each R of Formula (I) can be the same or different.

[0039] R of Formula (I) can have, independently, any suitable number of carbon atoms such as from 1 to 40 carbon atoms, such as from 2 to 32 carbon atoms, such as from 4 to 28 carbon atoms, such as from 6 to 24 carbon atoms, such as from 8 to 18 carbon atoms or from 8 to 24 carbon atoms, such as from 10 to 16 carbon atoms, such as from 12 to 14 carbon atoms, or from 8 to 40 carbon atoms, such as from 10 to 30 carbon atoms, such as from 12 to 24 carbon atoms, such as from 14 to 22 carbon atoms. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. In some embodiments, the number of carbon atoms in each R of Formula (I) can be, independently, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40. Each of the foregoing numbers can be preceded by the word “about,” “at least about,” “less than about,” or “more than about,” and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.

[0040] Each R of Formula (I) can be, independently, linear or branched, saturated or unsaturated (for example, at least one C=C double bond), cyclic or acyclic, aromatic or not aromatic. Regarding saturation, each R of Formula (I) can be, independently, fully saturated, partially unsaturated, or fully unsaturated.

[0041] Each R of Formula (I) can be, independently, an unsubstituted hydrocarbyl. An “unsubstituted hydrocarbyl” refers to a group that consists of hydrogen and carbon atoms only. Non-limiting examples of unsubstituted hydrocarbyl include an alkylgroup having from 1 to 40 carbon atoms such as n-butyl, iso-butyl, sec-butyl, and tertbutyl, pentyl, hexyl, heptyl, octyl, ethyl-2-hexyl, isooctyl, nonyl, n-decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, or isomers thereof.

[0042] In some embodiments, each R of Formula (I) can be, independently, a substituted hydrocarbyl. A “substituted hydrocarbyl” refers to an unsubstituted hydrocarbyl in which at least one hydrogen of the unsubstituted hydrocarbyl has been substituted with at least one heteroatom or heteroatom-containing group, such as one or more elements from Group 13-17 of the periodic table of the elements, such as halogen (F, Cl, Br, or I), O, N, Se, Te, P, As, Sb, S, B, Si, Ge, Sn, Pb, and the like, such as C(O)R*, C(O)NR*2, C(O)OR*, NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, SOx (where x = 2 or 3), BR*2, SiR*3, GeR*3, SnR*3, PbR*3, and the like, where R* is, independently, hydrogen or unsubstituted hydrocarbyl, or where at least one heteroatom has been inserted within the unsubstituted hydrocarbyl.

[0043] As used herein, reference to an R group, alkyl, substituted alkyl, hydrocarbyl, substituted hydrocarbyl, aromatic, or compound name without specifying a particular isomer (such as butyl) expressly discloses all isomers (such as n-butyl, isobutyl, sec-butyl, and tert-butyl). For example, reference to an R group having 3 or more carbon atoms expressly discloses all isomers thereof. When a compound is described herein such that a particular isomer, enantiomer or diastereomer of the compound is not specified, for example, in a formula or in a chemical name, that description is intended to include each isomer and enantiomer of the compound described individual or in any combination.

[0044] Any suitable polycyclic aromatic triamine described herein can be utilized for reactions described herein. For example, the polycyclic aromatic triamine of Formula (VII- A) can be utilized with any suitable aromatic aldehyde described herein. Any suitable aromatic aldehyde described herein can be utilized for reactions described herein. Embodiments may be combined with other embodiments.

[0045] Any suitable aromatic aldehyde, such as an aromatic monoaldehyde, an aromatic dialdehyde, an aromatic trialdehyde, or combinations thereof, can be utilized for inventive reactions described herein (for example, as shown in FIGS. 1A, IB, and2). By changing the aromatic aldehyde, a higher density or lower density of carbon framework can be incorporated into the resulting COF along with modification of the pore size. Furthermore, the aromatic aldehydes can include various functional groups (such as hydroxyl, halogen, among others) that can be utilized to further modify the pores of the COFs. These aromatic aldehydes operative herein can include one or more of the following structures represented by formulas (I-A)-(I-O):

[0046] In various structures described herein, CHO refers to an aldehyde functional groupwhere the wavy bond represents the connection to the aromatic aldehyde.

[0047] In some embodiments, the aromatic aldehyde comprises one or more of the following structures represented by formulas (I-Al)-(I-Ol):

[0048] H in each of formulas (I-Al)-(I-Ol) is a hydrogen atom on the aromatic ring(s); R in each of formulas (I-Al)-(I-Ol) is a group substituted for a hydrogen atom on the aromatic ring(s); and when x is more than 1, each R group is the same or different.

[0049] In Formula (I-Al), x is from 1-5 and x+y=6.

[0050] In Formula (I-B 1), x is from 1-8 and x+y=8.

[0051] In Formula (I-C 1 ), x is from 1-8 and x+y=8.

[0052] In Formula (I-Dl), x is from 1-15 and x+y=15.

[0053] In Formula (I-El), x is from 1-4 and x+y=4.

[0054] In Formula (I-F 1), x is from 1-4 and x+y=4.

[0055] In Formula (I-Gl), x is from 1-12 and x+y=12.

[0056] In Formula (I-Hl), x is from 1-2 and x+y=2.

[0057] In Formula (I-Il), x is from 1-3 and x+y=3.

[0058] In Formula (I-Jl), x is from 1-2 and x+y=2.

[0059] In Formula (I-Kl), x is from 1-2 and x+y=2.

[0060] In Formula (I-L 1 ), x is from 1-4 and x+y=4.

[0061] In Formula (I-Ml), x is from 1-3 and x+y=3.

[0062] In Formula (I-Nl), x is from 1-4 and x+y=4.

[0063] In Formula (1-01), x is from 1-5 and x+y=5.

[0064] Embodiments of the present disclosure also generally relate to a novel class of graphene-like two-dimensional covalent organic framework (COF) polymers. The graphene-like two-dimensional COF polymers described herein can have a highly stable, photoactive, semi-conducting aromatic backbone with intrinsically and exactly ordered nanometer sized pores. Unlike conventional technologies, COFs described herein can be functionalized with a variety of functional groups.

