Structural diversity in tetrakis(4-pyridyl)porphyrin supramolecular building blocks
Abstract
In memory of a pioneer in crystal engineering, Prof. Israel Goldberg, we report a series of new framework solids, based on the ligand tetrakis(4–pyridyl)porphyrin (TPyP). Spontaneous reactions of TPyP with seven different metal salts under liquid-liquid diffusion at ambient temperature show that the formation of ionic compounds is preferred to coordination polymers due to increased conformational freedom. Two coordination networks, {(HgI2)2(TPyP)}n·4nCHCl3∙2nTCE (TCE = 1,1,2,2–tetrachloroethane), and {(Ba(μ1,1–NCS)(μ1,1,3–NCS)(H2O)(MeCN))2(TPyP)}n·4nH2O, displayed a new isomeric form of the known [(HgI2)2(TPyP)]∞ polymeric motif, and a two-dimensional honeycomb polymeric motif linked by hydrogen-bonding into a three dimensional moganite (mog) net, respectively. Four protonated porphyrinic salts, [H3TPyP][PF6]3∙0.5TCE, [H2TPyP][I3]2·2MeOH, [H4TPyP][UO2Cl4]2·6MeCN, and [H4TPyP][Th(NO3)6][NO3]2, were observed which hydrogen bond to give one- or two-dimensional networks, or in the case of [H4TPyP][UO2Cl4]2·6MeCN, a discrete dinuclear hydrogen-bonded complex. In one case, a neutral, hydrogen-bonded complex, Ce(NO3)3(MeOH)3(H2O)·TPyP·TCE·H2O, was formed which adopts a three-dimensional, self-penetrated variant of the face-centered cubic (fcc) network. These new structures represent hybrid organic-inorganic crystalline compounds in which the multidentate porphyrin units, having both hydrogen bonding, as well as coordination functionalities, are interlinked through the inorganic connectors into self-assembled three-dimensional architectures. This work shows the relative stability of noncovalently bound vs. coordination networks as well as the effective potential of the TPyP building block to construct supramolecular assemblies in the presence or absence of coordinating ions as linkers.
Citation
Mishra , M K , Choudhary , H , Cordes , D B , Kelley , S & Rogers , R 2019 , ' Structural diversity in tetrakis(4-pyridyl)porphyrin supramolecular building blocks ' , Crystal Growth & Design , vol. 19 , no. 6 , pp. 3529-3542 . https://doi.org/10.1021/acs.cgd.9b00399
Publication
Crystal Growth & Design
Status
Peer reviewed
ISSN
1528-7483Type
Journal article
Rights
Copyright © 2019 American Chemical Society. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1021/acs.cgd.9b00399
Description
The authors would like to thank the University of Alabama Department of Chemistry and the University of Missouri-Columbia Department of Chemistry for support of this work.Collections
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