Please use this identifier to cite or link to this item: http://dspace.library.iitb.ac.in/xmlui/handle/100/17987
Title: 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
Authors: RAJAKANNU, P
HOWLADER, R
KALITA, AC
BUTCHER, RJ
MURUGAVEL, R
Keywords: Metal-Organic Frameworks
Tert-Butyl Phosphate
Secondary Building Units
Magnetic-Properties
Auxiliary Ligands
Solid-State
Di(Tert-Butyl)Phosphate Complexes
Structural Transformations
Lanthanide Phosphonates
Zinc Phosphates
Issue Date: 2015
Publisher: CHINESE CHEMICAL SOC
Citation: INORGANIC CHEMISTRY FRONTIERS, 2(1)55-66
Abstract: One dimensional metallophosphate coordination polymers {[M(dtbp)(2)(azopy)(H2O)(2)]center dot(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) over bar) 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 center dot center dot center dot 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)]center dot(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.
URI: http://dx.doi.org/10.1039/c4qi00149d
http://dspace.library.iitb.ac.in/jspui/handle/100/17987
ISSN: 2052-1553
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