[0065] In the Type 1 case shown in the reaction scheme 100 of FIG. 1A, polycyclic aromatic triamine 101 can be reacted with a benzaldehyde 103 (or derivative thereof) to form a tri azacoronene 105 via, for example, a Pictet-Spengler reaction. Suitable Pictet-Spengler reaction conditions are known. In another variation, the Type 2 case shown in FIG. IB, polycyclic aromatic triamine 101 can be reacted with an orthohydroxybenzaldehyde 107 (or derivative thereof), to form a pyrano-type compound 109 through displacement of a methoxy group by the hydroxy unit of the benzaldehyde.

[0066] FIG. 2 is an example reaction scheme 200 in which a dialdehyde (in this example, terephthalaldehde 201) is converted to a tri azacoronene of Formula (II) via the Type 1 protocol followed by condensation to form a single-pore COF of Formula (III) according to at least one embodiment of the present disclosure. Here, use of the dialdehyde (in this example, terephthalaldehde 201) can enable polymerization via both aldehyde moieties. A multi-pore COF 205 (structure not shown) can then be formed from the single-pore COF of Formula (III). Each R group in Formula (II) and Formula (III) can be, independently, any suitable R group such as those R groups described above for Formula (I). The single-pore COF of Formula (III) and multi-pore COF 205 can be referred to as COF polymers. The pore of the single-pore COF of Formula (III) is shown in FIG. 2. The pore can be defined by 6 subunits. One subunit is shown in blue in FIG. 2 and the remaining five subunits are shown in black.

[0067] To the inventors’ knowledge, this is the first report of the structures of Formula (II), Formula (III), and COF 205. Derivatives and variations of both the triamine and the aldehyde are proposed in which a variety of functional groups can be used to alter the pores of the COF. Such derivatives and variations can include functional groups that can be neutral, positively charged species, or negatively charged species depending on the environment.

[0068] Referring back to the COF of Formula (III), the aldehyde moieties present on the phenyl rings can enable polymerization by a condensation reaction (for example, self-polymerization or self-condensation) to form a COF 205 which is a multi-pore COF. Similarly, COF 205 can further polymerize through the aldehyde moieties.

[0069] FIGS. 3A-3B is an example reaction scheme 300 in which 2,5- dihydroxyterephthaldehyde 301 is converted into a pyrano compound of Formula (IV) via the Type 2 protocol followed by a condensation to yield an exemplary five-pore COF of Formula (VI) according to at least one embodiment of the present disclosure. The five-pore COF of Formula (VI) illustrates the graphene-like nature of the materials in that, for example, the backbone with either a continuous aromatic ring composed only of carbon and hydrogen or in other embodiments a pore defined by a ring of 6 subunits totaling more than 36 and less than 63 rings as shown in FIG. 2. One difference between the COFs described herein and graphene oxide is the highly ordered nanopore structure and the ability to selectively incorporate functionality within the pores. A space filling model 350 of an example Type 2 COF showing the graphitic nature is shown in FIG. 3C. The space filling model 350 shows the seven aromatic rings which make up the core of Formula (II).

[0070] The single-pore COF of Formula (V) is also shown in the reaction scheme. Although Formula (VI) shows the R group to be methyl (Me), it should be understood that any R group can be utilized. Each R group in Formula (IV), Formula (V), and Formula (VI) can be, independently, any suitable R group such as those R groups described above for Formula (I).

[0071] Referring back to Formula (V), the aldehyde moieties enable polymerization by a condensation reaction (for example, self-polymerization or self-condensation) to form the multi-pore COF of Formula (VI). Similarly, the multi-pore COF of Formula (VI) can further polymerize through the aldehyde moieties.

[0072] In some embodiments is provided a highly ordered COF with ionizable carboxylate groups and a pore size of about 5 nm to 25 nm. Such a COF can enable high membrane selectivity to only conduct cations smaller than a precise pore size threshold. Additionally, related example membrane materials can be synthesized to either increase or reduce this pore size threshold and / or to make anionic selective membranes (for example, ionizable amines).

[0073] These 2D-COF materials can be utilized to achieve the goal of a modifiable, highly ordered material and can be synthesized in a bottom-up approach, thereby providing both a stable aromatic backbone. The COF materials having functionalized pores can be formed from starting materials bearing desired functional groups that extend into the pore areas of the final COF material. Additionally, or alternatively, the COF materials can be formed by first forming the backbone and then replacing the moieties that extend into the pore areas with substituted moieties so as to modify pore properties. Such replacement chemistry is known and includes, for example, coupling reactions. Substituted moieties operative herein illustratively include halogens, amines, hydroxyls, carboxyls, peptides, ammoniums, oniums, alkanes, alkenes, silanes, sulfonyls, and phosphates. It is appreciated that with resort to chiral substituted moieties that chiral selectively is imparted to an example membrane.

[0074] FIG. 4A is an example reaction scheme 400 illustrating the use of a substituted triamine represented by Formula (VII-A) in reaction with an aromatic aldehyde (in this example, 2,5-dihydroxyterephthaldehyde 301) to form a COF according to at least one embodiment of the present disclosure. In FIG. 4A, each X of Formula (VII-A) can be, independently, hydrogen, a halogen (for example, F, Cl, Br, or I), or other functional group that can be replaced by a different functional group after the synthesis of the COF of Formula (VIII). In Formula (VIII), the wavy bonds indicate connections to remaining portions of the COF polymer similar to that shown in FIG. 3B such that a multi-pore COF can be formed. FIG. 4A also shows an example intermediate (or conversion product) that is formed during the polymerization or condensation to produce the COF of Formula (VIII). This example intermediate (or conversion product) has a structure represented by Formula (VII-B).

[0075] In some examples, each X is bromine (Br), such that the molecule represented by Formula (VII-A) is 2,3,6,7,10,11 -hexabromotriphenylene- 1, 5,9- triamine. In other embodiments, each X is chlorine (Cl), such that the molecule represented by Formula (VII-A) is 2,3,6,7,10,11 -hexachlorotriphenylene- 1, 5,9- tri amine.

