Structural Control of Nonadiabatic Bond Formation: The Photochemical Formation and Stability of Substituted 4a,4b-Dihydrotriphenylenes
Link to Publication: JPCA Publication
Contributing Authors: Josh Snyder, Art Bragg
Date Published: April 7, 2015
Nonadiabatic photocyclization makes bonds and is the first step in the photoinduced cyclodehydrogenation of ortho-arenes to yield polycyclic aromatic hydrocarbons. How molecular structure alters potential-energy landscapes, excited-state dynamics, and stabilities of reactants and intermediates underlies the feasibility of desirable photochemistry. In order to gain insight into these structure–dynamics relationships, we have used femtosecond transient absorption spectroscopy (TAS) to examine photoinduced dynamics of 1,2,3-triphenylbenzene (TPB) and ortho-quaterphenyl (OQTP), phenyl-subsituted analogues of ortho-terphenyl (OTP). Dynamics of TPB and OTP are quite similar: TPB exhibits fast (7.4 ps) excited-state decay with concomitant formation and vibrational relaxation of 9-phenyl-dihydrotriphenylene (9-phenyl DHT). In contrast, photoexcited OQTP exhibits multistate kinetics leading to formation of 1-phenyl DHT. Excited-state calculations reveal the existence of two distinct minima on the OQTP S1 surface and, together with photophysical data, support a mechanism involving both direct cyclization by way of an asymmetric structure and indirect cyclization by way of a symmetric quinoid-like minimum. Temperature-dependent nanosecond TAS was utilized to assess the relative stabilities of intermediates, substantiating the observed trend in photochemical reactivity OTP > OQTP > TPB. In total, this work demonstrates how specific structural variations alter the course of the excited-state dynamics and photoproduct stability that underlies desired photochemistry.