Semiconductive and proton-conductive porous hydrogen-bonded frameworks
A hydrogen bonded organic framework (HOF) includes at least one kind of organic linker with at least one functional group forming a hydrogen-bonded network, the functional group includes a hydroxyl group and a central atom of tetrahedral geometry, the HOF is semi-conductive, proton-conductive and porous, and can even be microporous. In some embodiments, the at least one functional group is phosphonic acid, phosphinic acid, arsonic acids, arsinic acids, phosphonate, arsonate and/or esters thereof including at least one hydroxyl group. A covalent organic framework (COF), is also provided based on an HOF for transforming the hydrogen bonds between the functional groups into covalent anhydride bonds via a condensation reaction or reactions known to form anhydrides.
1 . A hydrogen-bonded organic framework (HOF) comprising at least one organic linker with at least one functional group forming a hydrogen-bonded network,
wherein the at least one functional group comprises a hydroxyl group and a central atom of tetrahedral geometry, and
wherein the HOF is semi-conductive, proton-conductive and porous.
2 . The HOF according to claim 1 , wherein the central atom of the at least one functional group is selected from the group consisting of phosphorus (P), arsenic (As), antimony (Sb), silicon (Si), selenium (Se) and bismuth (Bi).
3 . The HOF according to claim 2 , wherein the at least one functional group of the at least one organic linker is selected from the group consisting of phosphonic acid, phosphinic acid, arsonic acids, arsenic acids, phosphonate, arsonate and/or esters thereof with at least one hydroxyl group.
4 . The HOF according to claim 1 , wherein the at least one organic linker is V-shaped, L-shaped, T-shaped, X-shaped, X-shaped tetrahedral, Y-shaped, star-shaped, linear or hexagonal geometrical core enabling a formation of void channels.
5 . The HOF according to claim 1 , wherein the at least one organic linker comprises porphyrin or phthalocyanine as a geometrical core.
6 . The HOF according to claim 1 , wherein the hydrogen-bonded network of the at least one functional group of the at least one organic linker forms one-dimensional hydrogen-bonded chains and/or two-dimensional hydrogen-bonded sheets.
7 . The HOF according to claim 1 , wherein the at least one organic linker forms two-dimensional hydrogen-bonded sheets, wherein the sheets assemble in multiple layers.
8 . The HOF according to claim 1 , wherein the at least one organic linker comprises at least two organic linkers of different structures.
9 . The HOF according to claim 1 , wherein the at least one organic linker comprises phenylphosphonic acid and/or 5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin (H 8 -TPPA).
10 . The HOF according to claim 1 , wherein the HOF consists of H 8 -TPPA and optionally phenylphosphonic acid.
11 . The HOF according to claim 1 , wherein the at least one functional group of the at least one organic linker forms one, two and/or three hydrogen bonds with each other.
12 . The HOF according to claim 1 , wherein the HOF has a band gap of between about ~0 eV and about ~4.0 eV.
13 . An electrode material comprising a proton exchange fuel cell having membrane material comprising the HOF according to claim 1 intermediate between a first layer generating either electron-hole pairs or excitons and a layer for separate extraction of differently charged carriers produced in the first layer to an external circuit.
14 . A covalent organic framework (COF), characterized in that it has been generated from the HOF according to claim 1 , by transforming the hydrogen bonds between the at least one functional group into covalent anhydride bonds via a condensation reaction or reactions known to form anhydrides.
15 . A method of synthetizing the HOF according to claim 1 , by combining the at least one organic linker of the HOF in a solution, wherein
the solution comprises a solvent;
and the solution is incubated at about 80° C.
16 . The HOF according to claim 5 , wherein the geometrical core comprises a bound metal, or a transition metal.
17 . The HOF according to claim 16 , wherein the bound metal is at least one of iron (Fe), palladium (Pd), zinc (Zn), copper (Cu), or nickel (Ni).
18 . The HOF according to claim 6 , wherein the at least one functional group also forms isolated hydrogen bonded clusters.
19 . The HOF according to claim 7 , wherein the hydrogen-bonded network extends in the two-dimensional hydrogen-bonded sheets and/or between the multiple layers.
20 . The HOF according to claim 8 , wherein the at least two organic linkers of different structures comprise identical functional groups.