[0076] The halogen atoms or other functional group represented by X in Formula (VIII) can be subsequently substituted after COF formation with a variety of different functional groups (illustrated as R1in the COF of Formula (IX)) as shown in theexample reaction scheme 450 of FIG. 4B. Each R1group in Formula (IX), can be, independently, any suitable R1group such as those R groups described above for Formula (I). In Formula (IX), the wavy bonds indicate connections to remaining portions of the COF polymer similar to that shown in FIG. 3B such that a multi-pore COF can be formed. It is contemplated that other polycyclic aromatic triamines substituted with a halogen or other functional group are contemplated. Such polycyclic aromatic triamines can include a core that includes an amine adjacent to a bay region. Illustrative, but non-limiting, examples of substituted polycyclic aromatic triamines can include triamines based on (or having a core of) triphenylene, picene, dibenzo[a,e]pyrene, 9,10-diphenylanthrenece, benzofb] fluoranthene, or combinations thereof, among others. It is also contemplated that other aromatic aldehydes can be used such as those represented by formulas (I-A)-(I-K). In some embodiments, for example, substitutions can be symmetric through a mirror plane of the base di- or trialdehyde.

[0077] FIG. 5A is an example reaction scheme 500 illustrating the use of a substituted aromatic aldehyde 303 in reaction with a substituted triamine of Formula (I) to form a COF according to at least one embodiment of the present disclosure. In FIG. 5A, each X1of aromatic aldehyde 303 can be, independently, hydrogen, a halogen (for example, F, Cl, Br, or I), or other functional group that can be replaced by a different functional group after the synthesis of the COF of Formula (X-A). In Formula (X-A), the wavy bonds indicate connections to remaining portions of the COF polymer similar to that shown in FIG. 3B such that a multi-pore COF can be formed. FIG. 5A also shows an example intermediate (or conversion product) that is formed during the polymerization or condensation to produce the COF of Formula (X-A). This example intermediate (or conversion product) has a structure represented by Formula (X-B).

[0078] In some examples, each X1is Br, such that the molecule represented by aromatic aldehyde 303 is 2,5-dibromo-3,6-dihydroxyterephthalaldehyde. In other embodiments, each X1is Cl, such that the molecule represented by aromatic aldehyde 303 is 2,5-dichloro-3,6-dihydroxyterephthalaldehyde. These and other disubstituted dihydroxyl aromatic aldehydes represent another class of aldehydes that can be utilized to form a variety of new COFs.

[0079] The halogen atoms or other functional group represented by X1in aromatic aldehyde 303 can be subsequently substituted after COF formation with a variety of different functional groups (illustrated as R2in the COF of Formula (XI)) as shown in the example reaction scheme 550 of FIG. 5B. Each R2group in Formula (XI), can be, independently, any suitable R2group such as those R groups described above for Formula (I). In Formula (XI), the wavy bonds indicate connections to remaining portions of the COF polymer similar to that shown in FIG. 3B such that a multi-pore COF can be formed. It is contemplated that other polycyclic aromatic triamines are contemplated. Such polycyclic aromatic triamines can include a core that includes an amine adjacent to a bay region. Illustrative, but non-limiting, examples of polycyclic aromatic triamines can include triamines based on (or having a core of) triphenylene, picene, dibenzo[a,e]pyrene, 9,10-diphenylanthrenece, benzo[b]fluoranthene, or combinations thereof, among others. It is also contemplated that other aromatic aldehydes substituted with a halogen or other functional group can be used such as aromatic aldehydes having a core represented by formulas (I-A)-(I-K). In some embodiments, for example, substitutions can be symmetric through a mirror plane of the base di- or tri-aldehyde.

[0080] Each COF of Formula (X-A) and the COF of Formula (XI) includes at least two different functional groups that extend within the pore — a first functional group which is the original alkoxy group (-OR) and a second functional group represented by X1or R2. As shown, the X1(which may be a halogen) is readily substituted before or after COF formation through various reactions using, for example, Grignard reagents, organolithiums, thiols, cyanates, imides, nitriles, metal catalyzed reagents, or combinations thereof, among others.

[0081] It is contemplated that any suitable aromatic aldehyde, aromatic dialdehyde, aromatic trialdehydes, or combinations thereof can be utilized. Such aldehydes can be substituted with various functional groups, such as hydroxyl, halogen, amino (e.g., substituted amines), allyl, or combinations thereof, among other functional groups. An example of an aromatic aldehyde substituted with an amine is shown in FIG. 6, where “P” in aromatic aldehyde 305 denotes a functional moiety attached to an amino nitrogen of the aldehyde. In reaction scheme 600, aromatic aldehyde 305 and polycyclic aromatic triamine 304 are reacted (e.g., condensed) to form a pyridine-type COF 309analogous to the pyrano derivatives described above with respect to the Type 2 COF. “P” in COF 309 can be amenable to subsequent reaction modification. As shown in FIG. 6, each pore of the COF 309 includes two different functional groups — an OR group and an amine with a variable P moiety (not phosphorous atom).

[0082] FIG. 7 is an example reaction scheme 700 in which Type 1 COFs of FIG. 1A are cross-linked using monomers such as allylic functionalized aromatic aldehydes (for example, 2,5-bis(allyloxy)terephthalaldehyde 701). The allylic functionalized aromatic aldehyde incorporates allyl groups into the resulting COF layers 703a, 703b (either single pore COF or multi-pore COF). These allyl groups of COF layers 703a, 703b can be subsequently cross-metathesized under any suitable reaction conditions 705 to produce cross-linked COFs having superimposed layers as shown in the COF of Formula (XII). By cross-linking the 2D COF layers (or sheets), the pores of each COF layer can form a channel. In some examples, cross-linking to form channels can be accomplished by only a small level of cross-linking (approximately 5%).

