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Syntheses, molecular and supramolecular structures, and magnetic properties of a mononuclear MnII and a dicyanamide-bridged one-dimensional CuII compound derived from enolic 4-terpyridone
Syntheses, molecular and supramolecular structures, and magnetic properties of a mononuclear manganese(II) compound [MnII(LH)2](ClO4)2 (1) and a dicyanamide-bridged one-dimensional copper(II) compound [CuII(LH)(mu1,5-dca)]n(NO3)n (2) derived from enolic 4-terpyridone (LH) have been described. The compounds 1 and 2 crystallize in monoclinic P 2 (1) / n and triclinic P over(1, ?) space groups, respectively, with the following unit cell parameters – 1: a = 8.8281(4) A?, b = 8.7736(4) A?, c = 39.7838(16) A?, beta = 95.719(1), and Z = 4; 2: a = 7.5342(3) A?, b = 8.9307(4) A?, c = 15.0189(8) A?, alpha = 73.0032(15), beta = 81.3701(16), gamma = 65.461(2), and Z = 2. In 1, the metal center is hexacoordinated by three pyridine nitrogens of each of the two enolic 4-terpyridones. In 2, the metal center is pentacoordinated by three pyridine nitrogens of 4-terpyridone and two nitrogens of two end-to-end (EE; mu1,5-) dicyanamide. The coordination geometries of 1 and 2 are distorted octahedral and distorted square pyramidal, respectively. Eight hydrogen bonds, six of C-H?O types and two of O-H?O types, link the complex cation [MnII(LH)2]2+ and two perchlorate anions into a three-dimensional network in 1. In the case of 2, seven hydrogen bonds, six of C-H?O types and one of O-H?O type, link the dicyanamide-bridged one-dimensional chains into a two-dimensional sheet consisting of interlinked one-dimensional double-chains. It may be noted that O-H group of enolic 4-terpyridone participates in hydrogen bonding interactions and in developing extended structures in both 1 and 2. Variable-temperature (2-300 K) magnetic susceptibility measurements of both the compounds have been performed to understand the possibility of spin transition in 1 and exchange interaction in 2. However, the susceptibility data of 1 indicate the existence of high-spin manganese(II) throughout the temperature range. In the case of 2, copper(II) centers are noninteracting which is related to the highly distorted coordination geometry of the metal ion.
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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI