Fullerene derivatives for photonic applications: design, synthesis and measurements
(i) for the calculation of the linear and non-linear optical (LandNLO) properties of molecules, crystalline solids and liquids and
(ii) the synthesis of several nano-structured materials.
The proposed transfer of knowledge (ToK) involves the understanding, implementation, extension and use of:
(i) a linear scaling method, because such approaches provide reliable results for the properties of systems involving hundreds of atoms at a computational costs, which scales linearly with the size of the system,
(ii) a recently proposed technique for the calculation of the vibrational contributions to the LandNLO properties of derivatives with high anharmonicities and
(iii) a technique for the synthesis of endohedral metallo-fullerenes and a method for their separation and isolation in pure form.
The proposed competence connected with our expertise on the calculation of the LandNLO properties of molecules and the synthesis of fullerene-based materials will be used
(i) to calculate the LandNLO properties of a selected series of charged - transfer fullerene derivatives, among which we note a series of endohedral metallo-fullerenes and substituted fullerenes (one or more carbon atoms of the cage have been substituted by hetero-atoms) and
(ii) to design a set of novel fullerene-based nano-hydrids and endohedral metallo-fullerenes, with optimum properties for photonic applications.
The more suitable (in terms of their NLO properties) of the designed compounds will be synthesized and characterized by the team of one of the participating partners, while their NLO properties will be measured by the group of another partner, employing the optical Kerr effect. By combining design/modeling, synthesis and characterization as well as measurements, we expect to take the full advantage of the proposed ToK and to maximize the added value.
NATIONAL HELLENIC RESEARCH FOUNDATION
Vas. Constantinou Ave. 48
Manthos PAPADOPOULOS (Dr)
UNIVERSITY OF CAMBRIDGE
UNIVERSITY OF GIRONA
NATIONAL HELLENIC RESEARCH FOUNDATION
Final Activity Report Summary - FDPA (Fullerene Derivatives For Photonic Applications: Design, Synthesis and Measurements)
A nuclear relaxation treatment of vibrational anharmonicity for a model fulleropyrrolidine molecule yields a first-order contribution that is substantially more important than the double harmonic term for the static first hyperpolarisability . Electronic and vibrational nuclear relaxation (NR) contributions to the dipole (hyper)polarisabilities of the endohedral fullerene Li@C60 and its monovalent cation [Li@C60]+ are calculated. Many results are new, while others differ significantly from those reported previously using more approximate methods. Whereas the NR contribution to the static linear polarisabilities is small in comparison with the corresponding electronic property, the opposite is true for the static hyperpolarisabilities.
The dipole moment and the (hyper)polarisabilities of C28 and Ti@C28 have been computed. The electronic and vibrational contributions are presented. We reported on the linear and nonlinear optical properties of C60-triphenylamine (TPhA) hybrids. The synthesised materials were prepared following the 1,3-dipolar cycloaddition of azomethine ylides onto the skeleton of C60 forming the TPhA-based monoadduct, equatorial bis-adduct and dumbell C60.
We have found that the total second-order hyperpolarisability of the C60-TphA-C60 system is several times larger than that of TPhA-C60. The results of experimental measurements are supported by quantum-chemical calculations. Endohedral fullerenes Gd@C82, as well as some di-Lu-based metallofullerenes, were produced. A coumarin derivative with a malonate unit has been synthesised and used for the preparation of a fullerene-coumarin dyad through the Bingel cyclopropanation method. Our studies clearly show the presence of electronic interactions between C60 and modified coumarin in the ground state; efficient electron-transfer quenching of the singlet excited state of the coumarin moiety by the appended fullerene sphere was also observed.
The redox potentials of the C60-coumarin dyad were determined and the energetics of the electron-transfer processes were evaluated. Isophthaloyl-bridged porphyrin dimer (IBP) forms a 1:1 complex with La@C82. Despite the photoactive character of the porphyrin moiety, the association ability of IBP for La@C82 is based exclusively on cooperative supramolecular forces, namely structural non-covalent interactions of the porphyrin rings as well as of the nitrogen atoms present in 1 with La@C82. The host-guest interaction between single-wall carbon nanotubes and azafullerenes encapsulated in them has been investigated by UV-vis-NIR absorption and photoluminescence spectroscopy. The interaction between SWCNTs and the encapsulated azafullerenes has been explained by weak intermolecular forces.
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