TY - JOUR
T1 - Synthesis and properties of rhodium(III) porphyrin cyclic tetramer and cofacial dimer
AU - Fukushima, Keiko
AU - Funatsu, Kenji
AU - Ichimura, Akio
AU - Sasaki, Yoichi
AU - Suzuki, Masamitsu
AU - Fujihara, Tetsuaki
AU - Tsuge, Kiyoshi
AU - Imamura, Taira
PY - 2003/5/19
Y1 - 2003/5/19
N2 - Rhodium(III) porphyrin complexes, [Rh(4-PyT3P)Cl]4 (1) and [Rh(2-PyTB3P)Cl]2 (2) (4-PyT3P = 5-(4-pyridyl)-10,15,20-tritolylporphyrinato dianion, 2-PytB3P = 5-(2-pyridyl)-10,15,20-tri(4-tert-butyl)phenylporphyrinato dianion), were self-assembled and characterized by 1H nuclear magnetic resonance spectroscopy, infrared spectroscopy, and electron spray ionization-mass spectroscopy methods. The spectroscopic results certified that the rhodium porphyrin complexes 1 and 2 have a cyclic tetrameric structure and a cofacial dimeric structure, respectively. The X-ray structure analysis of 1 confirmed the cyclic structure of the complex. The Soret bands of both oligomers were significantly broadened by excitonic interactions between the porphyrin units, compared to those observed for a corresponding analogue of Rh(TTP)(Py)Cl (TTP = 5,10,15,20-tetratolylporphyrinato dianion, Py = pyridine). Stepwise oxidation of the porphyrin rings in the oligomers was observed by cyclic voltammetry. The oligomers 1 and 2 are very stable in solution, and they slowly undergo reactions with pyridine to give corresponding monomer complexes only at high temperatures (∼80 °C).
AB - Rhodium(III) porphyrin complexes, [Rh(4-PyT3P)Cl]4 (1) and [Rh(2-PyTB3P)Cl]2 (2) (4-PyT3P = 5-(4-pyridyl)-10,15,20-tritolylporphyrinato dianion, 2-PytB3P = 5-(2-pyridyl)-10,15,20-tri(4-tert-butyl)phenylporphyrinato dianion), were self-assembled and characterized by 1H nuclear magnetic resonance spectroscopy, infrared spectroscopy, and electron spray ionization-mass spectroscopy methods. The spectroscopic results certified that the rhodium porphyrin complexes 1 and 2 have a cyclic tetrameric structure and a cofacial dimeric structure, respectively. The X-ray structure analysis of 1 confirmed the cyclic structure of the complex. The Soret bands of both oligomers were significantly broadened by excitonic interactions between the porphyrin units, compared to those observed for a corresponding analogue of Rh(TTP)(Py)Cl (TTP = 5,10,15,20-tetratolylporphyrinato dianion, Py = pyridine). Stepwise oxidation of the porphyrin rings in the oligomers was observed by cyclic voltammetry. The oligomers 1 and 2 are very stable in solution, and they slowly undergo reactions with pyridine to give corresponding monomer complexes only at high temperatures (∼80 °C).
UR - http://www.scopus.com/inward/record.url?scp=0037954263&partnerID=8YFLogxK
U2 - 10.1021/ic020652j
DO - 10.1021/ic020652j
M3 - 学術論文
AN - SCOPUS:0037954263
SN - 0020-1669
VL - 42
SP - 3187
EP - 3193
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 10
ER -