Abstract
AbstractDicopper complexes withN,N′‐p‐xylylenebis(cyclam or cyclen) and with the heteroditopicN,N′‐p‐xylylenebis(cyclam‐cyclen) were synthesized. An X‐ray study of theN,N′‐p‐xylylenebis(cyclen)dicopper complex showed that the copper(II) ion is five‐coordinate with an H2O molecule in apical position. With this ligand, a polymeric chain was also obtained in the presence of KSCN. The terminal donor atoms of the bridging NCS−anion are coordinated in apical position to the square‐pyramidal copper(II) ion. Two alternating kinds of Cu2L4+moieties are present in the chain, the first with two N4S chromophores and the second with two N5chromophores. EXAFS and XANES results are in agreement with a five‐coordinate copper ion in the cyclen unit and a six‐coordinate copper ion in the cyclam unit. Thermodynamic constants were determined by potentiometry. The existence of dinuclear Cu2L4+species (ligand/metal ratio < 1) and mononuclear CuLHn(2+n)+species (ligand/metal ratio > 1) were confirmed by an ESR study at variable pH. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
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