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Photophysical and Theoretical Insights on Fullerene/Zincphthalocyanine Supramolecular Interaction in Solution
journal contribution
posted on 2012-10-04, 00:00 authored by Anamika Ray, Kotni Santhosh, Sumanta BhattacharyaThe present article reports photophysical studies on
supramolecular
interaction of a zinc phthalocyanine derivative, namely, zinc-2,9,16,23-tetra-tert-butyl phthalocyanine (1) with C60 and C70 in solvents having varying polarity, i.e., toluene
and 1,2-dichlorobenzene (DCB). The interesting feature of the present
work is the observation of charge transfer (CT) absorption bands of
the fullerene/1 complexes in DCB. Utilizing the CT transition
energy, many important physicochemical parameters like vertical ionization
potential of 1, degrees of CT, oscillator strength, transition
dipole moment, and resonance energy of interaction have been determined
in the present case. The influences of 1 on the UV–vis
spectral characteristics of C60 and C70 have
been explained using a theoretical model that takes into account the
interaction between electronic subsystems of 1 with fullerenes.
Steady state fluorescence experiment elicits efficient quenching of
the fluorescence intensity of 1 in the presence of both
C60 and C70. The average binding constants of
the C60 and C70 complexes of 1 (estimated
by UV–vis and steady state fluorescence measurements) are determined
to be 18 330 dm3·mol–1 (12 595
dm3·mol–1) and 19 160 dm3·mol–1 (15 292 dm3·mol–1) in toluene (DCB), respectively. Lifetime
experiment yields a larger magnitude of charge separated rate constant
for the C70/1 species. The faster charge recombination
of the fullerene/1 systems observed in more polar solvent
results from solvent reorganization energies. Quantum chemical calculations
by the ab initio method explore the geometry and
electronic structure of the supramolecules and testify the significant
redistribution of charge between fullerenes and 1 during
fullerene/1 interaction. A variable temperature 13C NMR study nicely demonstrates that the end-on orientation
of C70 is very much responsible for the low selectivity
in binding between C60/1 and C70/1 systems. Free energy of charge recombination and
free energy of radical ion-pair formation signify that electron transfer
from the excited 1 to C60 and C70 in the C60/1 and C70/1 complexes, respectively, is an unlikely process. Finally, transient
absorption measurements in the visible region establish that energy
transfer from TC60* (and TC70*) to 1 occurs predominantly in both toluene and DCB,
which is subsequently confirmed by the consecutive appearance of the
triplet state of 1.
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Keywords
state fluorescence measurementsDCBab initio methoddmcharge recombinationtolueneCT transition energytemperature 13 C NMR studyinteractionUVquantum chemical calculationsC 70 complexestransferfullerenelifetime experiment yieldsarticle reports photophysical studiesC 70TCSteady state fluorescence experimentC 60
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