SPECTROSCOPIC STUDIES ON COPPER(II) COMPLEXES OF CHIRAL CYCLENS - [CUN4CL] CHROMOPHORES VARYING FROM SQUARE PYRAMIDAL TO TRIGONAL BIPYRAMIDAL STEREOCHEMISTRY

被引:25
作者
AZUMA, N
KOHNO, Y
NEMOTO, F
KAJIKAWA, Y
ISHIZU, K
TAKAKUWA, T
TSUBOYAMA, S
TSUBOYAMA, K
KOBAYASHI, K
SAKURAI, T
机构
[1] EHIME UNIV,FAC SCI,DEPT CHEM,MATSUYAMA,EHIME 790,JAPAN
[2] JACSO CORP,APPLICAT LAB,HACHIOJI,TOKYO 921,JAPAN
[3] RIKEN,WAKO,SAITAMA 35101,JAPAN
关键词
COPPER COMPLEXES; MACROCYCLIC LIGAND COMPLEXES;
D O I
10.1016/0020-1693(93)03677-3
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A series of five copper(II) complexes with four geometrically isomeric ligands of 1,4,7,10-tetrabenzyl-2,5,8,11-tetraethyl-1,4,7,10-tetraazacyclododecan and with (2R,5R,8R,11R)-2,5,8,11-tetraethyl-1,4,7,10-tetraazacyclododecane has been investigated by means of ESR, CD and MCD in solution. X-ray studies reported separately had shown that the [CuN4Cl] chromophores were distorted to varying extents from square pyramidal to trigonal bipyramidal geometry. The stability and rigidity of the molecular structure have enabled us to carry out a complementary study of the crystalline state and solution chemistry. The ground state Kramers doublets varied from 3d(x2-y2) to 3d(z2) type with increasing distortion around the copper ion. The orbital sequence of the 3d(1) positive hole, d(x2-y2)<d(z2)<d(yz,xz)<d(xy), has been obtained for the C-4v complexes. The 3d(xy) orbital is also the highest in energy for the complex with the 3d(z2) type ground state doublet. This complex exhibited superhyperfine splitting in the g, region due to the chlorine nucleus, which implies the principal z axis of the g tenser is along the Cu-Cl bond. The sign of the copper hyperfine tensors was determined by means of Swalen's treatment. The changing values of the orbital coefficients decreasing for the 3d(x2-y2) and increasing for the 3d(z2), 3d(xz) and 3d(yz) in the ground state doublets have been attributed to concomitant elongation of the in-plane Cu-N bond and reduction of the out-of-plane Cu-Cl bond length with the increasing distortion around the copper ions.
引用
收藏
页码:109 / 121
页数:13
相关论文
共 61 条
[1]  
Abe H., 1956, J PHYS SOC JPN, V11, P947
[2]   THEORY OF THE NUCLEAR HYPERFINE STRUCTURE OF PARAMAGNETIC RESONANCE SPECTRA IN CRYSTALS [J].
ABRAGAM, A ;
PRYCE, MHL .
PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL AND PHYSICAL SCIENCES, 1951, 205 (1080) :135-153
[3]   SYNTHESIS, STRUCTURE, AND SPECTROSCOPIC PROPERTIES OF COPPER(II) COMPOUNDS CONTAINING NITROGEN SULFUR DONOR LIGANDS - THE CRYSTAL AND MOLECULAR-STRUCTURE OF AQUA[1,7-BIS(N-METHYLBENZIMIDAZOL-2'-YL)-2,6-DITHIAHEPTANE]COPPER(II) PERCHLORATE [J].
ADDISON, AW ;
RAO, TN ;
REEDIJK, J ;
VANRIJN, J ;
VERSCHOOR, GC .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1984, (07) :1349-1356
[4]   SINGLE-CRYSTAL ESR-SPECTRA OF COPPER(II) COMPLEXES WITH GEOMETRIES INTERMEDIATE BETWEEN A SQUARE PYRAMID AND A TRIGONAL BIPYRAMID [J].
BENCINI, A ;
BERTINI, I ;
GATTESCHI, D ;
SCOZZAFAVA, A .
INORGANIC CHEMISTRY, 1978, 17 (11) :3194-3197
[5]   MAGNETISM IN FLORENCE [J].
BENELLI, C ;
GATTESCHI, D .
COORDINATION CHEMISTRY REVIEWS, 1992, 120 :137-161
[6]   TIME-DEPENDENT MEASUREMENTS AND MOLECULAR STRUCTURE - OZONE [J].
BERRY, RS .
REVIEWS OF MODERN PHYSICS, 1960, 32 (02) :447-454
[8]   PARAMAGNETIC RESONANCE IN DILUTED COPPER SALTS .1. HYPERFINE STRUCTURE IN DILUTED COPPER TUTTON SALTS [J].
BLEANEY, B ;
BOWERS, KD ;
INGRAM, DJE .
PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL AND PHYSICAL SCIENCES, 1955, 228 (1173) :147-157
[9]   PARAMAGNETIC RESONANCE IN CU(NH3)4SO4.H2O [J].
CARLSON, EH ;
SPENCE, RD .
JOURNAL OF CHEMICAL PHYSICS, 1956, 24 (02) :471-471
[10]  
DESIMONE RE, 1980, INORG NUCL CHEM LETT, V16, P23, DOI 10.1016/0020-1650(80)80086-9