Issue 7, 2017

The photophysics of naphthalene dimers controlled by sulfur bridge oxidation

Abstract

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.

Graphical abstract: The photophysics of naphthalene dimers controlled by sulfur bridge oxidation

Supplementary files

Article information

Article type
Edge Article
Submitted
22 Mar 2017
Accepted
20 Apr 2017
First published
24 Apr 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 4941-4950

The photophysics of naphthalene dimers controlled by sulfur bridge oxidation

C. Climent, M. Barbatti, M. O. Wolf, C. J. Bardeen and D. Casanova, Chem. Sci., 2017, 8, 4941 DOI: 10.1039/C7SC01285C

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements