Deciphering the ultrafast dynamics of a new tetraphenylethylene derivative in solutions: charge separation, phenyl ring rotation and CC bond twisting

Literature Information

Publication Date 2022-12-12
DOI 10.1039/D2CP05220B
Impact Factor 3.676
Authors

Mario de la Hoz Tomás, Mao Yamaguchi, Boiko Cohen, Ichiro Hisaki, Abderrazzak Douhal


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Abstract

Tetraphenylethylene (TPE) derivatives are one of the fundamental units for developing aggregation induced emission (AIE) scaffolds. However, the underlying mechanisms implicated in the relaxation of the excited TPE remain a topic of ongoing discussion, while the effect of bulky substituents on its photobehaviour is still under scrutiny. Here, we report a detailed study of the photophysical properties of a new symmetrical and bulky TPE derivative with terphenyl groups (TTECOOBu) in solvents of different polarities and viscosities. Using femto- to nanosecond (fs–ns) time-resolved absorption and emission techniques, we elucidated the role of the phenyl group rotations and core ethylene bond twisting in its behaviour. We demonstrate that TTECOOBu in DCM solutions undergoes a 600 fs charge separation along the ethylene bond leading to a resonance structure with a lifetime of ∼1 ns. The latter relaxes via two consecutive events: a twisting of the ethylene bond (∼ 9 ps) and a rotation of the phenyl rings (∼ 30 ps) leading to conformationally-relaxed species with a largely Stokes-shifted emission (∼ 12 500 cm−1). The formation of the red-emitting species clearly depends on the solvent viscosity and rigidity of the medium. Contrary to the photobehavior in the highly viscous triacetin or rigid polymer matrix of PMMA, a reversible mechanism was observed in DCM and DMF solutions. These results provide new findings on the ultrafast mechanisms of excited TPE derivatives and should help in the development of new molecular rotors with interesting AIE properties for photonic applications.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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