Molecular Design by Utilizing Heavier Elements and Molecular Size

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Molecules featuring multiple bonds between heavier elements : (1) Effects of very bulky groups were systematically investigated to make disilynes (Rsi。甦i), digermynes (Rge。瓱eR) and distannynes (RSn。甦nR) synthetically accessible and isolable. Several stable molecules were predicted, which are worthy of experimental testing and verification. Similar calculations were also carried out silanones (R_2Si=O) and silabenzenes. (2) Triple bonds between。。a heavier main group and a transition metal in (ヲヌ^3- C_3H_3)(CO)_2M。瓲R were investigated with M = Cr, W and E=Si, Ge, Sn, Pb. (3) The nature of the unusually short Ga-Ga bond in Na_2[RGaGaAR] (R=C_6H_3-2,6,-(C_6^H_2^-2,4,6-I-Pr_3)_2), which is of wide interest as the first example of a triple bond between Ga atoms, was successfully disclosed for the first time. (4) The properties and reactivities of Ge-Ge double bonds incorporated in a three-membered ring were investigated in collaboration with experiment.Hollow and spherical cage-like molecule … More s : (1) Determination of structures and electronic states as well as dynamic properties of encapsulated metals was performed for representative metallofullerenes such as La@C_<62>, Pr@C_<62>, La_2@C_<60>, Sc_3@C_<62> and Sc_<3-n>La_nN@C_<60> (n = 0 - 3). (2) As interesting molecular capsules, the structures and electronic properties of carcerands (spherical-like and bowled-shaped molecules with an enforced internal cavity) were investigated to provide theoretical insight into molecular recognition and self-assembly. The efficient synthesis of carceplexes (carcerands containing a guest molecule in the cavity) depends strongly on the template effects of guest molecules. Guest molecules play an important role in the preorganization of two bowl-like host molecules, which leads to the formation of a capsule-like intermediate, A similar theoretical study is also carried out for calix[4]arene by changing the phenol-OH and linkage parts. (5) The unique reactivity of cytochrome P450 were investigated by changing systematically the axial-ligand. Less