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Solvent Polarity Governs Ultrafast Structural Dynamics: A Case Study of 4-Dimethylamino-4′-carbomethoxydiphenylacetylene

Barak, A and Dhiman, N and Sturm, F and Rauch, F and Lakshmanna, YA and Findlay, KS and Beeby, A and Marder, TB and Umapathy, S (2022) Solvent Polarity Governs Ultrafast Structural Dynamics: A Case Study of 4-Dimethylamino-4′-carbomethoxydiphenylacetylene. In: Journal of Physical Chemistry C, 127 (12). pp. 5855-5865.

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Official URL: https://doi.org/10.1021/acs.jpcc.2c07691


The compound 4-dimethylamino-4′-carbomethoxydiphenylacetylene (DACM-DPA) is a donor-π-acceptor system that exhibits significant charge transfer character in the excited state in polar solvents. Femtosecond transient absorption measurements in n-hexane, acetonitrile, and methanol exhibit excited-state lifetimes of >2 ns, ∼500 ps, and ∼30 ps, respectively. Femtosecond Raman measurements of DACM-DPA elucidated the intricate structural dynamics during the excited-state evolution by revealing distinct vibrational signatures of DACM-DPA in these solvents. In the case of n-hexane solvent, vibrational bands at 2075 cm-1 (C≡C) and 1600 cm-1 (C═C) stretch exist throughout the excited-state lifetime. However, in the case of polar solvents, the amplitudes of vibrational frequencies at 2098 cm-1 (C≡C), 1618 cm-1 (C═C, acetonitrile), and 1603 cm-1 (C═C, methanol) diminish in a time period of 2.5 ps (acetonitrile) and 6.5 ps (methanol) along with the appearance of new bands at 2082 cm-1 (cumulene stretch) and 1582 cm-1 (quinoid stretch), clearly revealing the formation of an intramolecular charge-separated state. Furthermore, these experimental observations are corroborated by computations using DFT and TD-DFT.

Item Type: Journal Article
Publication: Journal of Physical Chemistry C
Publisher: American Chemical Society
Additional Information: The copyright for this article belongs to American Chemical Society.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 24 Apr 2023 10:17
Last Modified: 24 Apr 2023 10:17
URI: https://eprints.iisc.ac.in/id/eprint/81281

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