Department of Material and Life Science, Graduate School of Engineering, Osaka University, Suita, SORST (Japan) Science Technology Agency, Osaka 565-0871, Japan.
Chem Asian J. 2011 Jun 6;6(6):1416-22. doi: 10.1002/asia.201000822. Epub 2011 Apr 7.
A vanadium porphyrin, V(O)TMeOPP (1; TMeOPP=5, 10, 15, 20-tetrakis(4-methoxyphenyl)-21 H, 23H-porphyrin), has been synthesized by solvothermal reactions and characterized by single-crystal X-ray diffractions at room temperature and low temperature to reveal two different structures 1R and 1L, respectively. Both 1R and 1L crystallized in the orthorhombic system, but their space groups were different: Pbca and Pca2(1) for 1R and 1L, respectively. The cell parameters of a, b, and c were different and the cell volume of 1R was larger than that of 1L by circa 200 Å(3). 1R and 1L were characteristic of an isolated motif with a five-coordinate vanadium(IV) ion and a saddle-distorted nonplanar porphyrin macrocycle. Molecules of 1R were interconnected through hydrogen-bonding interactions to yield a 3D framework; whilst for the low-temperature phase 1L, there were more hydrogen-bonding interactions that link the molecules to construct a more-complex 3D supramolecular network. In a solution of acetone, the title compound exhibited purple and green colors at room temperature and low temperature, respectively, which is unprecedented for vanadium porphyrins. The spectral data of UV/Vis, FT-IR, and MALDI-TOF-MS of 1R and 1L are reported together with the electrochemical data.
一种钒卟啉，V（O）TMeOPP（1；TMeOPP=5,10,15,20-四（4-甲氧基苯基）-21H，23H-卟啉），通过溶剂热反应合成，并通过室温和低温下的单晶 X 射线衍射进行了表征，分别揭示了两种不同的结构 1R 和 1L。1R 和 1L 均结晶在正交晶系中，但它们的空间群不同：1R 为 Pbca，1L 为 Pca2(1)。a、b 和 c 的晶胞参数不同，1R 的晶胞体积比 1L 大约大 200 Å(3)。1R 和 1L 的特征是具有五配位的钒（IV）离子和马鞍形扭曲的非平面卟啉大环的孤立基序。1R 的分子通过氢键相互作用连接在一起，形成了一个 3D 骨架；而对于低温相 1L，存在更多的氢键相互作用，将分子连接起来，构建了一个更复杂的 3D 超分子网络。在丙酮溶液中，标题化合物在室温下呈现紫色，在低温下呈现绿色，这是钒卟啉前所未有的。还报道了 1R 和 1L 的 UV/Vis、FT-IR 和 MALDI-TOF-MS 的光谱数据以及电化学数据。
