TY - JOUR
T1 - Benzo-Tetrathiafulvalene- (BTTF-) Annulated Expanded Porphyrins
T2 - Potential Next-Generation Multielectron Reservoirs
AU - Jana, Atanu
AU - Ishida, Masatoshi
AU - Furuta, Hiroyuki
N1 - Funding Information:
A.J. is grateful to GITAM. Part of the work at Kyushu University was supported by Grants‐in‐Aid (JP19K05439, JP19H04586, and JP20H00406) from the Japan Society for the Promotion of Science (JSPS). The authors gratefully acknowledge Professor Dongho Kim and Dr. Young Mo Sung, Yonsei University, South Korea, for providing the TAS data; Dr. Inhyok Park and Professor Samson Lee, Gyeongsang National University, South Korea, for providing the crystallographic data; and Dr. Vincent M. Lynch, The University of Texas at Austin for his valuable feedback regarding the crystal graphic analysis of . BTT7‐F
Publisher Copyright:
© 2020 Wiley-VCH GmbH
PY - 2021/3/1
Y1 - 2021/3/1
N2 - Two sterically crowded benzo-tetrathiafulvalene (BTTF)-annulated expanded porphyrins (BTTF7-F and BTTF8) are synthesized. Detailed photophysical investigations reveal their intrinsic intramolecular charge transfer (CT) character, originated from partial electron transfer from electron-rich TTF units to the relatively electron-deficient macrocyclic core. This finding stands in contrast to what was observed in the previously reported Figure-of-eight conformer of BTTF-annulated [28]hexaphyrin (BTTF6), in which a typical π–π* electronic transition from HOMO to LUMO was observed. However, core expansion in BTTF7-F and BTTF8 makes the oligopyrrole macrocyclic cores relatively more electron-deficient, facilitating the effective intramolecular CT process. Comparative electrochemical investigations reveal that the current generated at the oxidative region is directly proportional to the number of TTF units attached to the macrocyclic core. This work demonstrates the control of the intramolecular CT process through incremental addition of TTF units to the macrocyclic core. Facile multielectron electrochemical oxidations of these expanded porphyrins suggest that they behave like potential multielectron reservoirs.
AB - Two sterically crowded benzo-tetrathiafulvalene (BTTF)-annulated expanded porphyrins (BTTF7-F and BTTF8) are synthesized. Detailed photophysical investigations reveal their intrinsic intramolecular charge transfer (CT) character, originated from partial electron transfer from electron-rich TTF units to the relatively electron-deficient macrocyclic core. This finding stands in contrast to what was observed in the previously reported Figure-of-eight conformer of BTTF-annulated [28]hexaphyrin (BTTF6), in which a typical π–π* electronic transition from HOMO to LUMO was observed. However, core expansion in BTTF7-F and BTTF8 makes the oligopyrrole macrocyclic cores relatively more electron-deficient, facilitating the effective intramolecular CT process. Comparative electrochemical investigations reveal that the current generated at the oxidative region is directly proportional to the number of TTF units attached to the macrocyclic core. This work demonstrates the control of the intramolecular CT process through incremental addition of TTF units to the macrocyclic core. Facile multielectron electrochemical oxidations of these expanded porphyrins suggest that they behave like potential multielectron reservoirs.
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U2 - 10.1002/chem.202005021
DO - 10.1002/chem.202005021
M3 - Article
C2 - 33347663
AN - SCOPUS:85099962385
SN - 0947-6539
VL - 27
SP - 4466
EP - 4472
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 13
ER -