双（二-μ-乙氧基-双（3,5-二叔丁基半醌基）二铜（II））配合物的晶体结构、分子结构及磁交换性质。密度泛函理论与实验磁化学之间的协同作用。

Crystal and molecular structure and magnetic exchange properties of bis(di-micro-ethoxo-bis(3,5-di-tert-butylsemiquinonato)dicopper(II)) complex. A synergy between DFT and experimental magnetochemistry.

作者信息

Bencini Alessandro, Dei Andrea, Sangregorio Claudio, Totti Federico, Vaz Maria G F

机构信息

INSTM Research Unit, Dipartimento di Chimica Università degli Studi di Firenze, via della Lastruccia 3, 50019 Sesto Fiorentino, Florence, Italy.

出版信息

Inorg Chem. 2003 Dec 1;42(24):8065-71. doi: 10.1021/ic034447v.

DOI:10.1021/ic034447v

PMID:14632527

Abstract

The compound bis(di-micro-ethoxo-bis(3,5-di-tert-butylsemiquinonato)dicopper(II)) has been synthesized and its structure was determined by single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, space group C2/c, with a = 37.736(8) A, b = 9.173(2) A, c = 23.270(5) A, beta = 122.24(3) degrees. The structure can be described as a Lewis adduct between two dinuclear Cu(DBSQ)(C(2)H(5)O) units (DBSQ = 3,5-di-tert-butyl-semiquinonato). The temperature dependence of the magnetic susceptibility was efficiently analyzed by a combined DFT/experimental approach, showing that a rather strong ferromagnetic interaction exists between the DBSQ(-) and the copper(II) ions modulated by an antiferromagnetic interaction between the two copper(II) ions of the dinuclear units. Weak antiferromagnetism between the two units in the unit cell was measured.

摘要

化合物双（二微乙氧基双（3,5-二叔丁基半醌基）二铜（II））已被合成，其结构通过单晶X射线衍射确定。该化合物结晶于单斜晶系，空间群C2/c，a = 37.736(8) Å，b = 9.173(2) Å，c = 23.270(5) Å，β = 122.24(3)°。该结构可描述为两个双核[Cu(DBSQ)(C₂H₅O)]₂单元（DBSQ = 3,5-二叔丁基半醌基）之间的路易斯加合物。通过结合密度泛函理论/实验方法有效分析了磁化率的温度依赖性，结果表明DBSQ⁻与铜（II）离子之间存在相当强的铁磁相互作用，该相互作用由双核单元中两个铜（II）离子之间的反铁磁相互作用调节。测量了晶胞中两个单元之间的弱反铁磁性。