Comprehensive Study on Mutual Interplay of Multiple V‑Shaped Ligands on the Helical Nature of a Series of Coordination Polymers and Their Properties

Abstract

V-shaped ligands are commonly used for helical coordination polymer synthesis. However, employment of multiple V-shaped ligands does not always lead to a helical network. The mutual interplay of two V-shaped ligands, which is neither easily predictable nor well documented, plays a major role directing the self-assembly of the resultant network. We report here the construction of a series of novel coordination polymers {[Ni­(OBA)­(H<sub>2</sub>MDP)­(H<sub>2</sub>O)]·(DMF)<sub>3</sub>}<sub><i>n</i></sub> (<b>1</b>),{[Ni­(FBA)­(H<sub>2</sub>MDP)]·(H<sub>2</sub>O)<sub>3</sub>·(DMF)}<sub><i>n</i></sub> (<b>2</b>),{[Ni<sub>2</sub>(IPA)<sub>2</sub>(H<sub>2</sub>MDP)<sub>2</sub>(H<sub>2</sub>O)]·(H<sub>2</sub>O)­(DMF)}<sub><i>n</i></sub> (<b>3</b>),{[Ni­(ADA)­(H2MDP)]·(MeOH)}<sub><i>n</i></sub> (<b>4</b>),[Ni­(TNBA)­(H<sub>2</sub>MDP)<sub>2</sub>]<sub><i>n</i></sub> (<b>5</b>), {[Ni­(PPA)­(H<sub>2</sub>MDP)<sub>2</sub>]·(H<sub>2</sub>O)<sub>2</sub>}<sub><i>n</i></sub> (<b>6</b>), {[Ni­(HDPA)<sub>2</sub>(H<sub>2</sub>MDP)<sub>2</sub>]}<sub><i>n</i></sub> (<b>7</b>), and [Ni­(SBA)­(H<sub>2</sub>MDP)]<sub><i>n</i></sub> (<b>8</b>) {where H<sub>2</sub>OBA = 4,4′<b>-</b>oxybis­(benzoic acid), H<sub>2</sub>FBA = 4,4′-(hexafluoroisopropylidene)­bis­(benzoic acid), H<sub>2</sub>IPA = isophthalic acid, H<sub>2</sub>ADA =1,3-adamantanediacetic acid, H<sub>2</sub>TNBA = 5,5′-dithiobis­(2-nitrobenzoic acid), H<sub>2</sub>PPA 1,4-phenylenedipropionic acid, H<sub>2</sub>DPA = diphenic acid H<sub>2</sub>SBA= 4,4′-sulfonyldibenzoic acid} using a combination of mixed V-shaped ligands. The deployment of bent ligands yields a rich variety of network topologies with various helical motifs comprising both the linkers and the individual one. A detailed gas sorption study of porous networks, as evident from the presence of distinct nanoporous voids and channels inside the structures, is also investigated. Furthermore, chirality associated with helical networks and their role as potential functional materials are verified by solid state circular dichroism spectra

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