[0083] Such cross-linking of the two dimensional (2D) COF sheets represents an additional variation in which COFs described herein can be modified. Cross-metathesis can be performed using any suitable reaction conditions 705 and any suitable catalysts such as Grubbs ruthenium catalysts. As such, Type 1 COFs can be readily cross-linked using, for example, allyl-functionalized monomers.

[0084] FIG. 8 is an example reaction scheme 800 in which a 2,2'-bipyridine (BIPY) dialdehyde 803 and a TATP-type compound 801 are reacted under conditions 805 to form a COF 807 that will coordinate metals. The BIPY ligands that coordinate metals can enable cross-linking of two or more layers (for example, layer 901 and layer 902) to produce cross-linked COFs having superimposed layers as shown in COF 900. By cross-linking the 2D COF layers (or sheets), the pores of each COF layer can form a channel.

[0085] Each R group of compound 801 can be, independently, any suitable R group such as those R groups described above for Formula (I).

[0086] With respect to aldehyde 803, M refers to any suitable metal, such as a those metals of Group 3 to Group 12 of the periodic table of the elements; L refers to a ligand; and x is an integer that refers to the number of ligands. Each M of aldehyde 803 can be the same or different and each L of aldehyde 803 can be the same or different.

[0087] For COF 807, M refers to any suitable metal, such as a those metals of Group 3 to Group 12 of the periodic table of the elements, L refers to a ligand, and x is an integer that refers to the number of ligands. Each M of COF 807 can be the same or different and each L of COF 807 can be the same or different. The dashed bonds shown in COF 807 indicate connections to remaining portions of the COF such that a multipore COF polymer layer (or sheet) can be formed.

[0088] A net effect of interlayer COF cross-linking as described herein (for example, with respect to FIGS. 7 and 8) is to form a stable three-dimensional structure with controlled positioning between pores in various layers. While crosslinking is depicted herein as being between two COFs, it is appreciated that the reactions detailed herein can be extended to create extended three-dimensional structures with any suitable number of layers such as 2, 3, 4, 5, 10, 20, 50 layers, or more. It is further appreciated that cross-linked layers can vary in at least one property such as pore size, pore electronegativity, chelated species in the pore, or combinations thereof, among other properties.

[0089] In some embodiments, COFs described herein can be selectively reacted with a cap species to selectively close a pore. In instances when the cap species is a precious metal or contaminating metal present in low concentrations such as radioactive contaminants, an example membrane serves as a cap species accumulator.

[0090] COFs described herein can enable a variety of uses and afford advantages relative to conventional materials. By way of example, some illustrative, but nonlimiting, uses are illustrated below:(a) Chemically selective membranes

[0091] COFs described herein can be utilized in chemically selective membranes. The ability to functionalize the nanopores of the COF structures described herein can allow for tailoring for transporting a specific chemical species. In fuel cells, redox flow batteries, electrolyzers and desalinization systems the selective transport of ions determines both the efficiency and cost of these devices. The special ability of the fluorocarbon polymer Nafion (Chemours) and related proton transport membranes is utilized in most advanced fuels cells. However, the cost of this fluorocarbon polymer is a major factor in the overall cost of these devices. Since both the size and thechemical composition of the COFs described herein can be rationally modified, membranes can be formed from such COFs that are specific to a particular ion.

[0092] For example, the nanopores of a COF can be functionalized with sulfonic acid groups, carboxylic acid groups, phosphate groups, or combinations thereof, among others that can be negatively charged in certain environments. Such negatively charged groups can enable charge and / or size selective transport. Here, a COF having negatively charged groups can be proton specific if the pore is small, or specific for larger cations if the pore is larger. As another example, the nanopores of a COF can be functionalized with amines, alkylamines, or combinations thereof, among others that can be positively charged in certain environments. Such positively charged groups can provide charge and / or size selective transport of anions. In some embodiments, functionalization of the COF nanopores with protonated ammonium cationic groups can result in a COF that can be utilized for charge and / or size selective transport of anions that is advantageous is advantageous in redox flow batteries since the crossover of transition metal cations, the preferred redox couples in these batteries, is one of the big issues in improving their efficiency and cycle life. With selective ion transport of a cation and anion, a bipolar membrane can then be constructed by layering the two or more 2D materials and in some embodiments cross-linking the two or more 2D layers together. Since the membrane materials themselves can be semiconducting, application of a potential to the two sides of the membrane, to drive the respective semiconductors into accumulation, can be utilized, thereby making obsolete the external anode and cathode used in conventional bipolar membrane devices.(b) Battery electrodes

[0093] COFs described herein can be utilized as battery electrodes or can form at least a portion of a battery electrode. The ability to construct specific sized and functionalized pores for redox couples such as lithium and sodium in a highly conducting scaffold addresses the current problems of charging cycle life decay due to morphological changes in a battery electrodes, regardless of whether an anode or a cathode. The rigid 2D structure and high stability of embodiments of COFs described herein can be utilized to overcome this longstanding challenge. Although the pure example materials can be semiconducting, reduction of cations used in batteries suchas lithium can be utilized to transform the example COF materials into a conductor by putting electrons into the conduction band and inserting the metal into the pores of the COF.(c) Sensors

[0094] COFs described herein can be utilized as sensors or can form at least a portion of a sensor. The combination of tunable chemical sensitivity of the pores and semiconducting properties makes the example materials attractive as chemical sensors and also useful for field-effect transistor (FET) based sensors. Such measurements can be combined with the ion selective membrane measurements but done on single or multiple layers of the synthesized 2D COF materials on a Si / SiC>2 substrate with e-beam lithography deposited source and drain electrodes as done on g-C2N. Most conventional FET sensors operate with only a monolayer of chemical functionality to influence the current flow. In contrast, the COFs described herein have chemical functionality incorporated throughout the bulk of the COF material and so single layers would not be required. Additionally, or alternatively, molecular tags can be utilized. By binding specific molecular tags to one or more rings that define a pore of the COF, the semiconducting properties of the COF can change to a detectable level when the molecular tag in turn binds a target species. A molecular tag operative herein can include an affinity tag, an epitope tag, a spectroscopic tag, or combinations thereof, among others.(d) Heterogeneous catalysis and electrocatalysis

[0095] COFs described herein can be utilized for heterogeneous catalysis and electrocatalysis. For example, COFs of the present disclosure can be utilized as a heterogeneous catalyst support. Here, the binding of catalytically active metal atoms in the functionalized nanopores of the COF can produce identical catalytic sites, unlike most conventional supported catalysts which are characterized as having polydispersity in the metal clusters.

