Coordination Asymmetry of a Dinuclear Copper(II) Complex: Synthesis, Structure, and Magnetism

フォーマット:

論文

責任表示:

Kayatani, Takayuki ; Hayashi, Yoshihito ; Suzuki, Masatatsu ; Inomata, Katsuhiko ; Uehara, Akira

言語:

英語

出版情報:

The Chemical Society of Japan = 日本化学会, 1996-01-01

著者名:

• Kayatani, Takayuki
• Hayashi, Yoshihito
• Suzuki, Masatatsu
• Inomata, Katsuhiko
• Uehara, Akira

掲載情報:

Bulletin of the Chemical Society of Japan

ISSN:

0009-2673      

巻:

69

通号:

2

開始ページ:

389

終了ページ:

397

バージョン:

publisher

概要:

A dicopper(II) complex with a novel unsymmetric dinucleating ligand, H2L-1, which can provide donor atom, coordination number, and geometric asymmetries at metal centers, [Cu2(L-1)(CH3COO)]ClO4·H2O·0.5NaClO4 (1), was synthesized, where H2L-1 is a racemic 1-bis(2-pyridylmethyl)amino-3-salicylideneaminopropan-2-ol. The ligand is a hybrid one of 1,3-bis[bis(2-pyridylmethyl)amino]propan-2-ol (Htpdp) and … 1,3-bis(salicylideneamino)propan-2-ol (H3L-2). Crystal structure of 1 was determined by X-ray crystallography. Complex 1 crystallizes in monoclinic space group C2/c with a = 42.704(8), b = 12.689(6), c = 29.008(9) Å, β = 128.28(1)°, and Z = 16. The crystal structure showed that two stereoisomers (1a and 1b) are present in solid state. This is attributable to the presence of an enantiomeric pair of L-1. Dinuclear cations consist of one square-planar site with a NO3 donor set and one five-coordinate site with a N3O2 donor set, which are linked by an endogenous alkoxide bridge of L-1 and an exogenous acetate bridge. A powdered sample of 1 shows weak antiferromagnetic interaction (2.60 B.M./Cu2 at 300 and 1.81 B.M./Cu2 at 5 K). Cryomagnetic data is analyzed using two exchange coupling constants, J1 = −0.18 cm−1 and J2 = −9.05 cm−1. EHMO calculations revealed that the observed weak antiferromagnetic interaction(s) compared with that found for [Cu2(L-2)(CH3COO)] (3) (J = −85 cm−1) is reasonably interpreted in terms of the energy gap and the nature of HOMO and LUMO. Some other physicochemical properties of the complex are discussed in comparison with those of the parent complexes, [Cu2(tpdp)(CH3COO)]2+ (2) and [Cu2(L-2)(CH3COO)] (3). 続きを見る

URL:

http://hdl.handle.net/2297/37766