Anamika Ray

Photophysical and theoretical investigations on fullerene/phthalocyanine supramolecular complexes.

The present paper reports the photophysical aspects of a very interesting and unique host-guest interaction between fullerene and phthalocyanines, viz., free base phthalocyanine (H2-Pc) and zinc-phthalocyanine (Zn-Pc), in toluene medium. Ground state electronic interaction between these two supramolecules has been evidenced from the observation of well-defined charge transfer (CT) absorption bands in the visible region. Vertical ionization potentials of the phthalocyanines have been determined utilizing CT transition energy. Magnitude of degrees of CT reveals that, in the ground state, 2-4% CT takes place. Binding constants (K) for the fullerene/phthalocyanine complexes were determined from the fluorescence quenching experiment. Large K values in the ranges approximately 4.7 x 10(4) to 7.3 x 10(4) and 2.3 x 10(4) to 2.5 x 10(4) dm(3) x mol(-1) were obtained for the 1:1 fullerene complexes of Zn and H 2-Pc, respectively. Values of K suggest that both H 2- and Zn-Pc could not serve as an efficient discriminators between C60 and C70. Theoretical calculations as well as (13)C NMR studies establish that the orientation of C 70 toward phthalocyanine is favored in end-on orientation, which proves that interaction between fullerenes and phthalocyanines were governed by the electrostatic mechanism rather than dispersive forces associated with pi-pi interaction.

Spectroscopic and theoretical investigations on effective and selective interaction of fullerenes C60 and C70 with a derivatized Zn-phthalocyanine: stabilization of charge-recombined state by side-on approach of C70.

The photophysical aspects of noncovalently linked fullerenes C(60) and C(70) with a designed metallophthalocyanine, namely, zinc-2,3,9,10,16,17,23,24-octakis-(octyloxy)-29H,31H-phthalocyanine (1) have been investigated employing various spectroscopic tools such as UV-vis absorption spectrophotometry, steady state and time-resolved fluorescence, along with solution state IR measurements in toluene medium. The ground state interaction between fullerenes and 1 is first evidenced from UV-vis measurements. Binding constants (K) for the complexes of C(60) and C(70) with 1 are determined to be 13,235 and 27,670 dm(3) x mol(-1), respectively. Steady state fluorescence experiment reveals efficient quenching of the excited singlet state of 1 in presence of both C(60) and C(70). Emission studies reveal K values of 8945 and 19,175 dm(3) x mol(-1) for C(60)/1 and C(70)/1 complexes, respectively. The magnitude of K suggests that 1 preferentially binds C(70) in comparison to C(60) as average selectivity in K of C(70) over C(60) is enumerated to be 2.0. Time resolved emission measurements establish that C(70)/1 complex is stabilized much more in comparison to C(60)/1 complex in terms of charge recombination. Liquid IR studies provide very good support in favor of ground state complexation between fullerenes and 1. Molecular mechanics calculations at force field model and semiempirical calculations employing third parametric method substantiate the strong binding between C(70) and 1, and at the same time, determine the orientation of bound guest (here C(70)) within the cavity of 1.

Photophysical and theoretical insights on fullerene/zincphthalocyanine supramolecular interaction in solution.

The 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 C(60) and C(70) 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 C(60) and C(70) 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 C(60) and C(70). The average binding constants of the C(60) and C(70) complexes of 1 (estimated by UV-vis and steady state fluorescence measurements) are determined to be 18,330 dm(3)·mol(-1) (12,595 dm(3)·mol(-1)) and 19,160 dm(3)·mol(-1) (15,292 dm(3)·mol(-1)) in toluene (DCB), respectively. Lifetime experiment yields a larger magnitude of charge separated rate constant for the C(70)/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 (13)C NMR study nicely demonstrates that the end-on orientation of C(70) is very much responsible for the low selectivity in binding between C(60)/1 and C(70)/1 systems. Free energy of charge recombination and free energy of radical ion-pair formation signify that electron transfer from the excited 1 to C(60) and C(70) in the C(60)/1 and C(70)/1 complexes, respectively, is an unlikely process. Finally, transient absorption measurements in the visible region establish that energy transfer from (T)C(60*) (and (T)C(70*)) to 1 occurs predominantly in both toluene and DCB, which is subsequently confirmed by the consecutive appearance of the triplet state of 1.

