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Issue 21, 2020
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Solid-state 1D → 3D transformation of polynitrile-based coordination polymers by dehydration reaction

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Abstract

In crystal structures of two chain coordination polymers [M(tcnopr3OH)2(H2O)2] (M = NiII and CoII; tcnopr3OH = [(NC)2CC(O(CH2)3OH)C(CN)2]) based on a N,O or N,N′-bridge polynitrile ligand, the parallel chains are connected via, respectively, C[triple bond, length as m-dash]N⋯H–O and O–H⋯O hydrogen bonds between uncoordinated functional groups of the ligand and coordinated water molecules. Upon heating, both solids undergo dehydration accompanied by degradation of their single crystals. Powder X-ray diffraction showed that non-isostructural triclinic single crystals transformed to isostructural monoclinic compounds. The solid-state reaction yielded 3D coordination polymers [M(tcnopr3OH)2] (M = NiII and CoII) based on a N,N′,O-connected tcnopr3OH. Although previously tens of complexes based on tcnopr3OH and similar anions were synthesized and X-ray characterized, none of these contain a tridentate polynitrile ligand. Thus, this study provides evidence that solid-state reactions allow obtaining novel coordination modes of polynitrile ligands. The possible pathways for the transformation of H-bonded networks to 3D coordination polymers are discussed on the basis of the topological approach. Applicability of the topological approach to predict possible networks of solid-state reaction products based on the crystal structures of initial compounds is demonstrated.

Graphical abstract: Solid-state 1D → 3D transformation of polynitrile-based coordination polymers by dehydration reaction

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Article information


Submitted
11 Mar 2020
Accepted
23 Apr 2020
First published
23 Apr 2020

Dalton Trans., 2020,49, 7084-7092
Article type
Paper

Solid-state 1D → 3D transformation of polynitrile-based coordination polymers by dehydration reaction

A. O. Dmitrienko, M. I. Buzin, Z. Setifi, F. Setifi, E. V. Alexandrov, E. D. Voronova and A. V. Vologzhanina, Dalton Trans., 2020, 49, 7084
DOI: 10.1039/D0DT00917B

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