TY - JOUR
T1 - Synthesis, Optical Properties, and Electrochemical Behavior of 5,10,15,20-Tetraaryl-5,15-diazaporphyrin-Amine Hybrids
AU - Satoh, Yuna
AU - Fujita, Yutaro
AU - Muramatsu, Naoya
AU - Furukawa, Ko
AU - Ikoma, Tadaaki
AU - Minoura, Mao
AU - Nakano, Haruyuki
AU - Matano, Yoshihiro
N1 - Funding Information:
This work was supported by JSPS KAKENHI (18H01961 to YM, and 18K05036, 21K04980 to HN) and the Research Program of ?Five-star Alliance? in ?NJRC Mater. & Dev.? (20214029), a research grant of Nihon Kagaku Kenkyukai (492(R)) to TI. We also express our gratitude to the SPring-8 synchrotron, where synchrotron radiation experiments were performed at the BL40XU beamline with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (proposals 2020A0557, 2020A0834, 2020A1056, 2020A1644, 2020A1656, and 2021A1592).
Funding Information:
This work was supported by JSPS KAKENHI (18H01961 to YM, and 18K05036, 21K04980 to HN) and the Research Program of “Five‐star Alliance” in “NJRC Mater. & Dev.” (20214029), a research grant of Nihon Kagaku Kenkyukai (492(R)) to TI. We also express our gratitude to the SPring‐8 synchrotron, where synchrotron radiation experiments were performed at the BL40XU beamline with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (proposals 2020A0557, 2020A0834, 2020A1056, 2020A1644, 2020A1656, and 2021A1592).
Publisher Copyright:
© 2021 Wiley-VCH GmbH.
PY - 2021/10
Y1 - 2021/10
N2 - This work reports a series of covalently linked hybrids comprising 5,10,15,20-tetraaryl-5,15-diazaporphyrinoids (M-TADAP; M = Ni, Zn, Cu) and amines. M-TADAP-amine hybrids were prepared via the metal-templated cyclization of the corresponding metal(II)-dipyrrin complexes and redox reactions on the DAP unit. In the UV/vis/near-IR absorption spectra of the hybrids containing an 18π-electron DAP ring, broad charge-transfer bands were observed, reflecting the electron-donating property of the para-aminophenyl groups and the electron-accepting property of the 18π TADAP dication. The electrochemical behavior of the M-TADAP-amine hybrids was strongly dependent on the structure of the peripheral amine units. Further electrochemical oxidation of the hybrids bearing N-Ph groups conceivably generated amine-centered radicals, which sequentially underwent irreversible coupling to form benzidine-linked M-TADAP polymer films. The Ni-TADAP-benzidine polymer exhibited the electric conductivity of 2×10−3 S m−1.
AB - This work reports a series of covalently linked hybrids comprising 5,10,15,20-tetraaryl-5,15-diazaporphyrinoids (M-TADAP; M = Ni, Zn, Cu) and amines. M-TADAP-amine hybrids were prepared via the metal-templated cyclization of the corresponding metal(II)-dipyrrin complexes and redox reactions on the DAP unit. In the UV/vis/near-IR absorption spectra of the hybrids containing an 18π-electron DAP ring, broad charge-transfer bands were observed, reflecting the electron-donating property of the para-aminophenyl groups and the electron-accepting property of the 18π TADAP dication. The electrochemical behavior of the M-TADAP-amine hybrids was strongly dependent on the structure of the peripheral amine units. Further electrochemical oxidation of the hybrids bearing N-Ph groups conceivably generated amine-centered radicals, which sequentially underwent irreversible coupling to form benzidine-linked M-TADAP polymer films. The Ni-TADAP-benzidine polymer exhibited the electric conductivity of 2×10−3 S m−1.
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U2 - 10.1002/cplu.202100429
DO - 10.1002/cplu.202100429
M3 - Article
C2 - 34669265
AN - SCOPUS:85118212687
VL - 86
SP - 1476
EP - 1486
JO - ChemPlusChem
JF - ChemPlusChem
SN - 2192-6506
IS - 10
ER -