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

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journal contribution
posted on 2023-03-17, 17:37 authored by Arvind Barak, Nishant Dhiman, Floriane Sturm, Florian Rauch, Yapamanu Adithya Lakshmanna, Karen S. Findlay, Andrew Beeby, Todd B. Marder, Siva Umapathy
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.