Tracking Twisted Intramolecular Charge Transfer and Isomerization Dynamics in 9-(2,2-Dicyanovinyl) Julolidine Using Femtosecond Stimulated Raman Spectroscopy

School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China

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Corresponding author: E-mail: huangyf@shanghaitech.edu.cn; liuwm@shanghaitech.edu.cn

摘要

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Abstract: Understanding the mechanism of how micro-environments affect molecular rotors helps the design and development of molecular sensors. Here, we utilized femtosecond stimulated Raman spectroscopy, helped by quantum chemical calculation, to study the structural dynamics of 9-(2,2-dicyanovinyl) julolidine in cyclohexane, THF, and DMSO solvents. The obtained hydrogen out-of-plane (HOOP) mode and symmetric/anti-symmetric stretching of two nitriles (C≡N) indicate the rotation of the C₇=C₈ double bond and C4−C₇ single bond in the excited-state which provide two non-radiative decay channels to effectively quench the excited-state population on local excited (LE) state via isomerization and twisted intramolecular charge transfer (TICT). In nonpolar solvent, the excited molecule in the LE state radiatively relaxes to the ground state or performs rotation motions via isomerization and TICT to deactivate fluorescence in the LE state. In the polar solvent, the isomerization plays a role to quench the LE state population; simultaneously, an ultrafast intramolecular charge transfer (ICT) from LE state to emissive ICT state was followed by an TICT between ICT state and dark ICT’ state.
- Femtosecond stimulated Raman spectroscopy /
- Twisted intralomecular charge transfer /
- Isomerization /
- Hydrogen out-of plane mode

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1. (a) Natural and zwitterionic molecular structure of JDMN, (b) proposed model for JDMN in nonpolar solvent, and (c) proposed model for JDMN in polar solvent.

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Figure 1. (a) Steady-state absorption and (b) fluorescence spectra of JDMN in cyclohexane, THF, and DMSO; The blue dashed line (Cyclo Abs) in (b) is the mirror image of the absorption spectrum in cyclohexane.

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Figure 2. (a) FSRS spectra of JDMN in cyclohexane, THF, and DMSO under 1100 cm⁻¹. (b) Transient Raman amplitudes of the HOOP mode in three solvents.

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Figure 3. DFT calculation showing the optimized structure of (a) HOOP mode, (b) anti-symmetric (C≡N) stretching mode, and (c) symmetric (C≡N) stretching mode.

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Figure 4. Two-dimensional plot of the FSRS spectra of JDMN in (a) cyclohexane, (b) THF, and (c) DMSO above 2000 cm⁻¹. Transient Raman amplitudes of vibrational modes in (d) cyclohexane, (e) THF, and (f) DMSO.

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Figure 5. The difference in peak frequency between the symmetric and the anti-symmetric stretching modes in (a) cyclohexane (45 cm^-1), (b) THF (39 cm^-1), and (c) DMSO (32 cm^-1) at delayed time zero of FSRS spectra.

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