A New Class of Heterobinuclear Complexes: Crystal Structure and Magnetism of Copper(II)-Nickel(II) Complexes Incorporating Two Different Macrocyclic Ligands

Abstract

Three novel oxamido-bridged heterobinuclear copper(II)-nickel(II) complexes incorporating two different tetraazamacrocyclic compounds were synthesized and characterized by IR, ESR, and electronic spectra. They are of the formulas [(CuL 1 )Ni(rac-cth)](ClO) 42´H2 O (1), [Cu(L 2 )Ni(rac-cth)](ClO 4 ) 2´0 .5 EtOH (2), and [(CuL 3 )Ni(rac-cth)](ClO 4 ) 2´H2 O (3). L 1 , L 2 , and L 3 are the dianions of diethyl 5, 6,7,8,16,17-hexahydro-6,7-dioxo-15H-dibenzo[e,n][1,4,8,12]tetraazacyclopentadecine-13,19-dicarboxylate, diethyl 5,6,7,8,15,16-hexahydro-6,7-dioxodibenzo[1,4,8,11]tetraazacyclotetracine-13,18-dicarboxylate, and diethyl 5,6,7,8,15,16-hexahydro-15-methyl-6,7-dioxodibenzo[1,4,8,11]tetraazacyclotetradecine-13,18-dicarboxylate, respectively, and rac-cth is rac-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane. The crystal structures of 1 and 2 were determined by single-crystal X-ray analysis. The Ni II ion is pseudooctahedrally coordinated. The coordination geometry around the Cu II ion in 2 is slightly distorted square planar, while that in 1 shows significant distortion towards a tetrahedral structure. The temperature dependence of the magnetic susceptibility for 1 and 2 was analyzed by means of the Hamiltonian H Ã À 2JS Ã 1´S Ã 2 , leading to J À 63.9 and À 67.4 cm À1 for 1 and 2, respectively.

Hydrothermal Syntheses, Crystal Structures, Magnetism and Fluorescence Quenching of Oxamidato‐Bridged Pentanuclear CuII4LnIII Complexes Containing Macrocyclic Ligands (Ln = Eu, Tb) and the Crystal Structure of a Hexanuclear NiII5SmIII Complex

“…With these facts in mind and in continuation of our work on polynuclear macrocyclic complexes,20−22 the macrocyclic oxamido‐copper ( II ) and oxamido‐nickel( II ) complexes were used as ligands to synthesize new complexes. The result is that two novel pentanuclear Cu II 4 Ln III complexes (Ln = Eu, Tb) and one hexanuclear Ni II 5 Sm III complex have been isolated and structurally characterized, the magnetic and fluorescent properties of 1 and 2 have also been subjected to a preliminarily investigation.…”

A new heterotrinuclear macrocyclic complex: bis(μ-diethyl 5,6,7,8,15,16-hexahydro-6,7-dioxo-5,8,14,17-tetraazadibenzo[a,g]cyclotetradecine-13,18-dicarboxylato)-1κ4N:2κ2O6,O7;2κO6,O7:3κ4N-dimethanoldinickel(II)zinc(II) bis(perchlorate)

“…Polynuclear complexes are currently of considerable interest and have been researched widely. Black & Moss (1987) first synthesized a series of ML-like complexes (L is diethyl 5,6,7,8,15,16-hexahydro-6,7-dioxo-5,8,14,17-tetraazadibenzo-[a,g]cyclotetradecine-13,18-dicarboxylate), and many polynuclear complexes with interesting structures and properties have been synthesized using these mononuclear complexes as ligands (Gao et al, 2001;Zhang et al, 2003;Sun et al, 2004;. We have synthesized a number of heterotrinuclear complexes with NiL-like ligands Li, Yu et al, 2002;.…”

Synthesis, crystal structure of a new tetranuclear Ni 2 II Cu 2 II complex containing a macrocyclic ligand

“…Recently, many oxamido-bridged polynuclear complexes containing macrocyclic have been prepared, because these precursors are particularly suitable for designing heterometallic complexes [3][4][5][6][7][8][9]. However, from the synthetic point of view, few studies of those containing oxamide and thiocyanate mix-bridged polynuclear have been made.…”