Excited-state symmetry breaking in 9,10-dicyanoanthracene-based quadrupolar molecules: the effect of donor-acceptor branch length
File(s)
Published version
Author(s)
Szakacs, Zoltan
Glocklhofer, Florian
Plasser, Felix
Vauthey, Eric
Type
Journal Article
Abstract
Excited-state symmetry breaking is investigated in a series of symmetric 9,10-dicyanoanthracenes linked to electron-donating groups on the 2 and 6 positions via different spacers, allowing for a tuning of the length of the donor–acceptor branches. The excited-state properties of these compounds are compared with their dipolar single-branch analogues. The changes in electronic structure upon their optical excitation are monitored by transient electronic spectroscopy in the visible and near-infrared regions as well as by transient vibrational spectroscopy in the mid-infrared. Our results reveal that, with the shortest branches, electronic excitation remains distributed almost symmetrically over the molecule even in polar environments. Upon increasing the donor–acceptor distance, excitation becomes unevenly distributed and, with the longest one, it fully localises on one branch in polar solvents. The influence of the branch length on the propensity of quadrupolar dyes to undergo excited-state symmetry breaking is rationalised in terms of the balance between interbranch coupling and solvation energy.
Date Issued
2021-07-28
Date Acceptance
2021-07-01
Citation
Physical Chemistry Chemical Physics, 2021, 23 (28), pp.15150-15158
ISSN
1463-9076
Publisher
Royal Society of Chemistry
Start Page
15150
End Page
15158
Journal / Book Title
Physical Chemistry Chemical Physics
Volume
23
Issue
28
Copyright Statement
This journal is © the Owner Societies 2021 This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
License URL
Identifier
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000672996400001&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=a2bf6146997ec60c407a63945d4e92bb
Subjects
2-PHOTON ABSORPTION
Chemistry
Chemistry, Physical
CHROMOPHORES
DESIGN
DYNAMICS
ELECTRON
EXCIPLEX FORMATION
FLUORESCENCE
INTRAMOLECULAR CHARGE-TRANSFER
OPTOELECTRONIC PROPERTIES
Physical Sciences
Physics
Physics, Atomic, Molecular & Chemical
Science & Technology
SOLVENT
Publication Status
Published
Date Publish Online
2021-07-02