The Influence of the Axial Ligand on the Solid-State Structures of Pentacoordinate Manganese Tetraphenylporphyrin Complexes
The Influence of the Axial Ligand on the Solid-State Structures of Pentacoordinate Manganese Tetraphenylporphyrin Complexes
复制标题
轴向配体对五配位四苯基卟啉锰配合物固态结构的影响
DOI：
--
复制
发表时间：
1998
期刊：
影响因子：
--
通讯作者：
Allan H. White
中科院分区：
文献类型：
--
作者：
P. Turner;M. Gunter;B. Skelton;Allan H. White
Mn(TPP)(NCO)，Mn(TPP)(CH3CO2).0·5C7H8，Mn(TPP)(NCS).0·5C7H8，Mn(TPP)(BR).C7H8，Mn(TPP)(I).C7H8以及已报道的结构：Mn(TPP)(Cl).(CH3)2CO，Mn(TPP)(Cl).C7H8，Mn(TPP)(NO2).C6H6，Mn(TPP)(NO3).2C6H6，Mn(TPP)(OSO3H)，用Mn(TPP)(H2O)·-SO3CF3和Mn(TPP)(CN)·CHCl3研究了轴向阴离子在五配位四苯基锰卟啉配合物晶体堆积中的作用。甲苯溶剂的堆积策略的比较表明，轴向阴离子可以立体地决定晶格堆积基元。在所研究的结构中，似乎有一系列的堆积策略，由支撑Mn(TPP)(BR).C7H8和Mn(TPP)(Cl).C7H8晶格的优雅的“一起缝隙”组装模式领导。已被用来评估固态络合物间相互作用的测量参数被证明是晶体堆积敏感的。这一点在具有两个结晶学独立分子的Mn(TPP)(I)·C7H8的结构中很明显。金属离子从卟啉中心的位移由轴向配位场决定；然而，这种本征性质也依赖于晶体堆积。也就是说，碘配位场本身受晶体堆积相互作用的影响。类质同象的Mn(TPP)(CH3CO2).0·5C7H8和Mn(TPP)(NCS).0·5C7H8结构也具有两个结晶学上独立的分子，表明轴向配位体场强可以通过调节卟啉对金属的电荷给予来影响固态下的络合物间的相互作用。
The crystal structures of Mn(tpp)(NCO), Mn(tpp)(CH3CO2).0·5C7H8, Mn(tpp)(NCS).0·5C7H8, Mn(tpp)(Br).C7H8, Mn(tpp)(I).C7H8 and the previously reported structures Mn(tpp)(Cl).(CH3)2CO, Mn(tpp)(Cl).C7H8, Mn(tpp)(NO2).C6H6, Mn(tpp)(NO3).2C6H6, Mn(tpp)(OSO3H), Mn(tpp)(H2O).-SO3CF3 and Mn(tpp)(CN).CHCl3 are used to assess the role of the axial anion in the crystal packing of pentacoordinate manganese tetraphenylporphyrin complexes. A comparison of the packing strategies adopted by the toluene solvates suggests that the axial anion can sterically determine the lattice packing motif. Amongst the structures examined, there appears to be a hierarchy of packing strategies led by the elegant ‘slot together’ assembly pattern underpinning the Mn(tpp)(Br).C7H8 and Mn(tpp)(Cl).C7H8 lattices. The metrical parameters that have been used to assess intercomplex interactions in the solid state are shown to be crystal packing sensitive. This is clearly evident in the structure of Mn(tpp)(I).C7H8 which has two crystallographically independent molecules. The displacement of the metal ion from the porphyrin core is determined by the axial ligand field; however, this otherwise intrinsic property is also crystal packing dependent. That is, the iodo ligand field itself is modulated by crystal packing interactions. The isomorphous Mn(tpp)(CH3CO2).0·5C7H8 and Mn(tpp)(NCS).0·5C7H8 structures, which also have two crystallographically independent molecules, indicate that the axial ligand field strength can influence intercomplex interactions in the solid state, by moderating charge donation from the porphyrin to the metal.