V. P. Vasiliev

Simulation of highly emissive states based on ligand-to-metal charge transfer

Properties of the frontier orbitals of a d0-organometallic complex with promising photoluminescent and photosensor characteristics have been systematically studied by modern quantum-chemical methods. It has been demonstrated that the lowest electronically excited states are related to charge transfer from high-lying ligand-centered molecular orbitals to the predominantly metal-centered lowest unoccupied molecular orbital. Such an approach makes it possible to predict complexes with promising spectral-luminescent properties, including catalytic precursors of early transition metals.

Frontier orbitals and ligand-to-metal charge transfer electronic transitions in d 0 -metal complexes

Properties of frontier orbitals and low-energy electronic transitions in a d0-organometallic complex have been studied by TDDFT and DFT methods using B3LYP hybrid functional and 3-21G*, 6-31G**, SDD, CEP-121G, and DGDZVP basis sets. It has been shown that the electronic transition between frontier orbitals in the excitation and absorption spectra is associated with charge transfer mainly from π-type ligands to a central metal d0-ion. The good agreement of the data (the shape and band position of the spectra of electronic absorption and excitation, energy of electronic transitions, and strength of the harmonic oscillator) of quantum-chemical and photophysical studies is demonstrated.

Nature of ligand-to-metal charge transfer states in the metallocene series M(η 5 :η 1 -CpCMe 2 CB 10 H 10 C) 2 (M = Ti, Zr, Hf)

aInstitute of Problems of Chemical Physics, Russian Academy of Sciences, 1 prosp. Akad. Semenova, 142432 Chernogolovka, Moscow Region, Russian Federation. Fax: (496) 522 5636. E mail: gloukova@mail.ru bSouthern Scientific Center, Russian Academy of Sciences, 41 ul. Chekhova, 344006 Rostov on Don, Russian Federation cSouthern Federal University, 105/42 ul. B. Sadovaya, 344006 Rostov on Don, Russian Federation

Unusual effect of carborane ligands on the electronic properties of d 0-metal complexes

Modern quantum-chemical and photophysical methods have been used to study the structure of the frontier molecular orbitals and the nature of ligand-to-metal charge transfer (LMCT) transitions of structurally complex d0-metallocenes. It has been shown that such metal complexes with carboranyl ligands have emissive LMCT states with preferential charge transfer from aromatic π-ligands to the metal and a large electric dipole moment. The electronic excitation and absorption spectra were simulated for the first time, and dipole moments of metal complexes containing metal–carbon σ- and π-bonds were estimated, which is of fundamental importance for the development of molecular photonics.

Photophysical properties of the d0 π-complex in binary media

The luminescent properties of a d0 metal complex in binary aprotic media in which preferential solvation can occur were studied at room temperature. It was shown that the luminescence quantum yield for the complex in liquid solutions is sensitive to changes in the multilayer solvation shell.