TY - JOUR
T1 - NH Tautomerism of a Quadruply Fused Porphyrin
T2 - Rigid Fused Structure Delays the Proton Transfer
AU - Saegusa, Yuta
AU - Ishizuka, Tomoya
AU - Shiota, Yoshihito
AU - Yoshizawa, Kazunari
AU - Kojima, Takahiko
N1 - Funding Information:
This work was supported by Grants-in-Aid (Nos. 25410033, 15K13710, 16K05739, 17H03117, 24109014, and 24245011) and a Grant-in-Aid for JSPS Fellows (16J05288 to Y.S.) from Japan Society for the Promotion of Science (JSPS). T.I. also appreciates financial support from The Tokuyama Science Foundation.
PY - 2018/1/11
Y1 - 2018/1/11
N2 - We report herein NH tautomerism of a freebase derivative of a quadruply fused porphyrin (H2QFP-Mes, 3), which has one mesityl group at one of the β-positions of the nonfused pyrroles to lower the structural symmetry, allowing us to observe the NH tautomerism with 1H NMR spectroscopy. Compound 3 was revealed to have the two inner NH protons on the two nonfused pyrroles, and the NH tautomerism of 3 was evidenced by variable-temperature (VT) 1H NMR experiments in various deuterated solvents. The VT-NMR studies revealed that the activation barrier for the NH tautomerism of 3 was larger than that of tetraphenylporphyrin. The positive activation entropy (ΔS‡ = 89 J mol-1 K-1), determined for the NH tautomerism, can be explained by dissociation of the π-π stacked dimer structure of 3 in the ground state, as evidenced by the crystal structure and NMR measurements. On the basis of the kinetic studies and density functional theory calculations, the stability of intermediates in the NH tautomerism of 3 and the transition states have been discussed in detail.
AB - We report herein NH tautomerism of a freebase derivative of a quadruply fused porphyrin (H2QFP-Mes, 3), which has one mesityl group at one of the β-positions of the nonfused pyrroles to lower the structural symmetry, allowing us to observe the NH tautomerism with 1H NMR spectroscopy. Compound 3 was revealed to have the two inner NH protons on the two nonfused pyrroles, and the NH tautomerism of 3 was evidenced by variable-temperature (VT) 1H NMR experiments in various deuterated solvents. The VT-NMR studies revealed that the activation barrier for the NH tautomerism of 3 was larger than that of tetraphenylporphyrin. The positive activation entropy (ΔS‡ = 89 J mol-1 K-1), determined for the NH tautomerism, can be explained by dissociation of the π-π stacked dimer structure of 3 in the ground state, as evidenced by the crystal structure and NMR measurements. On the basis of the kinetic studies and density functional theory calculations, the stability of intermediates in the NH tautomerism of 3 and the transition states have been discussed in detail.
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U2 - 10.1021/acs.jpcb.7b10945
DO - 10.1021/acs.jpcb.7b10945
M3 - Article
C2 - 29224345
AN - SCOPUS:85040609013
VL - 122
SP - 316
EP - 327
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
SN - 1520-6106
IS - 1
ER -