Theoretical Study of Topographical Features around the Conical Intersections of Fluorene-Based Light-Driven Molecular Rotary Motor
Theoretical Study of Topographical Features around the Conical Intersections of Fluorene-Based Light-Driven Molecular Rotary Motor
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DOI：
10.1021/jp401781a
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发表时间：
2013-05-02
影响因子：
2.9
通讯作者：
Amatatsu, Yoshiaki
中科院分区：
文献类型：
--
作者：
Amatatsu, Yoshiaki
Topographical features around the conical intersection (CIX) of a fluorene-based light driven molecular rotary motor have been examined by means of ab initio molecular orbital calculations. The model molecule is a derivative of 9-(2-phenyl-2-cyclopenten-1-ylidene)-9H-fluorene (PCPF) where PCPF is bridged by a pentamethylene chain between the 2 position of the phenyl group and the pseudoaxial position of the C-5 atom in the 2-cyclopenten-1-ylidene ring. This model molecule (denoted by M5-PCPF) has been very recently reported as a candidate for a light driven molecular motor with constant rotation. The conical intersection for the photoprocess of the ethylenic C=C torsion reported there (denoted by CIX1), which exclusively leads to a product of P'-M5-PCPF, is found to be classified as a sloped-type CIX. Another CIX reported at the present time (CIX2) exclusively goes back to a reactant of P-M5-PCPF, whereas CIX2 is also classified as a sloped-type CIX. At the stable geometry in S-1 around the CIX region (S-1-geometry), the 2-cyclopenten-1-ylidene rotor takes a perpendicular twist against the fluorene stator, but the fluorene stator does not wag so much against the C=C rotary axis. The wagging motions of the fluorene stator from S-1-geometry to the opposite directions lead to CIX1 and CIX2, respectively.
