Ultrafast Dynamics of the Excited States of 1-(p-Nitrophenyl)-2-(hydroxymethyl)pyrrolidine

Radiation & Photochemistry Division, Bhabha Atomic Research Centre, Mumbai, India.
The Journal of Physical Chemistry A (Impact Factor: 2.69). 03/2012; 116(9):1993-2005. DOI: 10.1021/jp209271u
Source: PubMed


The dynamics of the excited states of 1-(p-nitrophenyl)-2-(hydroxymethyl)pyrrolidine (p-NPP) has been investigated using the subpicosecond transient absorption spectroscopic technique in different kinds of solvents. Following photoexcitation using 400 nm light, conformational relaxation via twisting of the nitro group, internal conversion (IC) and the intersystem crossing (ISC) processes have been established to be the three major relaxation pathways responsible for the ultrafast deactivation of the excited singlet (S(1)) state. Although the nitro-twisting process has been observed in all kinds of solvents, the relative probability of the occurrence of the other two processes has been found to be extremely sensitive to solvent polarity, because of alteration of the relative energies of the S(1) and the triplet (T(n)) states. In the solvents of lower polarity, the ISC is predominant over the IC process, because of near isoenergeticity of the S(1)(ππ*) and T(3)(nπ*) states. On the other hand, in the solvents of very large polarity, the energy of the S(1)(ππ*) state becomes lower than those of both the T(3)(nπ*) and T(2)(nπ*/ππ*) states, but those of the T(1)(ππ*) state and the IC process to the ground electronic (S(0)) state are predominant over the ISC, and hence the triplet yield is nearly negligible. However, in the solvents of medium polarity, the S(1) and T(2) states become isoenergetic and the deactivation of the S(1) state is directed to both the IC and ISC channels. In the solvents of low and medium polarity, following the ISC process, the excited states undergo IC, vibrational relaxation, and solvation in the triplet manifold. On the other hand, following the IC process in the Franck-Condon region of the S(0) state, the vibrationally hot molecules with the twisted nitro group subsequently undergo the reverse nitro-twisting process via dissipation of the excess vibrational energy to the solvent or vibrational cooling.

5 Reads
  • Source
    • "Fig. 12. Simplified scheme for the potential energy surfaces along the nitro torsion/ wag and the amino planarization coordinates for the singlet excited state of 4DNS- B3 in CH 2 Cl 2 . Modified from Ref. [74]. of structural changes are $3.2 and $5.3 kcal/mol, respectively. The small S 0 –S 1 energy gap (8.5 kcal/mol) for the TICT geometry accounts for the ultrafast internal conversion and thus the lack of emission of the TICT state. "
    [Show abstract] [Hide abstract]
    ABSTRACT: The decay pathways with relative quantum efficiencies for photoexcited trans-aminostilbenes in dilute organic solutions at ambient temperature are reviewed. Like the case of the parent trans-stilbene, fluorescence and the vinylene C&9552;C torsion are two important decay pathways for trans-aminostilbenes. However, a new pathway, that is, formation of a TICT state by twisting the phenylene-amino C−N bond, dominates the excited-state deactivation of some trans-aminostilbenes in medium and/or highly polar solvents. On the basis of the quantum yields of fluorescence (Φf) and the trans → cis isomerization (Φtc) in solvents of different polarity, the TICT-forming activity of trans-aminostilbenes could be readily probed. The TICT states could be unambiguously characterized with ring-bridged model compounds, profiles of the emission spectra, and variable-temperature emission spectra. The interplay among fluorescence, the trans → cis isomerization, and the TICT state formation strongly depends on the nature and position of the amino group(s), the solvent polarity, and the other substituents that significantly perturb the steric and/or electronic properties. This provides a unique opportunity toward the design of novel fluorescent probes, light-emitting materials, and molecular switches.
    Journal of Photochemistry and Photobiology A Chemistry 05/2015; 312. DOI:10.1016/j.jphotochem.2015.05.031 · 2.50 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: {Zinc 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine} (ZnPC) exists as monomeric species in DMSO and is reasonably strong fluorescent. But ZnPC forms H-aggregates in water and hexafluoroisopropanol, which are strong hydrogen bonding solvents. Nanoaggregates are nearly nonemissive. Transient absorption spectroscopic technique has been used to investigate the excited state relaxation processes in both monomeric and aggregated forms of ZnPC. The lifetime of the S1 state of the monomoric form in DMSO is long (τ = 3.4 ns) but the excited states of ZnPC nanoaggregates show much faster ground state recovery (within 100 ps). The longest lifetime component, τ3, which is independent of excitation density, has been assigned to the unimolecular decay of the S1-exciton in the absence of annihilation reaction, while τ1 and τ2 are the lifetimes obtained by the two-component fit of the nonexponential decay arising due to the time-dependent decay rates of the S1-excitons because of diffusive migration controlled exciton - exciton annihilation reaction. Rates of the annihilation reaction (2.0 × 10–6 cm3s–1) and exciton migration (4.3 × 10–5 m2/s) as well as diffusion length (about 85 nm) of the S1-exciton created in the ZnPC nanoaggregates in HFIP have been determined.
    The Journal of Physical Chemistry C 07/2012; 116(28):15155–15166. DOI:10.1021/jp304369r · 4.77 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Ab initio molecular dynamics including nonadiabatic and spin–orbit couplings on equal footing is used to unravel the deactivation of cytosine after UV light absorption. Intersystem crossing (ISC) is found to compete directly with internal conversion in tens of femtoseconds, thus making cytosine the organic compound with the fastest triplet population calculated so far. It is found that close degeneracy between singlet and triplet states can more than compensate for very small spin–orbit couplings, leading to efficient ISC. The femtosecond nature of the ISC process highlights its importance in photochemistry and challenges the conventional view that large singlet–triplet couplings are required for an efficient population flow into triplet states. These findings are important to understand DNA photostability and the photochemistry and dynamics of organic molecules in general.
    Journal of Physical Chemistry Letters 11/2012; 3:3090-3095. DOI:10.1021/jz301312h · 7.46 Impact Factor
Show more