New Photophysical Insights in Noncovalent Interaction between Fulleropyrrolidine and a Series of Zincphthalocyanines

The present article reports, for the first time, the photophysical aspects of noncovalent interaction of a fullerene derivative, namely, C(60) pyrrolidine tris-acid ethyl ester (PyC(60)) with a series of zincphthalocyanines, for example, underivatized zincphthalocyanine (1), zinc-1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (2), and zinc-2,3,9,10,16,17,23,24-octakis-(octyloxy)-29H,31H-phthalocyanine (3) in toluene. Ground state electronic interaction of PyC(60) with 1, 2 and 3 has been evidenced from the observation of well-defined charge transfer (CT) absorption bands in the visible region. Utilizing the CT transition energy, vertical electron affinity (E(A)(v)) of PyC(60) is determined. Steady state fluorescence experiment enables us to determine the value of binding constant (K) in the magnitude of 2.60 × 10(4) dm(3)·mol(-1), 2.20 × 10(4) dm(3)·mol(-1), and 1.27 × 10(4) dm(3)·mol(-1) for the noncovalent complexes of PyC(60) with 1, 2, and 3, respectively. K values of PyC(60)-ZnPc complexes suggest that PyC(60) is incapable of discriminating between 1, 2, and 3 in solution. Lifetime experiment signifies the importance of static quenching phenomenon for our presently investigated supramolecules and it yields larger magnitude of charge separated rate constant for the PyC(60)-1 species in toluene. Photoinduced energy transfer between PyC(60) and ZnPc derivatives, namely, 1, 2, and 3, in toluene, has been evidenced with nanosecond laser photolysis method by observing the transient absorption bands in the visible region; transient absorption studies establish that energy transfer from (T)PyC(60)* to the ZnPc occurs predominantly, as confirmed by the consecutive appearance of the triplet states of PyC(60). Theoretical calculations at semiempirical level (PM3) evoke the single projection geometric structures for the PyC(60)-ZnPc systems in vacuo, which also proves that interaction between PyC(60) and ZnPc is governed by the electrostatic mechanism rather than dispersive forces associated with π-π interaction.

Photophysical investigations on supramolecular fullerene/phthalocyanine charge transfer interactions in solution

The photophysical features of non-covalently linked fullerenes C60 and C70 with a designed free-base phthalocyanine, namely, 2,3,9,10,16,17,23,24-octakis-(octyloxy)-29H,31H-phthalocyanine (1) have been investigated employing various spectroscopic tools like UV-vis absorption spectrophotometry, steady state and time resolved fluorescence along with proton NMR measurements in toluene. The ground state interaction between fullerenes and 1 is nicely demonstrated with the appearance of well defined charge transfer absorption bands in the visible region of the electronic spectra. Steady state fluorescence experiment reveals efficient quenching of the excited singlet state of 1 in presence of both C60 and C70. The average values of binding constants for the non-covalent complexes of C60 and C70 with 1 are determined to be ~18,150 and ~32,000 dm(3) mol(-1), respectively. The magnitude of K suggests that 1 preferentially binds C70 in comparison to C60 although average value of selectivity in binding is measured to be low (~1.75). Time resolved emission measurements establish photoinduced energy transfer from the excited singlet state of 1 to fullerene in toluene. Measurements of free energy of electron transfer and free energy of radical ion-pair formation elicit that C70/1 complex is stabilized more in comparison to C60/1 complex regarding generation of charge-separated state. Proton NMR studies provide very good support in favor of effective ground state complexation between fullerenes and 1. Semi empirical theoretical calculations on fullerene/1 systems in vacuo substantiate the stronger binding between C70 and 1 in comparison to C60/1 system in terms of heat of formation value of the respective complexes, and determine the orientation of bound guest (here C70) towards the plane of 1 during complexation.

