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Nandita Ghosh

Publications and source records attributed to Nandita Ghosh.

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Steric guided change of electron transfer mechanism in benzene.

In fluorescence quenching study via electron transfer (ET), the quenching rate constant (k(q)) values generally decrease with lowering of quencher concentration, since smaller concentration of quencher always leads to a red shift in the donor-acceptor (D-A) distance in ET [M. Tachiya, S. Murata, J. Phys. Chem. 96 (1992) 8441; S. Murata, M. Tachiya, J. Phys. Chem. 100 (1996) 4064; L. Burel, M. Mastafavi, S. Murata, M. Tachiya, J. Phys. Chem. A 103 (1999) 5882]. However, while doing a comparative study with different carbazole (CZ) derivatives-1,4-dicyanobenzene (DCB) systems in benzene (BZ), we observed a deviation from that normal behaviour. It was found that for all of them with lower quencher (DCB) concentration, k(q) values actually increase instead of the expected reduction. Exceptionally, for simple CZ (C12H9N) with decrease in concentration of DCB, k(q) values can even reach the order of energy transfer (10(11) s(-1)). Interestingly, it is not observed when toluene (TL) or xylene (XY) is used as solvent. To explain this unique observation, a sandwich type of molecular structure is predicted, where BZ sliding in between CZ and DCB brings them closer enough, imparting more through bond character to CZ-DCB interaction and hence a higher rate of ET (k(q)) is observed [L. Burel, M. Mastafavi, S. Murata, M. Tachiya, J. Phys. Chem. A. 103 (1999) 5882].

Benzene↗

Steric effect on fluorescence quenching.

In this communication we have reported the steric effect on the fluorescence quenching rate constants of the electron transfer (ET) process. We have done a comparative study using donor (D)-acceptor (A) systems with different exergonicity (-deltaG(f)). Different carbazole derivatives (CZ): 1,4-dicyanobenzene (DCB) systems (-deltaG(f) = 0.7-0.8 eV) were found to be among those limiting systems that show a clear-cut steric dominance in the process of fluorescence quenching. It is known that with increasing exergonicity the ET distance increases and hence steric dependence becomes insignificant. On the other hand, with decreasing exergonicity the ET distance decreases and a pronounced steric dominance should be observed. However, in the D-A systems having lower exergonicity compared to CZ-DCB systems, this steric dominance is observed only in polar medium. In non-polar medium due to exciplex formation the D-A distance effectively becomes much longer and therefore no steric dominance is observed.

Carbazoles↗

Influence of steric factors on exciplex energy and magnetic field effect.

With the advent of spin chemistry, magnetic field effect (MFE) on exciplex luminescence has emerged as an important domain of research. MFE is a diffusion controlled phenomenon and hence is solvent dielectric (epsilon) dependent. It maximizes at a particular epsilon (epsilon(max)) for a specific exciplex system. Various attempts have been made to explain the variation of this epsilon(max) from one exciplex to another. In our present work we have succeeded for the first time to enmark the energy of exciplex (E(ex)) as the prime factor in determining the epsilon(max). We have indicated a definite inverse correlation (1:1) between epsilon(max) and E(ex). We have also tried to correlate some parameters that are important in exciplex formation, e.g. Charton's steric constant (nu(c)), repulsive energy (R(e)) and E(ex).

Carbazoles↗