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Synthesis and characterization of chromium(III) octaphenylporphyrin complexes with various axial ligands: An insight into porphyrin distortion |
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| Authors: | Ryosuke Harada Hisashi ōkawa Seigo Yamauchi |
| Institution: | a Department of Chemistry, Faculty of Sciences, Kyushu University, 6-10-1 Hakozaki, Higashi-Ku, Fukuoka 812-8581, Japan b Department of Materials Science and Technology, Faculty of Science and Technology, Hirosaki University, 3 Bunkyo-cho, Hirosaki, Aomori 036-8561 c Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira 2-1-1, Aoba-Ku, Sendai 980-8577, Japan |
| Abstract: | Influence of axial ligands, MeCN, H2O, py, and piperidine (pip), on distortion of (2,3,5,10,12,13,15,20-octaphenylporphinato)chromium(III), Cr(OPP)]+, was investigated by X-ray crystallography and UV-vis and ESR spectroscopies. In crystal structures of Cr(OPP)(MeCN)(H2O)]ClO4 · MeCN and Cr(OPP)(H2O)2]ClO4 · 3THF, the OPP2− ligand had a planar structure. On the other hand, crystal structures of Cr(OPP)(pip)2]ClO4 · 2CH2Cl2 and Cr(OPP)(py)2]ClO4 exhibited a waved structure and a saddle-shaped structure with ruffling, respectively. In the UV-vis spectrum of Cr(OPP)(py)2]ClO4 in CH2Cl2, the large red shift of the Soret band was observed. Furthermore, the small D value of 0.10 cm−1 was obtained for Cr(OPP)(py)2]ClO4 from the ESR spectrum in frozen 1,2-dichloroethane solution at 5 K. These results suggest that the OPP2− ligand is distorted both in solid and in solution, and that the axial ligand would exert some effects on the porphyrin distortion. |
| Keywords: | Chromium Porphyrin Ligand effects X-ray diffraction EPR spectroscopy |
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