Issue 1, 2015

Role of 4,4′-bipyridine versus longer spacers 4,4′-azobipyridine, 1,2-bis(4-pyridyl)ethylene, and 1,2-bis(pyridin-3-ylmethylene)hydrazine in the formation of thermally labile metallophosphate coordination polymers

Abstract

One dimensional metallophosphate coordination polymers {[M(dtbp)2(azopy)(H2O)2]·(azopy)}x (M = Mn (1); Co (2); Cu (3); Cd (4)) have been synthesized from the reaction of a suitable metal precursor with di-tert-butylphosphate (dtbp-H) in the presence of ditopic linker 4,4′-azobipyridine (azopy) in a 1 : 2 : 2 stoichiometric ratio. Isostructural compounds 1–4 have been characterized by analytical and spectroscopic methods and single crystal X-ray diffraction studies. Single crystal X-ray diffraction measurements further reveal that compounds 1–3 (all C2/c) and 4 (P[1 with combining macron]) are linear 1D coordination polymers. The uncoordinated 4,4′-azobipyridine in the lattice is responsible for the conversion of these 1D coordination polymers into 3D supramolecular assemblies through O–H⋯N hydrogen bonding interactions between coordinated water and N-centers of an azopy ligand. Similar reactions carried out using 1,2-bis(4-pyridyl)ethylene (bpe) as the linker yielded compounds having the formula {[M(dtbp)2(bpe)(H2O)2]·(bpe)}x (M = Mn (5); Co (6); Cu (7); Ni (8)). Compounds 5–8 have been characterized by analytical and spectroscopic methods. Preliminary single crystal X-ray diffraction studies carried out on poorly diffracting crystals of 5 and 6 establish their isostructural nature to 1–4, also displaying a similar supramolecular aggregation behaviour. A longer ditopic N,N′-donor ligand, 1,2-bis(pyridin-3-ylmethylene)hydrazine (bph), has been used in place of bpe/azoby to synthesize 1-dimensional coordination polymers [{M(bph)(H2O)4}{(dtbp)2}] (M = Ni (9) and M = Co (10)) and [Cd(bph)3(dtbp)2]n (11) which have completely different structural motifs when compared to 1–4.

Graphical abstract: Role of 4,4′-bipyridine versus longer spacers 4,4′-azobipyridine, 1,2-bis(4-pyridyl)ethylene, and 1,2-bis(pyridin-3-ylmethylene)hydrazine in the formation of thermally labile metallophosphate coordination polymers

Supplementary files

Article information

Article type
Research Article
Submitted
25 Sep 2014
Accepted
20 Nov 2014
First published
21 Nov 2014

Inorg. Chem. Front., 2015,2, 55-66

Author version available

Role of 4,4′-bipyridine versus longer spacers 4,4′-azobipyridine, 1,2-bis(4-pyridyl)ethylene, and 1,2-bis(pyridin-3-ylmethylene)hydrazine in the formation of thermally labile metallophosphate coordination polymers

P. Rajakannu, R. Howlader, A. Ch. Kalita, R. J. Butcher and R. Murugavel, Inorg. Chem. Front., 2015, 2, 55 DOI: 10.1039/C4QI00149D

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