Premium
Porphyrinylboranes Synthesized via Porphyrinyllithiums
Author(s) -
Fujimoto Keisuke,
Yorimitsu Hideki,
Osuka Atsuhiro
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201502215
Subject(s) - porphyrin , intramolecular force , chemistry , lithium (medication) , photochemistry , butyllithium , boron , nucleophile , electrochemistry , dimer , medicinal chemistry , polymer chemistry , organic chemistry , catalysis , electrode , medicine , endocrinology
As the most nucleophilic porphyrins , meso‐ or β‐lithiated porphyrins were generated by iodine–lithium exchange reactions of the corresponding iodoporphyrins with n ‐butyllithium at −98 °C. Porphyrinyllithiums thus prepared were used for synthesis of dimesitylporphyrinylboranes through reactions with fluorodimesitylborane. The boryl groups proved to serve as an electron‐accepting unit to alter the photophysical and electrochemical properties. In addition, 5‐diarylamino‐15‐dimesitylboryl‐substituted donor–accepter porphyrins showed increased intramolecular charge‐transfer character in the S 1 state. Furthermore, the reaction of β‐lithiated porphyrin with dichloromesitylborane provided a boron‐bridged porphyrin dimer, which exhibited a conjugative interaction between two porphyrin units through the vacant p‐orbital on the boron center.