含有硝酰氮氧双自由基的二维和三维Cu(hfac)₂配合物

2D and 3D Cu(hfac)2 complexes with nitronyl nitroxide biradicals.

作者信息

Tretyakov Eugene, Fokin Sergei, Romanenko Galina, Ikorskii Vladimir, Vasilevsky Sergei, Ovcharenko Victor

机构信息

International Tomography Center, Siberian Branch of the Russian Academy of Sciences, 630090, Novosibirsk, Russia.

出版信息

Inorg Chem. 2006 May 1;45(9):3671-8. doi: 10.1021/ic060132e.

DOI:10.1021/ic060132e

PMID:16634600

Abstract

Reactions between Cu(hfac)2 and nitronyl nitroxide biradicals 1,4-bis[4-(4,4,5,5-tetramethyl-3-oxide-1-oxyl-4,5-dihydro-1H-imidazol-2-yl)pyrazol-1-yl]butane (L4) and 1,8-bis[4-(4,4,5,5-tetramethyl-3-oxide-1-oxyl-4,5-dihydro-1H-imidazol-2-yl)pyrazol-1-yl]octane (L8) gave respectively a framework compound [Cu(hfac)2]2L4 and a layered polymer compound [Cu(hfac)2]2L8. The framework of [Cu(hfac)2]2L4 consists of 66-membered condensed metallocycles. Inside the framework, the structure has macrohelixes (pitch approximately 25 A) extending along the [001] crystallographic direction. All the helixes have the same direction of winding; the crystals, therefore, are optically active, the structure corresponding either to P-isomer (P4(1)2(1)2) or to M-isomer (P4(3)2(1)2). The long distances between the Cu atoms and the O atoms of the coordinated >N-O groups (Cu-O 2.351-2.467 A) are responsible for ferromagnetic exchange interactions in Cu2+-O-N< and >N-O-Cu2+-O-N< exchange clusters.

摘要

Cu(hfac)₂与氮氧自由基双自由基1,4 - 双[4 - (4,4,5,5 - 四甲基 - 3 - 氧化 - 1 - 氧代 - 4,5 - 二氢 - 1H - 咪唑 - 2 - 基)吡唑 - 1 - 基]丁烷（L4）以及1,8 - 双[4 - (4,4,5,5 - 四甲基 - 3 - 氧化 - 1 - 氧代 - 4,5 - 二氢 - 1H - 咪唑 - 2 - 基)吡唑 - 1 - 基]辛烷（L8）反应，分别得到一种骨架化合物[Cu(hfac)₂]₂L4和一种层状聚合物化合物[Cu(hfac)₂]₂L8。[Cu(hfac)₂]₂L4的骨架由66元稠合金属环组成。在骨架内部，结构具有沿[001]晶向延伸的大螺旋（螺距约25 Å）。所有螺旋具有相同的缠绕方向；因此，晶体具有光学活性，其结构对应于P - 异构体（P4(1)2(1)2）或M - 异构体（P4(3)2(1)2）。配位的>N - O基团的Cu原子与O原子之间的长距离（Cu - O 2.351 - 2.467 Å）导致了Cu²⁺ - O - N<和>N - O - Cu²⁺ - O - N<交换簇中的铁磁交换相互作用。