Spectroscopic and structural insights on molecular assembly consisting high potential zinc phthalocyanine photosensitizer attached to PyC60 through non-covalent interaction

Efforts to improve the ease of self-assembly formation through non-covalent interaction has led to the development of zinc phthalocyanine (zinc-2,9,16,23-tetra-tert-butyl phthalocyanine, i.e., ZnPc) as a high potential photosensitizer molecule towards C60 pyrrolidine tris-acid ethyl ester (PyC60) in toluene and 1,2-dichlorobenzene (DCB). Steady state fluorescence experiment elicits efficient quenching of the fluorescence intensity of both H2- and ZnPc in presence of PyC60. The average value of binding constant for PyC60/H2-Pc and PyC60/ZnPc systems in toluene (DCB) are determined to be 9910 (13,460) and 12,710 (24,060) dm(3) mol(-1), respectively. Lifetime experiment yields ∼3 times larger magnitude of charge separated rate constant for the PyC60/ZnPc system compared to PyC60/H2-Pc in toluene. Photoinduced energy transfer between PyC60 and H2- (/ZnPc) has been evidenced with nanosecond laser photolysis method; transient absorption studies establish that energy transfer from (T)PyC60(∗) to H2- and ZnPc occurs predominantly, as confirmed by the consecutive appearance of the triplet states of PyC60.

Absorption spectrophotometric, fluorescence, transient absorption and quantum chemical investigations on fullerene/phthalocyanine supramolecular complexes.

The present paper reports the photophysical investigations on supramolecular interaction of a phthalocyanine derivative, namely, 2,9,16,23-tetra-tert-butyl-29H,31H-Pc (1) with C(60) and C(70) in toluene. The binding constants of the C(60) and C(70) complexes of 1 are estimated to be 27,360 and 25,205 dm(3), respectively. Transient absorption measurements in the visible region establishes that energy transfer from C60*T (and C70*T) to 1 occurs predominantly in toluene which is subsequently confirmed by the consecutive appearance of the triplet states of 1. Quantum chemical calculations at DFT level of theory explore the geometry and electronic structure of the supramolecules and testify the significant redistribution of charge between fullerenes and 1.

Remarkable decrease in binding strength for a phthalocyanine–fulleropyrrolidine non-covalent system in the presence of silver nanoparticles

Silver nanoparticles with size of 5–15 nm reduce the binding constant of a phthalocyanine–fulleropyrrolidine system from ∼1.78 × 104 dm3 mol−1 to ∼1.31 × 103 dm3 mol−1 in toluene.

Photophysical and theoretical insights on non-covalently linked fullerene–zinc phthalocyanine complexes

The photo-physical aspects of non-covalently linked assemblies of a series of fullerenes, namely, C60, C70, tert-butyl-(1,2-methanofullerene)-61-carboxylate (1) and [6,6]-phenyl C70 butyric acid methyl ester (2) with a designed zinc phthalocyanine (ZnPc), viz., zinc-1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (3) in toluene medium are studied employing absorption spectrophotometric, steady state and time resolved fluorescence spectroscopic measurements. Of central interest in these investigations is the preferential binding of various fullerenes with ZnPc in toluene. The ground state interaction between fullerenes and 3 is first evidenced from UV-Vis measurements. Steady state fluorescence experiment reveals efficient quenching of the excited singlet state of 3 in presence of both underivatized and derivatized fullerenes. K values for the complexes of C60, C70, 1 and 2 with 3 are determined to be 6500, 22,230, 47,800 and 54,770 dm3 mol(-1), respectively. The magnitude of K suggests that 3 preferentially binds C70 and derivatized C70 in comparison to C60 and 1. Time resolved emission measurements establish that C(70)-3 and 2-3 complexes are stabilized much more in comparison to C(60)-3 and 1-3 systems in terms of charge separation process. Semi empirical calculations employing third parametric method substantiate the strong binding of C70 and its derivative with 3 in terms of heat of formation values of the respective complexes, and at the same time, determine the orientation of bound guest (here fullerenes) with the molecular plane of 3.

Photophysical insights into fullerene–porphyrazine supramolecular interactions in solution

This communication reports UV-vis, fluorescence and quantum chemical investigations on the supramolecular interactions of a porphyrazine derivative, namely, 2,7,12,17-tetra-tert-butyl-5,10,15,20-tetraaza-21H,23H-porphine (1) with C60 and C70 in toluene and dichlorobenzene. A synergistic combination of rigidity in the host molecule and a shape-selective binding motif give rise to the strongest binding of C60 with porphyrazine.