Computational Design of a Family of Light-Driven Rotary Molecular Motors with Improved Quantum Efficiency.
Computational Design of a Family of Light-Driven Rotary Molecular Motors with Improved Quantum Efficiency.
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DOI：
10.1021/acs.jpclett.5b02575
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发表时间：
2016-01-07
期刊：
影响因子：
--
通讯作者：
Filatov M
中科院分区：
文献类型：
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作者：
Nikiforov A;Gamez JA;Thiel W;Filatov M
利用量子化学计算和非绝热分子动力学模拟，提出并研究了两种基于N-烷基化茚满苯并吡咯骨架的新型光驱动分子旋转电机。这些新型电机执行纯轴向旋转，旋转循环的光化学步骤由快速键长交替运动主导，从而能够超快地进入 S1/S0 交叉点。预计新型电机的量子效率将高于目前可用的合成全碳氢化合物电机。值得注意的是，量子效率不受最小能量圆锥形交叉点的形貌（峰值与倾斜）的影响，而 S1 衰减时间取决于形貌以及相对于 S1 最小值的交叉点的能量。控制电机旋转方向的是轴向手性（螺旋性），而不是点手性。
Two new light-driven molecular rotary motors based on the N-alkylated indanylidene benzopyrrole frameworks are proposed and studied using quantum chemical calculations and nonadiabatic molecular dynamics simulations. These new motors perform pure axial rotation, and the photochemical steps of the rotary cycle are dominated by the fast bond-length-alternation motion that enables ultrafast access to the S1/S0 intersection. The new motors are predicted to display a quantum efficiency higher than that of the currently available synthetic all-hydrocarbon motors. Remarkably, the quantum efficiency is not governed by the topography (peaked versus sloped) of the minimum-energy conical intersection, whereas the S1 decay time depends on the topography as well as on the energy of the intersection relative to the S1 minimum. It is the axial chirality (helicity), rather than the point chirality, that controls the sense of rotation of the motor.