量子化学计算研究自由基相互作用的双稳态轮烷的穿梭机理

Shuttling mechanism the bistable rotaxane based on the radical interaction by quantum chemical calculations

设计了一种氧化还原驱动的可切换的双稳态轮烷。以双百草枯-对苯双自由基双阳离子环(CBPQT^(2(·+)))作为大环分子,主链分子上有2个结合位点,即4,4′-联吡啶自由基阳离子BIPY^(·+)和2,6-二氧亚萘基(DOP)位点。运用密度泛函理论对大环分子在主链分子上的运动机理进行研究,并通过量子力学理论计算分析大环分子CBPQT^(2(·+))与主链分子上2个结合位点BIPY^(·+)和DOP之间的弱相互作用,证明了氧化还原反应控制自由基络合物的形成和解离可以驱动CBPQT^(2(·+))环沿着主链分子的2个结合位点间实现往复运动。

We designed a switchable bistable rotaxane consisted of the cyclobis(paraquat-p-phenylene)bisradical dicationic(CBPQT^(2(·+)))ring and a main chain,concluding the recognition sites 4,4′-bipyridinium radical cationic(BIPY^(·+))and 2,6-dioxynaphthalen(DOP).The density functional theory(DFT)was used to analyze the motion mechanism of ring along the main chain A.Quantum mechanics calculations were used to analyze the noncovalent interaction between the CBPQT^(2(·+))ring and the two recognition sites.It proves that the generation and dissociation of the trisradical tricationic complex controlled by the redox reaction could drive the reciprocating motion of the CBPQT^(2(·+))ring along the main chain between the two recognition sites.