Issue 29, 2007

4,4′-Bipyridazine: a new twist for the synthesis of coordination polymers

Abstract

A new polydentate ligand 4,4′-bipyridazine (4,4′-bpdz) was prepared by employing inverse electron demand cycloaddition of 1,2,4,5-tetrazine. A unique combination of structural simplicity, ampolydentate character and efficient donor properties towards Cu(I), Cu(II) and Zn(II) provide wide new possibilities for the synthesis of coordination polymers incorporating the 4,4′-bpdz module either as a bi-, tri- or tetradentate connector between the metal ions. 1D coordination polymers Cu2(4,4′-bpdz)(CH3CO2)4·4H2O and Zn(4,4′-bpdz)(NO3)2, and interpenetrated (4,4)-nets in [Cu(4,4′-bpdz)2(H2O)2]S2O6 were closely related to 4,4′-bipyridine compounds. 1D “ladder-like” polymer Cu2(4,4′-bpdz)3(CF3CO2)4 and the unprecedented 3D binodal net ({86}{63;83}) in [Cu3(4,4′-bpdz)6(H2O)4](BF4)6·6H2O were based upon a combination of linear and angular organic bridges. Complex [Cu3(OH)2(4,4′-bpdz)3(H2O)2{CF3CO2}2](CF3CO2)2·2H2O has a “NbO-like” 3D topology incorporating discrete dihydroxotricopper(II) clusters linked by tri- and tetradentate ligands. The tetradentate function of the 4,4′-bpdz ligand was especially relevant for copper(I) complexes, which adopt layered Cu2X2(4,4′-bpdz) (X = Cl, Br) or 3D chiral framework (X = I) structures based upon infinite (CuX)n chains. The electron deficient character of the ligand was manifested by short anion–π interactions (O–π 3.02–3.20; Cl–π 3.35 Å), which may be involved as a factor for controlling the supramolecular structure.

Graphical abstract: 4,4′-Bipyridazine: a new twist for the synthesis of coordination polymers

Supplementary files

Article information

Article type
Paper
Submitted
15 Mar 2007
Accepted
20 Apr 2007
First published
09 May 2007

Dalton Trans., 2007, 3140-3148

4,4′-Bipyridazine: a new twist for the synthesis of coordination polymers

K. V. Domasevitch, I. A. Gural'skiy, P. V. Solntsev, E. B. Rusanov, H. Krautscheid, J. A. K. Howard and A. N. Chernega, Dalton Trans., 2007, 3140 DOI: 10.1039/B703911E

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