[0096] Of interest in catalysis are “two nanopore” systems where two nanopores can be designed to bind several different metals that each perform a separate role in a catalytic reaction such as substrate binding, electron transfer, or proton transfer. Theconducting nature of COFs described herein can allow them to be used directly as electrocatalytic electrodes in fuel cell or electrolysis cells that utilize multistep electronproton coupled reactions that usually use a carbon support that for small metal clusters of active metals such as Pt.

[0097] Use of COFs described herein in these non-limiting applications can improve future energy technologies that significantly impact society.ExperimentalExample 1

[0098] In a glass microwave vial with a microwave specific stir bar, triaminetriphenylhexamethoxy (100 mg, 0.22 mmol, 1 eq) with anhydrous dimethylformamide (DMF, 4 mL) was added. The mixture was stirred in open air for 30 seconds, then dihydroxyterepthaldehyde (54 mg, 0.33 mmol, 1.5 eq) and 120 pL triflic acid were added. The resulting mixture was then microwaved for 2 h at 200°C, cooled for 30 min, ppt with water, and filtered using a fine frit filter washing with excess water and ethanol. The black solid product was placed in a Soxhlet extractor and extracted with water and ethanol for 12 hours each, then dried using supercritical CO2. The crystallinity was determined to be ordered pore structure and was confirmed by SAED using a transmission electron microscope as shown in FIG. 10.Example 2: Synthesis of Selected MonomersExample 2-1 : Synthesis of 2,5-diformylterephthalic acid (I-H)

[0099] It is noted that 2,5-diformylterephthalic acid exists in three tautomeric forms: I-H(a), I-H(b), and I-H(c). In an oven dried Parr reaction bottle equipped with a gas regulator, 2,5-dibromoterephthaldehyde (1.60 g, 5.40 mmol), Pd(OAc)2 (61 mg,0.27 mmol), and Xantphos (317 mg, 0.55 mmol) were dissolved in dry THF (50 ml) under an argon atmosphere. The reaction mixture was flushed with carbon monoxide (CO), and then distilled water (4 mL) and tri ethylamine (EtsN, 3.2 ml) were added to the reaction mixture. The Parr bottle was then purged with CO via three fill-release cycles to a final pressure of 80 psi. The reaction was stirred for 22 h at 80°C, cooled to room temperature and vented, and the solution was transferred to a round bottom flask. The solvent was removed under vacuum to provide a red solid, which was suspended in 75 ml water and basified to a pH of 10-11 with 2M sodium hydroxide (NaOH). The aqueous layer was washed with di chloromethane (CH2CI2, 3 x 75 ml) to remove yellow-colored impurities. The aqueous layer was then acidified to pH 2 with 6M hydrochloric acid (HC1) producing a colorless solution. The aqueous layer was extracted with ethyla acetate (EtOAc, 3 x 100 ml), dried over sodium sulfate (Na2SO4) and evaporated on a rotary evaporator. The solid was further dried under high vacuum to give 2,5-diformylterephthalic acid I-H, which was used as isolated (930 mg, 78% yield).1H NMR in DMSO-de displayed a mixture of I-H(a) and I-H(b), while in CDCI3 only I-H(b).

[0100] JHNMR of I-H(b) in CDCI3: 5 10.45 (s, 1H), 8.41 (s, 1H) 7.97 (s, 1H), 6.66 (s, 1H) 3.75 (s, 1H, OH), COOH resonance not observed.1H NMR of I-H(a) in DMSO- de: 5 8.46 (brs, 2H, OH), 8.08 (s, 2H, Ar-H), 6.80 (brs, 2H, CH acetal); Xb 5 10.52 (s, 1H, COOH), 10.29 (s, 1H, CHO), 8.46 (brs, 1H, OH), 8.18 (s, 1H, Ar-H), 8.14 (s, 1H, Ar-H), 6.75 (brs, 1H, CH acetal). IR: 3393, 3047, 1746, 1686, 1614 cm1. (MALDI- TOF) m / z: calculated for CioHeOe [M - H] 221.0086; observed 221.0694.

[0101] FIG. HA shows the 'H NMR spectrum of 2,5-diformylterephthalic acid tautomers in DMSO-de, FIG. 11B shows the 'H NMR spectrum of 2,5- diformylterephthalic acid monoaldehyde monomer in CDCI3, and FIG. 12 shows the infrared (IR) spectrum of 2,5-diformylterephthalic acid.Example 2-2: Synthesis of 2-nitroterephthaldehyde (I-I)

[0102] In a round bottom flask, terephthaldehyde (1.00 g, 7.45 mmol) and sulfuric acid (H2SO4, 6.0 mL) were cooled to 0°C in an ice bath, stirring until all the terephthaldehyde had dissolved. A solution of nitric acid (HNO3, 2 mL) and H2SO4 (2 mL) was added dropwise and then the mixture was heated to 50°C for 1 h. The mixture was cooled to room temperature, poured into ice water and extracted with EtOAc (3 x 100 mL). The combined organic phases were washed with saturated aqueous sodium bicarbonate (NaHCCh, 6 * 100 mL) until the aqueous layer was colorless. The organic layer was washed with water (l x 200 mL) then brine (l x 200 mL) and dried over magnesium sulfate (MgSCh). Evaporation of the solvent gave 2-nitroterephthaldehyde (I-I) as a yellow solid (1.08 g, 81% yield) that was used as obtained. 2- nitroterephthaldehyde (I-I) was characterized as follows: 'H NMR (CDCI3): 5 10.51 (s, 1H), 10.20 (s, 1H), 8.64 (d, 1H, J = 1Hz), 8.30 (dd, 1H, J = 1 & 8Hz), 8.14 (d, 1H, J = 8Hz).13C NMR (CDCI3): 5189.0, 187.4, 149.8, 139.6, 135.0, 134.4, 130.8, 125.1. IR: 2867, 1690, 1528, 1351, 1181, 795, 751 cm4.

