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基于氧化还原活性四硫富瓦烯的亚氨基吡嗪配体的配位配合物:合成、一种自由基阳离子盐、晶体结构及电化学

Coordination complexes with the redox active tetrathiafulvalene based imino-pyrazine ligand: syntheses, a radical cation salt, crystal structures and electrochemistry.

作者信息

Cosquer Goulven, Pointillart Fabrice, Le Gal Yann, Golhen Stéphane, Cador Olivier, Ouahab Lahcène

机构信息

Organométalliques et Matériaux Moléculaires, UMR 6226 CNRS-UR1 Sciences Chimiques de Rennes, Université de Rennes 1, 35042 Rennes Cedex, France.

出版信息

Dalton Trans. 2009 May 14(18):3495-502. doi: 10.1039/b815865g. Epub 2009 Mar 20.

Abstract

The tetrathiafulvalene based 2-immino-pyrazine derivative (TTF-CHN-2-pyz) () was synthesized and characterized. Its radical cation salt ( (+)PF(6)(-)) was prepared as single crystals by electrocrystallisation. (+)PF(6)(-) crystallizes in the triclinic P1 space group. Four 1 : 2 bis(hexafluoroacetylacetonate)M(ii) complexes coordinated with were prepared (M = Mn for , M = Co for , M = Cu for and M = Zn for ). Complex crystallizes in the monoclinic C2/c space group, complexes and crystallize in the triclinic space group P1. Two pyrazine N atoms from two different donors are coordinated in cis configuration for and trans configuration for and to the metallic ion of M(hfac)(2) (hfac(-)=hexafluoroacetylacetonate anion). The manganese atom adopts a pseudo-compressed octahedral geometry while the copper and the zinc ions adopt axially elongated octahedral geometries. Both crystal packing structures and electrochemical properties are appropriate for their potential use as starting molecular bricks for conducting and magnetic materials.

摘要

合成并表征了基于四硫富瓦烯的2-亚氨基吡嗪衍生物(TTF-CHN-2-pyz)()。通过电结晶法制备了其自由基阳离子盐((+)PF₆⁻)的单晶。(+)PF₆⁻以三斜晶系P1空间群结晶。制备了四种与1:2双(六氟乙酰丙酮)M(ii)配合物配位的化合物(对于,M = Mn;对于,M = Co;对于,M = Cu;对于,M = Zn)。配合物以单斜晶系C2/c空间群结晶,配合物和以三斜晶系空间群P1结晶。来自两个不同供体的两个吡嗪N原子以顺式构型与M(hfac)₂(hfac⁻ = 六氟乙酰丙酮阴离子)的金属离子配位,而以反式构型配位。锰原子采用伪压缩八面体几何构型,而铜和锌离子采用轴向拉长的八面体几何构型。晶体堆积结构和电化学性质都适合它们作为导电和磁性材料的起始分子构建单元的潜在用途。

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