The Assembly of Dinuclear Alkoxido‐Bridged Cu^II Halide Complexes of Pyridine Alcohols To Form Tetranuclear and Polynuclear Compounds: Synthesis, Structure, and Magnetic Properties

Abstract

Abstract Reaction of CuX 2 (X = Cl, Br) with pyridine alcohol ligands [2‐(hydroxymethyl)pyridine = Hhmp, 2‐(hydroxyethyl)pyridine = Hhep and 2‐(hydroxypropyl)pyridine = Hhpp] affords a series of new Cu II alkoxide complexes with a similar Cu 2 O 2 structural motif: a dinuclear complex, [Cu 2 (hpp) 2 Br 2 ] ( 1 ), two tetranuclear compounds, [Cu 4 (hpp) 4 Br 4 ] ( 2 ) and [Cu 4 (hpp) 4 Cl 4 ] ( 3 ), and polynuclear chains, [Cu 2 (hep) 2 Cl 2 ] n ( 4 ) and [Cu 2 (Hhmp) 2 Cl 4 ] n ( 5 ). The dinuclear complex 1 represents the basic building unit of the four other materials. In this family of compounds, the pyridine alcohol type ligands (Hhmp, Hhep, or Hhpp) provide the two alkoxido functions that bridge the Cu II centers. The tetranuclear analogues exhibit an unusual structure of the defect dicubane‐like type with two missing vertices. The one‐dimensional polymers 4 and 5 are composed of Cu 2 O 2 dinuclear units interlinked through bridging chlorido ligands to form infinite chains. The analysis of the magnetic susceptibility measurements indicates the presence of strong antiferromagnetic coupling between the S = 1/2 Cu II metal ions through the bis(alkoxido) bridge. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)