TY - JOUR
T1 - Synthesis, Structural and Optical Properties of Tetrabenzoporphyrin Complexes Bearing Four or Eight Peripheral Phenyl Groups
AU - Furuyama, Taniyuki
AU - Okujima, Tetsuo
AU - Muramatsu, Kota
AU - Takahashi, Yuichi
AU - Mikami, Akihiro
AU - Fukumura, Tomoteru
AU - Mori, Shigeki
AU - Nakae, Takahiro
AU - Takase, Masayoshi
AU - Uno, Hidemitsu
AU - Kobayashi, Nagao
N1 - Funding Information:
This work was supported by JSPS KAKENHI Grant Numbers 18K19071 (TF), JP26410052 (TO), JP25110003 (HU), and 18K05076 (NK). TF also thanks The Kyoto Technoscience Center Foundation and Kanazawa University SAKIGAKE Project 2018. We thank the Advanced Research Support Center in Ehime University for permission in obtaining the MALDI-TOF mass spectra.
Publisher Copyright:
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/6/2
Y1 - 2019/6/2
N2 - A series of free-base and phosphorus(V) complexes of tetrabenzoporphyrin (TBP) and some phosphorus(V) porphyrins containing four or eight phenyl groups on the periphery have been synthesized and characterized by X-ray crystallography, electronic absorption, and magnetic circular dichroism (MCD) spectroscopy, together with quantum chemical calculations. All phosphorus TBP and meso-tetraphenyl porphyrin complexes adapted ruffled conformations due to the small P(V) ion, although the Zn(II)TBPs containing eight phenyl (Φ) groups at the so-called β and α positions showed planar and saddled structures in the solid state, due to, respectively, marginal or severe steric hindrance between the neighboring Φ groups. All P(V)TBPs showed the Soret and Q bands beyond 450 and 700 nm, respectively, which are some of the longest wavelengths exhibited by metallated TBPs reported to date. Of the eight Φ group-substituted P(V)TBPs, those substituted at α positions always showed absorption bands at longer wavelengths than those at β positions, which was reproduced by calculated absorption spectra. The Soret band positions of meso-tetraphenylated P(V) species without fused benzo-groups (ca. 430–440 nm) were also some of the longest among metalloporphyrins of this type.
AB - A series of free-base and phosphorus(V) complexes of tetrabenzoporphyrin (TBP) and some phosphorus(V) porphyrins containing four or eight phenyl groups on the periphery have been synthesized and characterized by X-ray crystallography, electronic absorption, and magnetic circular dichroism (MCD) spectroscopy, together with quantum chemical calculations. All phosphorus TBP and meso-tetraphenyl porphyrin complexes adapted ruffled conformations due to the small P(V) ion, although the Zn(II)TBPs containing eight phenyl (Φ) groups at the so-called β and α positions showed planar and saddled structures in the solid state, due to, respectively, marginal or severe steric hindrance between the neighboring Φ groups. All P(V)TBPs showed the Soret and Q bands beyond 450 and 700 nm, respectively, which are some of the longest wavelengths exhibited by metallated TBPs reported to date. Of the eight Φ group-substituted P(V)TBPs, those substituted at α positions always showed absorption bands at longer wavelengths than those at β positions, which was reproduced by calculated absorption spectra. The Soret band positions of meso-tetraphenylated P(V) species without fused benzo-groups (ca. 430–440 nm) were also some of the longest among metalloporphyrins of this type.
KW - Absorption spectra
KW - Electronic structure
KW - Phenyl group
KW - Phosphorus
KW - Tetrabenzoporphyrin
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U2 - 10.1002/ejoc.201900528
DO - 10.1002/ejoc.201900528
M3 - Article
AN - SCOPUS:85066104782
VL - 2019
SP - 3224
EP - 3235
JO - Justus Liebigs Annalen der Chemie
JF - Justus Liebigs Annalen der Chemie
SN - 0075-4617
IS - 20
ER -