High-Pressure Study of Oxo-bridged Mixed-Valent MnIII/MnIV Dimers High-Pressure Study of Oxo-bridged Mixed-Valent MnIII/MnIV Dimers
High-Pressure Study of Oxo-bridged Mixed-Valent MnIII/MnIV Dimers High-Pressure Study of Oxo-bridged Mixed-Valent MnIII/MnIV Dimers
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氧桥混合价 MnIII/MnIV 二聚体的高压研究 氧桥混合价 MnIII/MnIV 二聚体的高压研究
DOI：
10.1515/znb-2010-0302
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发表时间：
2010
期刊：
影响因子：
--
通讯作者：
E. Brechin
中科院分区：
文献类型：
--
作者：
A. Prescimone;J. Sánchez;K. Kamenev;J. Warren;A. Lennie;M. Murrie;S. Parsons;E. Brechin
结合高压单晶X射线衍射和高压SQUID磁强计已被用来研究两个氧桥混合价锰III/锰IV二聚体。[Mn_2O_2（bpy）_4]（ClO_4）_3·3CH_3CN，（1·3CH_3CN; bpy = 2，2 ′-联吡啶）的压缩压力为2.0 GPa，而[Mn_2O_2（bpy）_4]（PF_6）_3·2CH_3CN·1H_2O，（2·2CH_3CN·1H_2O）的晶体学测量压力为4.55 GPa。[Mn 2 O2（bpy）4]3+的PF 6盐以前从未报道过，而1已被报道为水合物和不同的晶体空间群。流体静压力的应用对两种复合物的结构造成了显著的扭曲和修改。特别地，在配合物1·3CH 3CN中，Mn-Mn分离由于一些Mn-O键长的收缩而减少，而在2·2CH 3CN·1H 2 O中，Mn-O-Mn桥连角和Mn-O键长基本上不变。有趣的是，2·2CH 3CN·1H 2 O在几乎所有的Mn-N键中也显示出恒定的收缩。配合物的磁性分别为1·3CH_3CN和2·2CH_3CN·1H_2 O，其磁性分别为0.87GPa和0.84GPa。氧桥混合价MnIII/MnIV二聚体的高压研究氧桥混合价MnIII/MnIV二聚体的高压研究
A combination of high-pressure single crystal X-ray diffraction and high-pressure SQUID magnetometry has been used to study two oxo-bridged mixed-valent MnIII/MnIV dimers. [Mn2O2(bpy)4](ClO4)3·3CH3CN, (1·3CH3CN; bpy = 2,2ʹ-bipyridine) has been compressed to 2.0 GPa whilst [Mn2O2(bpy)4](PF6)3·2CH3CN·1H2O, (2·2CH3CN·1H2O) could be measured crystallographically up to 4.55 GPa. The PF6 salt of [Mn2O2(bpy)4]3+ has never been reported before while 1 has been reported as a hydrate and in a different crystallographic space group. The application of hydrostatic pressure imposes significant distortions and modifications in the structures of both complexes. In particular, in complex 1·3CH3CN the Mn-Mn separation is reduced by the contraction of some of the Mn-O bond lengths, whilst in 2·2CH3CN·1H2O the Mn-O-Mn bridging angles and the Mn-O bond lengths are substantially unchanged. Interestingly 2·2CH3CN·1H2O also shows a constant contraction in nearly all the Mn-N bonds. The magnetic behaviour of the complexes has been measured up to 0.87 GPa for 1·3CH3CN and 0.84 GPa for 2·2CH3CN·1H2O. Graphical Abstract High-Pressure Study of Oxo-bridged Mixed-Valent MnIII/MnIV Dimers High-Pressure Study of Oxo-bridged Mixed-Valent MnIII/MnIV Dimers