Similarities of artificial photosystems by ruthenium oxo complexes and native water splitting systems

The nature of chemical bonds of ruthenium(Ru)-quinine(Q) complexes, mononuclear [Ru(trpy)(3,5-t-Bu(2)Q)(OH2)](ClO4)(2) (trpy 2,2' : 6',2 ''-terpyridine, 3,5-di-tert-butyl-1,2-benzoquinone) (1), and binuclear [Ru-2(btpyan)(3,6-di-Bu(2)Q)(2)(OH2)](2+) (btpyan = 1,8-bis(2,2' : 6',2 ''-terpyrid-4'-yl)anthracene,3,6-t-Bu(2)Q = 3,6-di-tert-butyl-1,2-benzoquinone) (2), has been investigated by broken-symmetry (BS) hybrid density functional (DFT) methods. BS DFT computations for the Ru complexes have elucidated that the closed-shell structure (2b) Ru(II)-Q complex is less stable than the open-shell structure (2bb) consisting of Ru(III) and semiquinone (SQ) radical fragments. These computations have also elucidated eight different electronic and spin structures of tetraradical intermediates that may be generated in the course of water splitting reaction. The Heisenberg spin Hamiltonian model for these species has been derived to elucidate six different effective exchange interactions (J) for four spin systems. Six J values have been determined using total energies of the eight (or seven) BS solutions for different spin configurations. The natural orbital analyses of these BS DFT solutions have also been performed in order to obtain natural orbitals and their occupation numbers, which are useful for the lucid understanding of the nature of chemical bonds of the Ru complexes. Implications of the computational results are discussed in relation to the proposed reaction mechanisms of water splitting reaction in artificial photosynthesis systems and the similarity between artificial and native water splitting systems.