Ultrafast Dynamics of Hydrogen Bond Breaking and Making in the Excited State of Fluoren-9-one: Time-Resolved Visible Pump–IR Probe Spectroscopic Study

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• 作者：Rajib Ghosh ; Aruna K. Mora ; Sukhendu Nath ; Dipak K. Palit
• 刊名：Journal of Physical Chemistry B
• 出版年：2017
• 出版时间：February 9, 2017
• 年：2017
• 卷：121
• 期：5
• 页码：1068-1080
• 全文大小：807K
• ISSN：1520-5207

文摘

The fluoren-9-one (FL) molecule, with a single hydrogen bond-accepting site (C═O group), has been used as a probe for investigation of the dynamics of a hydrogen bond in its lowest excited singlet (S₁) state using the subpicosecond time-resolved visible pump–IR probe spectroscopic technique. In 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), a strong hydrogen bond-donating solvent, the formation of an FL–alcohol hydrogen-bonded complex in the ground electronic (S₀) state is nearly complete, with a negligible concentration of the FL molecule remaining free in solution. In addition to the presence of a band due to the hydrogen-bonded complex in the transient IR spectrum recorded immediately after photoexcitation of FL in HFIP solution, appearance of the absorption band due to a free C═O stretch provides confirmatory evidence of ultrafast photodissociation of hydrogen bonds in some of the complexes formed in the S₀ state. The peak-shift dynamics of the C═O stretch bands reveal two major relaxation pathways, namely, vibrational relaxation in the S₁ state of the free FL molecules and the solvent reorganization process in the hydrogen-bonded complex. The latter process follows bimodal exponential dynamics involving hydrogen bond-making and hydrogen bond-reorganization processes. The similar lifetimes of the S₁ states of the FL molecules, both free and hydrogen-bonded, suggest establishment of a dynamic equilibrium between these two species in the excited state. However, investigations in two other weaker hydrogen bond-donating solvents, namely, trifluoroethanol (TFE) and perdeuterated methanol (CD₃OD), reveal different features of peak-shift dynamics because of the prominence of the vibrational relaxation process over the hydrogen bond-reorganization process during the early time.