TY - JOUR
T1 - Oxamato-bridged trinuclear NiIICuIINiII complexes with irregular spin state structures and a binuclear NiIICuII complex with an unusual supramolecular structure
T2 - Crystal structure and magnetic properties
AU - Gao, E. Q.
AU - Tang, J. K.
AU - Liao, D. Z.
AU - Jiang, Z. H.
AU - Yan, S. P.
AU - Wang, G. L.
PY - 2001/6/18
Y1 - 2001/6/18
N2 - Four oxamato-bridged heterotrinuclear NiIICuIINiII complexes of formula {[Ni(bispictn)]2Cu(pba)}(ClO4) 2·2.5H2O (1), {[Ni(bispictn)]2Cu(pbaOH)}(ClO4)2 ·H2O (2), {[Ni(cth)]2Cu(pba)}(ClO4)2 (3), and {[Ni(cth)]2Cu(opba)}(ClO4)2· H2O (4) and a binuclear NiIICuII complex of formula [Cu(opba)Ni(cth)]·CH3OH (5) have been synthesized and characterized by means of elemental analysis, IR, ESR, and electronic spectra, where pba = 1,3-propylenebis-(oxamato), pbaOH = 2-hydroxyl-1,3-propylenebis(oxamato), opba = o-phenylenebis(oxamato), bispictn = N,N′-bis(2-pyridylmethyl)-1,3-propanediamine, and cth = rac-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane. The crystal structures of 1, 3, and 5 have been determined. The structures of complexes 1 and 3 consist of trinuclear cations and perchlorate anions, and that of 5 consists of neutral binuclear molecules which are connected by hydrogen bonds and π-π interactions to produce a unique supramolecular "double" sheet. In the three complexes, the copper atom in a square-planar or axially elongated octahedral environment and the nickel atom in a distorted octahedral environment are bridged by the oxamato groups, with Cu···Ni separations between 5.29 and 5.33 Å. The magnetic properties of all five complexes have been investigated. The χMT versus T plots for 1-4 exhibit the minimum characteristic of antiferromagnetically coupled NiCuNi species with an irregular spin state structure and a spin-quartet ground state. The χMT versus T plot for 5 is typical of an antiferromagnetically coupled NiCu pair with a spin-doublet ground state. The NiII-CuII isotropic interaction parameters for the five complexes were evaluated and are between 102 and 108 cm-1 (Ĥ = -JŜCu·ŜNi).
AB - Four oxamato-bridged heterotrinuclear NiIICuIINiII complexes of formula {[Ni(bispictn)]2Cu(pba)}(ClO4) 2·2.5H2O (1), {[Ni(bispictn)]2Cu(pbaOH)}(ClO4)2 ·H2O (2), {[Ni(cth)]2Cu(pba)}(ClO4)2 (3), and {[Ni(cth)]2Cu(opba)}(ClO4)2· H2O (4) and a binuclear NiIICuII complex of formula [Cu(opba)Ni(cth)]·CH3OH (5) have been synthesized and characterized by means of elemental analysis, IR, ESR, and electronic spectra, where pba = 1,3-propylenebis-(oxamato), pbaOH = 2-hydroxyl-1,3-propylenebis(oxamato), opba = o-phenylenebis(oxamato), bispictn = N,N′-bis(2-pyridylmethyl)-1,3-propanediamine, and cth = rac-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane. The crystal structures of 1, 3, and 5 have been determined. The structures of complexes 1 and 3 consist of trinuclear cations and perchlorate anions, and that of 5 consists of neutral binuclear molecules which are connected by hydrogen bonds and π-π interactions to produce a unique supramolecular "double" sheet. In the three complexes, the copper atom in a square-planar or axially elongated octahedral environment and the nickel atom in a distorted octahedral environment are bridged by the oxamato groups, with Cu···Ni separations between 5.29 and 5.33 Å. The magnetic properties of all five complexes have been investigated. The χMT versus T plots for 1-4 exhibit the minimum characteristic of antiferromagnetically coupled NiCuNi species with an irregular spin state structure and a spin-quartet ground state. The χMT versus T plot for 5 is typical of an antiferromagnetically coupled NiCu pair with a spin-doublet ground state. The NiII-CuII isotropic interaction parameters for the five complexes were evaluated and are between 102 and 108 cm-1 (Ĥ = -JŜCu·ŜNi).
UR - https://www.scopus.com/pages/publications/0035907434
U2 - 10.1021/ic001023h
DO - 10.1021/ic001023h
M3 - 文章
C2 - 11399184
AN - SCOPUS:0035907434
SN - 0020-1669
VL - 40
SP - 3134
EP - 3140
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 13
ER -