[0103] FIG. 13A shows a 'H NMR spectrum of 2-nitroterephthaldehyde, FIG. 13B shows an expanded region of theJH NMR spectrum of FIG. 13A, FIG. 14A shows the13C NMR spectrum of 2-nitroterephthaldehyde in CDCI3, and FIG. 14B shows an IR spectrum of 2-nitroterephthaldehyde.Example 2-3: Synthesis of 2-bromo-6-nitroterephthalaldehyde (I-J)

[0104] In a round bottom flask, 2-nitroterephthaldehyde (I-I) (89.8 mg, 0.500 mmol) was suspended in sulfuric acid (1.0 mL) and 1, 3 -dibromo5, 5 -dimethylhydantoin (215 mg, 1.50 mmol) was added as a solid at room temperature. The mixture was stirred for 24 h at room temperature, then poured into water and filtered, and washing the solid with water. Drying gave 2-bromo-6-nitroterephthalaldehyde (I-J) as a yellow solid (97.0 mg, 75% yield) that was used as obtained. 2-bromo-6-nitroterephthalaldehyde (I-J) was characterized as follows: ’H NMR (CDCh): 5 10.33 (s, 1H), 10.11 (s, 1H), 8.55 (s, 1H), 8.44 (s, 1H).Example 2-4: Synthesis of 2,5-diformyl-3-nitrobenzoic acid (I-K)

[0105] It is noted that 2,5-diformyl-3-nitrobenzoic acid exists in two tautomeric forms: I-K(a) and I-K(b). In an oven dried Parr reaction bottle equipped with a gas regulator, 2,5-dibromoterephthaldehyde (1.60 g, 5.40 mmol), Pd(OAc)2 (61 mg, 0.27 mmol), and Xantphos (317 mg, 0.55 mmol) were dissolved in dry THF (50 ml) under an argon atmosphere. The reaction mixture was flushed with carbon monoxide (CO), and then distilled water (4 mL) and tri ethylamine (EtsN, 3.2 ml) were added to the reaction mixture. The Parr bottle was then purged with CO via three fill-release cycles to a final pressure of 80 psi. The reaction was stirred for 22 h at 80°C, cooled to roomtemperature and vented, and the solution was transferred to a round bottom flask. The solvent was removed under vacuum to provide a red solid, which was suspended in 75 ml water and basified to a pH of 10-11 with 2M sodium hydroxide (NaOH). The aqueous layer was washed with di chloromethane (CH2CI2, 3 x 75 ml) to remove yellow-colored impurities. The aqueous layer was then acidified to pH 2 with 6M hydrochloric acid (HC1) producing a colorless solution. The aqueous layer was extracted with ethyla acetate (EtOAc, 3 x 100 ml), dried over sodium sulfate (Na2SC>4) and evaporated on a rotary evaporator. The solid was further dried under high vacuum to give 2,5-diformyl-3-nitrobenzoic acid I-K, which was used as isolated.

[0106] Embodiments of the present disclosure generally relate to COFs and to methods of forming COFs. Unlike conventional technologies, COFs described herein can have a highly ordered nanopore structure and can have the ability to selectively incorporate functionality within those pores. Embodiments described herein can, for example, be amenable to interlayer cross linking to provide superimposed pores. COFs described herein can be 2D graphitic-type materials with a unique combination of properties, such as electronic conductivity, filtration properties, gas transport abilities, catalyst binding properties, ion transport properties, or combinations thereof, among other properties.EMBODIMENTS LISTING:

[0107] The present disclosure provides, among others, the following embodiments, each of which can be considered as optionally including any alternate embodiments:

[0108] Clause 1 : A composition, comprising: a first two-dimensional covalent organic framework (COF) having an aromatic backbone defining at least one hexagonal pore with either a continuous aromatic ring composed only of carbon and hydrogen or the pore defined by a ring of 6 subunits totaling more than 36 and less than 63 rings, wherein the first two-dimensional covalent organic framework is configured to be functionalized with a variety of functional groups.

[0109] Clause 2: The composition of Clause 1, wherein the aromatic backbone is semi-conducting.

[0110] Clause 3 : The composition of Clause 1 or Clause 2, wherein the at least one pore has a diameter that is from about 5 nm to about 25 nm.[OHl] Clause 4: The composition of any one of Clauses 1-3, wherein a hydrogen atom of the COF is substituted with an unsubstituted hydrocarbyl, a substituted hydrocarbyl, or a functional group comprising at least one element from Group 13-17 of the periodic table of the elements.

[0112] Clause 5: The composition of any one of Clauses 1-4, wherein a hydrogen atom of the COF is substituted with an alkoxy moiety having the formula -OR, where R is a Ci-Ce alkyl, Ci-Ce ester, or Ci-Ce amide.

[0113] Clause 6: The composition of any one of Clauses 1-5, wherein a hydrogen atom of the COF is substituted with a halogen, amine, hydroxyl, carboxyl, peptide, alkanyl, alkenyl, silane, sulfonyl, phosphate, or combinations thereof.

[0114] Clause 7: The composition of any one of Clauses 1-6, wherein a hydrogen atom of the COF is substituted with an ionizable functional group, or a hydrogen atom of the COF is substituted with a functional group that alters the at least one pore, the functional group comprising a neutral species, a positively charged species, a negatively charged species, or combinations thereof.

[0115] Clause 8: The composition of any one of Clauses 1-7, wherein a hydrogen atom of the COF is substituted with an ammonium, onium, or combinations thereof.

[0116] Clause 9: The composition of any one of Clauses 1-8, further comprising a metal ion chelated in the at least one pore.

[0117] Clause 10: The composition of any one of Clauses 1-9, further comprising a second two-dimensional covalent organic framework cross-linked to the first two- dimensional covalent organic framework by a cross-linker.

