Thermodynamics and Photodynamics of a Monoprotonated Porphyrin Directly Stabilized by Hydrogen Bonding with Polar Protic Solvents.
Addition of 1 equiv of TFA to an acetone solution containing dodecaphenylporphyrin (H2DPP) in the presence of 10 % MeOH (v/v) resulted in selective formation of a monoprotonated form (H3DPP+), in sharp contrast to protonation of H2DPP directly affording a diprotonated form (H4DPP2+) in acetone in the absence of MeOH. The crucial role of MeOH for selective H3DPP+formation was interpreted as hydrogen-bonding stabilization of H3DPP+, since a MeOH molecule was found to form hydrogen bonds with an NH proton of H3DPP+in the crystal. The selectivity of H3DPP+formation was evaluated by the formation yield of H3DPP+, which increased when elevating the portion of MeOH (0-10 %) in acetone with saturation behavior, suggesting that H3DPP+is stabilized by hydrogen bonding with MeOH even in solution, together with the thermodynamic parameters determined from a van't Hoff plot based on the spectroscopic titration. Femto- and nanosecond laser flash photolysis allowed us to elucidate the photodynamics of H3DPP+in intermolecular photoinduced electron transfer (ET) from ferrocene derivatives as one-electron donors to the triplet excited state of H3DPP+as an electron acceptor. The second-order rate constants of the ET reactions were evaluated in light of the Marcus theory of ET. The reorganization energy of ET was determined to be 1.87 eV, which is slightly larger than that of H4DPP2+in acetonitrile (1.69 eV), due to larger structural change upon ET than that of H4DPP2+.
Department of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba and CREST (JST), 1-1-1 Tennoudai, Tsukuba, Ibaraki, 305-8571, Japan.
Wataru
W
Suzuki
Department of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba and CREST (JST), 1-1-1 Tennoudai, Tsukuba, Ibaraki, 305-8571, Japan.
Hiroaki
H
Kotani
Department of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba and CREST (JST), 1-1-1 Tennoudai, Tsukuba, Ibaraki, 305-8571, Japan.
Tomoya
T
Ishizuka
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka, 565-0871, Japan.|Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 120-750, South Korea.
Kei
K
Ohkubo
Institute for Materials Chemistry and Engineering, Kyushu University, Motooka, Nishi-Ku, Fukuoka, 819-0395, Japan.
Yoshihito
Y
Shiota
Institute for Materials Chemistry and Engineering, Kyushu University, Motooka, Nishi-Ku, Fukuoka, 819-0395, Japan.
Kazunari
K
Yoshizawa
Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 120-750, South Korea.|Faculty of Science and Technology, Meijo University, SENTAN, Science and Technology Agency (JST), Nagoya, Aichi, 468-8502, Japan.
Shunichi
http://orcid.org/0000-0002-3559-4107
S
Fukuzumi
Department of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba and CREST (JST), 1-1-1 Tennoudai, Tsukuba, Ibaraki, 305-8571, Japan.
Takahiko
http://orcid.org/0000-0001-9941-8375
T
Kojima
electron transfer; hydrogen bonds; monoprotonated porphyrins; nonplanar porphyrins; polar protic solvents