Citation: Guo Ni, Wang Bin, Liu Fengyi. Theoretical Design and Mechanistic Study on a Light-Driven Molecular Rotary Motor with B=N Axis[J]. Acta Chimica Sinica, ;2018, 76(3): 196-201. doi: 10.6023/A17110509 shu

Theoretical Design and Mechanistic Study on a Light-Driven Molecular Rotary Motor with B=N Axis

School of Chemistry and Chemical Engineering, Shaanxi Normal University, Key Laboratory for Macromolecular Science of Shaanxi Province, Xi'an 710119, China

Corresponding author: Liu Fengyi, fengyiliu@snnu.edu.cn
Received Date: 27 November 2017
Available Online: 22 March 2018
Fund Project: the National Natural Science Foundation of China 21473107the National Natural Science Foundation of China 21636006Project supported by the National Natural Science Foundation of China (Nos. 21473107, 21636006) and Fundamental Research Funds for the Central Universities (No. GK201502002)Fundamental Research Funds for the Central Universities GK201502002

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Light-driven molecular motors have attracted overwhelming attention due to their potential applications in a wide range of fields. Despite of the great successes obtained in alkene-based light-driven molecular motors and switches, scientists pursuing high-efficient alternatives with superior working mechanisms have never suspended. In this report, a promising model of light-driven rotary motor, namely BN-stilbene motor, constructed by replacing the central C=C axis of a CC-stilbene rotary motor with a polar B=N bond, was rationally designed. Multireference Complete Active Space Self-Consistent Field (CASSCF) method and Time-Dependent Density Functional (TDDFT) theory were applied to study the mechanism of BN-stilbene, along with the Complete Active Space Second-Order Perturbation Theory (CASPT2) energy corrections. Our calculations show that the B=N axis well preserves the conjugation of between the rotor and stator, leading to four ground-state helical conformers (i.e., cis-stable, trans-unstable, trans-stable and cis-unstable), whose geometries and energies are in line with their counterparts in CC-stilbene motor; in addition, BN-stilbene has similar absorption spectra and more slopped excited-state potential energy curves at Franck-Condon region, which can fascinate a spontaneous rotary motion around B=N axis, thus generates directional photo-induced isomerization from cis-stable to trans-unstable (or from trans-stable to cis-unstable). Moreover, the barriers for helical inversions (trans-unstable → trans-stable or cis-unstable → cis-stable) are found to be lower than those of the reversed thermal rotations (i.e., cis-stable → trans-unstable and trans-stable → cis-unstable), which further insures the unidirectionality of rotation. These features sufficiently allow BN-stilbene to serve as a candidate for light-driven molecular rotary motor. Finally and most importantly, as compared with that of CC-stilbene, the photoisomerization mechanism of BN-stilbene motor shows advantages in nonadiabatic transition:Due to the introducing of polar B=N axis, the S₁/S₀ conical intersections of BN system are both geometrically and energetically closer to the excited-state intermediate, which is thus expected to improve the nonadiabatic transition probabilities and the unidirectionality of the rotation. Therefore, the BN-stilbene motor is expected to perform a unidirectional, repetitive 360° rotation upon sequential applying of photo and thermal inputs. The findings suggest BN-hetero stilbene as a promising type of light-driven rotary motor and may inspire the design and synthesis of novel molecular motors.
- photoisomerization,
- molecular motor,
- conical intersection,
- nonradiative transition,
- polar axis of rotation
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