[0118] Clause 11 : The composition of claim 10, wherein the cross-linker is derived fromwherein:M is a metal;L is a ligand;x is the number of ligands; and when x is greater than 1, each L is the same or different.

[0119] Clause 12: A method of forming the composition of any one of Clauses 1- 11, the method comprising: reacting a polycyclic aromatic triamine with an aromatic aldehyde to form a conversion product and reacting the conversion product by polymerization or selfcondensation to form the COF.

[0120] Clause 13: The method of Clause 12 wherein the polycyclic aromatic triamine comprises core structure comprising triphenylene, picene, dibenzo[a,e]pyrene, 9,10-diphenylanthrenece, or benzo[b]fluoranthene; and three hydrogen atoms of the core structure are substituted with an amine.

[0121] Clause 14: The method of Clause 12 or Clause 13, wherein a hydrogen atom of the polycyclic aromatic triamine is substituted with an unsubstituted hydrocarbyl, a substituted hydrocarbyl, or a functional group comprising at least one element from Group 13-17 of the periodic table of the elements.

[0122] Clause 15: The method of any one of Clauses 12-14, wherein at least one hydrogen atom of the polycyclic aromatic triamine is substituted with an alkoxy (-OR*) group; R* is a C1-C20 unsubstituted hydrocarbyl or a C1-C20 substituted hydrocarbyl; and when more than one hydrogen atom is substituted with the alkoxy (-OR*) group, each R* is the same or different.

[0123] Clause 16: The method of Clause 15, wherein the alkoxy group is a methoxy (-OMe) group.

[0124] Clause 17: The method of any one of Clauses 12-16, wherein at least one hydrogen atom of the polycyclic aromatic triamine is substituted with a halogen.

[0125] Clause 18: The method of any one of Clauses 12-16, wherein the polycyclic aromatic triamine is hexahalogenated.

[0126] Clause 19: The method of any one of Clause 12-17, wherein a hydrogen atom of the aromatic aldehyde is substituted with an unsubstituted hydrocarbyl, a substituted hydrocarbyl, or a functional group comprising at least one element from Group 13-17 of the periodic table of the elements.

[0127] Clause 20: The method of any one of Clauses 12-19, wherein a hydrogen atom of the aromatic aldehyde is substituted with a hydroxy, alkoxy, halogen, carboxy, amine, or nitro.

[0128] Clause 21 : The method of any one of Clause 12-20, wherein the aromatic aldehyde comprises an aromatic dialdehyde, an aromatic trialdehyde, or combinations thereof.

[0129] Clause 22: The method of any one of Clauses 12-21, wherein the aromatic aldehyde comprises one or more of:wherein:H in each of formulas (I-Al)-(I-Ol) is a hydrogen atom on the aromatic ring(s);R in each of formulas (I-Al)-(I-Ol) is a group substituted for a hydrogen atom on the aromatic ring(s); x in each of formulas (I-Al)-(I-Ol) is the number of R groups; y in each of formulas (I-Al)-(I-Ol) is the number of hydrogen atoms; and when x is more than 1, each R group is the same or different.

[0130] Clause 23: The method of any one of Clauses 12-22, wherein each R of formulas (I-Al)-(I-Ol) is, independently, an unsubstituted hydrocarbyl, a substituted hydrocarbyl, or a functional group comprising at least one element from Group 13-17 of the periodic table of the elements.

[0131] Clause 24: The method of any one of Clauses 12-23, wherein each R of formulas (I-Al)-(I-Ol) is, independently, hydroxy (-OH), alkoxy (-OR*), halogen (F, Cl, Br, or I), carboxy (-CO2H), amine (NH2), alkylamine (NR*2), or nitro (-NO2); R* is a C1-C20 unsubstituted hydrocarbyl or a C1-C20 substituted hydrocarbyl; and each R* is the same or different.

[0132] Clause 25: The method of any one of Clauses 12-24, wherein each R is independently, a Cl -CIO unsubstituted hydrocarbyl or a Cl -CIO substituted hydrocarbyl.

[0133] Clause 26: The method of any one of Clauses 12-25, wherein the aromatic aldehyde comprises at least two bromine atoms.

[0134] Clause 27: A device, comprising: the composition of any one of Clauses 1- 11.

[0135] Clause 28: The device of Clause 27, wherein the device is a chemically selective membrane, a battery electrode, a sensor, a heterogeneous catalyst, or an electrocatalyst.

[0136] Clause 29: A use of the composition of any one of Clauses 1-8 in a device.

[0137] Clause 30: A composition, comprising: a polymer derived from a monomer represented by one or more of:Formula (XIII) wherein: each R of Formula (II), Formula (IV), Formula (X-B), or Formula (XIII) is, independently, hydrogen, an unsubstituted hydrocarbyl, a substituted hydrocarbyl, or a functional group comprising at least one element from Group 13-17 of the periodic table of the elements; each X and X1of Formula (VII-B) and Formula (X-B) is, independently, hydrogen or a halogen; and each P of Formula (XIII) is, independently, hydrogen, an unsubstituted hydrocarbyl, a substituted hydrocarbyl, or a functional group comprising at least one element from Group 13-17 of the periodic table of the elements.

[0138] In the foregoing, reference is made to embodiments of the disclosure. However, it should be understood that the disclosure is not limited to specific described embodiments. Instead, any combination of the following features and elements, whether related to different embodiments or not, is contemplated to implement and practice the disclosure. Furthermore, although embodiments of the disclosure may achieve advantages over other possible solutions and / or over the prior art, whether or not a particular advantage is achieved by a given embodiment is not limiting of the disclosure. Thus, the foregoing aspects, features, embodiments and advantages are merely illustrative and are not considered elements or limitations of the appended claims except where explicitly recited in a claim(s). Likewise, reference to “the disclosure” shall not be construed as a generalization of any inventive subject matterdisclosed herein and shall not be considered to be an element or limitation of the appended claims except where explicitly recited in a claim(s).

[0139] As is apparent from the foregoing general description and the specific aspects, while forms of the aspects have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including.” Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “Is” preceding the recitation of the composition, element, or elements and vice versa, such as the terms “comprising,” “consisting essentially of,” “consisting of’ also include the product of the combinations of elements listed after the term.

[0140] References cited herein are incorporated by reference herein in their entirety to indicate the state of the art as of their publication or filing date and it is intended that this information can be employed herein, if needed, to exclude specific embodiments that are in the prior art.

[0141] For purposes of this present disclosure, and unless otherwise specified, all numerical values within the detailed description and the claims herein are modified by “about” or “approximately” the indicated value, and consider experimental error and variations that would be expected by a person having ordinary skill in the art. For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. For example, the recitation of the numerical range 1 to 5 includes the subranges 1 to 4, 1.5 to 4.5, 1 to 2, among other subranges. As another example, the recitation of the numerical ranges 1 to 5, such as 2 to 4, includes the subranges 1 to 4 and 2 to 5, among other subranges. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Forexample, the recitation of the numerical range 1 to 5 includes the numbers 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, among other numbers. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

[0142] As used herein, the indefinite article “a” or “an” shall mean “at least one” unless specified to the contrary or the context clearly indicates otherwise. For example, embodiments comprising “an aldehyde” include embodiments comprising one, two, or more aldehydes, unless specified to the contrary or the context clearly indicates only one aldehyde is included.

[0143] While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

ClaimsWhat is claimed is:

1. A composition, comprising: a first two-dimensional covalent organic framework (COF) having an aromatic backbone defining at least one hexagonal pore with either a continuous aromatic ring comprising carbon and hydrogen or the pore defined by a ring of 6 subunits totaling more than 36 and less than 63 rings, wherein the first two-dimensional covalent organic framework is configured to be functionalized with a variety of functional groups.

2. The composition of claim 1, wherein the aromatic backbone is semi-conducting.

3. The composition of claim 1, wherein the at least one pore has a diameter that is from about 5 nm to about 25 nm.

4. The composition of claim 1, wherein a hydrogen atom of the COF is substituted with an unsubstituted hydrocarbyl, a substituted hydrocarbyl, or a functional group comprising at least one element from Group 13-17 of the periodic table of the elements5. The composition of claim 1, wherein a hydrogen atom of the COF is substituted with an alkoxy moiety having the formula -OR, where R is a Ci-Ce alkyl, Ci-Ce ester, or Ci-Ce amide.

6. The composition of any one of claims 1-5, wherein a hydrogen atom of the COF is substituted with a halogen, amine, hydroxyl, carboxyl, peptide, alkanyl, alkenyl, silane, sulfonyl, phosphate, or combinations thereof.

7. The composition of claim 1, wherein: a hydrogen atom of the COF is substituted with an ionizable functional group; or a hydrogen atom of the COF is substituted with a functional group that alters the at least one pore, the functional group comprising a neutral species, a positively charged species, a negatively charged species, or combinations thereof.

8. The composition of claim 1, wherein a hydrogen atom of the COF is substituted with an ammonium, onium, or combinations thereof.

9. The composition of claims 1, further comprising: a metal ion chelated in the at least one pore.

10. The composition claim 1, further comprising a second two-dimensional covalent organic framework cross-linked to the first two-dimensional covalent organic framework by a cross-linker.

11. The composition of claim 10, wherein the cross-linker is derived fromwherein:M is a metal;L is a ligand; x is the number of ligands; and when x is greater than 1, each L is the same or different.

12. A method of forming the composition of claim 1, the method comprising: reacting a polycyclic aromatic triamine with an aromatic aldehyde to form a conversion product; and reacting the conversion product by polymerization or self-condensation to form the COF.

13. The method of claim 12, wherein: the polycyclic aromatic triamine comprises core structure comprising triphenylene, picene, dibenzo[a,e]pyrene, 9,10-diphenylanthrenece, or benzo [b] fluoranthene; andthree hydrogen atoms of the core structure are substituted with an amine.

14. The method of claim 12, wherein a hydrogen atom of the polycyclic aromatic triamine is substituted with an unsubstituted hydrocarbyl, a substituted hydrocarbyl, or a functional group comprising at least one element from Group 13-17 of the periodic table of the elements.

15. The method of claim 12, wherein: at least one hydrogen atom of the polycyclic aromatic triamine is substituted with an alkoxy (-OR*) group;R* is a C1-C20 unsubstituted hydrocarbyl or a C1-C20 substituted hydrocarbyl; and when more than one hydrogen atom is substituted with the alkoxy (-OR*) group, each R* is the same or different.

16. The method of claim 12, wherein at least one hydrogen atom of the polycyclic aromatic triamine is substituted with a halogen.

17. The method of claim 12, wherein the aromatic aldehyde comprises an aromatic dialdehyde, an aromatic trialdehyde, or combinations thereof.

18. The method of claim 12, wherein the aromatic aldehyde comprises one or more of:wherein:H in each of formulas (I-Al)-(I-Ol) is a hydrogen atom on the aromatic ring(s);R in each of formulas (I-Al)-(I-Ol) is a group substituted for a hydrogen atom on the aromatic ring(s); x in each of formulas (I-Al)-(I-Ol) is the number of R groups; y in each of formulas (I-Al)-(I-Ol) is the number of hydrogen atoms; and when x is more than 1, each R group is the same or different.

19. The method of claim 18, wherein each R of formulas (I-Al)-(I-Ol) is, independently, an unsubstituted hydrocarbyl, a substituted hydrocarbyl, or a functional group comprising at least one element from Group 13-17 of the periodic table of the elements.

20. The method of claim 19, wherein: each R of formulas (I-Al)-(I-Ol) is, independently, hydroxy (-OH), alkoxy (- OR*), halogen (F, Cl, Br, or I), carboxy (-CO2H), amine (NH2), alkylamine (NR*2), or nitro (-NO2);R* is a C1-C20 unsubstituted hydrocarbyl or a C1-C20 substituted hydrocarbyl; and each R* is the same or different.

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