Ultrafast relaxation dynamics of the ecited states of 1-amino- and 1-(N,N-dimethylamino)-fluoren-9-ones

Varne, Mahendra ; Samant, Vaishali ; Mondal, Jahur A. ; Nayak, Sandip K. ; Ghosh, Hirendra N. ; Palit, Dipak K. (2009) Ultrafast relaxation dynamics of the ecited states of 1-amino- and 1-(N,N-dimethylamino)-fluoren-9-ones ChemPhysChem, 10 (17). pp. 2979-2994. ISSN 1439-4235

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Official URL: http://onlinelibrary.wiley.com/doi/10.1002/cphc.20...

Related URL: http://dx.doi.org/10.1002/cphc.200900309

Abstract

The dynamics of the excited states of 1-aminofluoren-9-one (1AF) and 1-(N,N-dimethylamino)-fluoren-9-one (1DMAF) are investigated by using steady-state absorption and fluorescence as well as subpicosecond time-resolved absorption spectroscopic techniques. Following photoexcitation of 1AF, which exists in the intramolecular hydrogen-bonded form in aprotic solvents, the excited-state intramolecular proton-transfer reaction is the only relaxation process observed in the excited singlet (S1) state. However, in protic solvents, the intramolecular hydrogen bond is disrupted in the excited state and an intermolecular hydrogen bond is formed with the solvent leading to reorganization of the hydrogen-bond network structure of the solvent. The latter takes place in the timescale of the process of solvation dynamics. In the case of 1DMAF, the main relaxation pathway for the locally excited singlet, S1(LE), or S1(ICT) state is the configurational relaxation, via nearly barrierless twisting of the dimethylamino group to form the twisted intramolecular charge-transfer, S1(TICT), state. A crossing between the excited-state and ground-state potential energy curves is responsible for the fast, radiationless deactivation and nonemissive character of the S1(TICT) state in polar solvents, both aprotic and protic. However, in viscous but strong hydrogen-bond-donating solvents, such as ethylene glycol and glycerol, crossing between the potential energy surfaces for the ground electronic state and the hydrogen-bonded complex formed between the S1(TICT) state and the solvent is possibly avoided and the hydrogen-bonded complex is weakly emissive.

Item Type:Article
Source:Copyright of this article belongs to John Wiley and Sons.
Keywords:Charge Transfer; Excited States; Hydrogen Bonds; Molecular Dynamics; Transient Absorption Spectroscopy
ID Code:34255
Deposited On:31 Mar 2011 06:08
Last Modified:31 Mar 2011 06:08

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