Magnetostructural Correlations in Bis(m(2)-phenoxide)-Bridged Macrocyclic Dinuclear Copper(II) Complexes. Influence of Electron-Withdrawing Substituents on Exchange Coupling.

摘要: Macrocyclic dicopper(II) complexes derived from 2,6-di(R)formylphenols and various linking diamines are surveyed their magnetic structural properties assessed. For those systems with "flat" dinuclear centers no electronic perturbations associated electron-withdrawing ligands or ligand groups, the exhibit a "straight-line" relationship between exchange integral phenoxide bridge angle. Within angle range 98.8-104.7 degrees, 11 included -2J in 689-902 cm(-)(1). When species present, either as groups bound to macrocycle itself, considerable suppression of antiferromagnetic component is observed. Single-crystal X-ray diffraction studies reported for three complexes. [Cu(2)(L1)(H(2)O)(2)]F(2)(CH(3)OH)(2) (1) crystallized triclinic system, space group Po, = 8.1878(5) A, b 9.0346(7) c 10.4048(7) alpha 103.672(6) beta 101.163(5) gamma 104.017(5) Z 1. [Cu(2)(L2)Cl(2)] [Cu(2)(L2) (H(2)O)(2)]Cl(ClO(4)).5.5H(2)O (2) monoclinic P2(1)/n, 14.4305(5) 24.3149(8) 18.6584(8) 111.282(3) 4. [Cu(2)(L3)(H(2)O)(2)](BF(4))(2) (3) 8.6127(4) 8.6321(7) 10.8430(10) 74.390(10) 86.050(10) 76.350(10) 2. Square pyramidal copper ion stereochemistries observed all cases, axially coordinated halogens water molecules. Strong (-2J 784(8) cm(-)(1), Cu-O-Cu 103.65(10) degrees (1); 801(11) 102.4(3), 107.5(3), 102.9(3), 106.1(3) (2); 689(3) 98.8(4) (3)). The presence CN on periphery macrocyclic leads substantially reduced exchange.