TY - JOUR
T1 - Synthesis, Photophysical, and Electrochemical Properties of Pyrenes Substituted with Donors or Acceptors at the 4- or 4,9-Positions
AU - Ji, Lei
AU - Krummenacher, Ivo
AU - Friedrich, Alexandra
AU - Lorbach, Andreas
AU - Haehnel, Martin
AU - Edkins, Katharina
AU - Braunschweig, Holger
AU - Marder, Todd B.
PY - 2018/4/6
Y1 - 2018/4/6
N2 - We report herein an efficient and direct functionalization of the 4,9-positions of pyrene by Ir-catalyzed borylation. Three pinacol boronates (-Bpin), including 4-(Bpin)-2,7-di-(tert-butyl)pyrene (5), 4,9-bis(Bpin)-2,7-di-(tert-butyl)pyrene (6), and 4,10-bis(Bpin)-2,7-di-(tert-butyl)pyrene (7) were synthesized. The structures of 6 and 7 have been confirmed by single-crystal X-ray diffraction. To demonstrate the utility of these compounds, donor (NPh2) substituted compounds 4-diphenylamino-2,7-di-(tert-butyl)pyrene (1) and 4,9-bis(diphenylamino)-2,7-di-(tert-butyl)pyrene (2) have been synthesized on a gram scale. Acceptor (BMes2) substituted compounds 4,9-bis(BMes2)pyrene (3) and 4,9-bis(BMes2)-1,2,3,6,7,8-hexahydropyrene (4) were synthesized for comparison. The photophysical and electrochemical properties of compounds 1-4 have been studied both experimentally and theoretically. The S0S1 transitions of the 4,9-disubstituted pyrenes, 1-3, are allowed, with moderate fluorescence quantum yields and radiative decay rates. The photophysical and electrochemical properties of 1-3 were compared with the 2,6-naphthalenylene-cored compound 4 as well as the previously reported 2,7- and 1,6- pyrenylene-cored compounds.
AB - We report herein an efficient and direct functionalization of the 4,9-positions of pyrene by Ir-catalyzed borylation. Three pinacol boronates (-Bpin), including 4-(Bpin)-2,7-di-(tert-butyl)pyrene (5), 4,9-bis(Bpin)-2,7-di-(tert-butyl)pyrene (6), and 4,10-bis(Bpin)-2,7-di-(tert-butyl)pyrene (7) were synthesized. The structures of 6 and 7 have been confirmed by single-crystal X-ray diffraction. To demonstrate the utility of these compounds, donor (NPh2) substituted compounds 4-diphenylamino-2,7-di-(tert-butyl)pyrene (1) and 4,9-bis(diphenylamino)-2,7-di-(tert-butyl)pyrene (2) have been synthesized on a gram scale. Acceptor (BMes2) substituted compounds 4,9-bis(BMes2)pyrene (3) and 4,9-bis(BMes2)-1,2,3,6,7,8-hexahydropyrene (4) were synthesized for comparison. The photophysical and electrochemical properties of compounds 1-4 have been studied both experimentally and theoretically. The S0S1 transitions of the 4,9-disubstituted pyrenes, 1-3, are allowed, with moderate fluorescence quantum yields and radiative decay rates. The photophysical and electrochemical properties of 1-3 were compared with the 2,6-naphthalenylene-cored compound 4 as well as the previously reported 2,7- and 1,6- pyrenylene-cored compounds.
KW - absorption
KW - aromatic compounds
KW - hydrocarbons
KW - redox reactions
KW - substituents
UR - https://pubs.acs.org/doi/10.1021/acs.joc.7b03227
U2 - 10.1021/acs.joc.7b03227
DO - 10.1021/acs.joc.7b03227
M3 - Article
SN - 0022-3263
VL - 83
SP - 3599
EP - 3606
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 7
ER -