Bis(tercarbazole) pyrene and tetrahydropyrene derivatives: photophysical and electrochemical properties, theoretical modeling, and OLEDs

Abstract

2,7-Bis(3,3′′,6,6′′-tetra(tert-butyl)-9′H-9,3′:6′,9′′-tercarbazol-9-yl)-4,5,9,10-tetrahydropyrene (3) and 2,7-bis(3,3′′,6,6′′-tetra(tert-butyl)-9′H-9,3′:6′,9′′-tercarbazol-9-yl)pyrene (4), along with a model compound, 3,3′′,6,6′′-tetra(tert-butyl)-9′-(4-(tert-butyl)phenyl)-9′H-9,3′:6′,9′′-tercarbazole (6), have been synthesized using microwave-assisted palladium-catalyzed coupling and compared to analogous 3,6-di(tert-butyl)carbazol-9-yl species (1, 2, and 5). Time-dependent density functional theory (TDDFT) calculations reveal absorption with quadrupolar (ter)carbazole-to-bridge CT character for 1–4. Compound 4 is unusual in showing dual fluorescence in a number of solvents; the longer wavelength feature of which is markedly more solvatochromic than the bands of the other compounds. Following the observed three oxidations on the TCz model compound 6, compounds 3 and 4 can be electrochemically reversibly oxidized to hexacations with four oxidation and three oxidation steps in a 2 : 2 : 1 : 1 and a 2 : 2 : 2 current ratio, respectively. Tercarbazole derivatives 3 and 4 have been used as the emissive layers of simple solution-processed few-layer organic light-emitting diodes.