The photophysics of naphthalene dimers controlled by sulfur bridge oxidation

作者：Climent Claudia; Barbatti Mario; Wolf Michael O; Bardeen Christopher J; Casanova David^*

来源：Chemical Science, 2017, 8(7): 4941-4950.

DOI：10.1039/c7sc01285c

In this study we investigate in detail the photophysics of naphthalene dimers covalently linked by a sulfur atom. We explore and rationalize how the oxidation state of the sulfur-bridging atom directly influences the photoluminescence of the dimer by enhancing or depriving its radiative and non-radiative relaxation pathways. In particular, we discuss how oxidation controls the amount of electronic transfer between the naphthalene moieties and the participation of the SOn bridge in the low-lying electronic transitions. We identify the sulfur electron lone-pairs as crucial actors in the non-radiative decay of the excited sulfide and sulfoxide dimers, which are predicted to proceed via a conical intersection (CI). Concretely, two types of CI have been identified for these dimers, which are associated with the photo-induced pyramidal inversion and reverse fragmentation mechanisms found in aryl sulfoxide dimers. The obtained results and conclusions are general enough to be extrapolated to other sulfur-bridged conjugated dimers, therefore proportionating novel strategies in the design of strongly photoluminescent organic molecules with controlled charge transfer.

• 出版日期2017-7-1