Yao Chao-Yi, Lin Hong-Yu, Morgenfurt Philip, Keyes Tia E, de Silva A Prasanna
School of Chemistry and Chemical Engineering, Queen's University Belfast BT9 5AG UK
School of Chemical Sciences, Dublin City University Dublin 9 Ireland.
Chem Sci. 2022 Aug 26;13(36):10856-10867. doi: 10.1039/d2sc03617g. eCollection 2022 Sep 21.
Shape-switchable cyclophane hosts allow the controlled capture and release of reactive polypyridineRu(ii) complexes in water. This gives rise to a network of host-guest binding, acid-base reactions in ground and excited states, and chemical redox interconversions. In the case of (2-(2'-pyridyl)imidazole)Ru(ii) complexes, several molecular logic gate arrays of varying complexity emerge as a result. Cyclophane-induced 'off-on' switching of luminescence in neutral solution is found to originate from two features of these aromatic hosts: enhancement of radiative decay by the polarizable host and the suppression of nonradiative decay involving deprotonation by reducing the water content within the deep host cavity. These are examples of nanometric coordination chemistry/physics being controlled by inclusion in an open box. The aromatic units of the macrocycle are also responsible for the shape-switching mechanism of wall collapse/erection.
可形状切换的环番主体能够在水中对活性聚吡啶钌（II）配合物进行可控的捕获和释放。这引发了一个由主客体结合、基态和激发态的酸碱反应以及化学氧化还原相互转化构成的网络。就（2 - （2'-吡啶基）咪唑）钌（II）配合物而言，由此出现了几种复杂度各异的分子逻辑门阵列。发现在中性溶液中环番诱导的发光“关 - 开”切换源自这些芳香族主体的两个特性：可极化主体增强辐射衰变，以及通过减少深主体腔内的含水量抑制涉及去质子化的非辐射衰变。这些是通过纳入一个开放盒子来控制纳米级配位化学/物理的实例。大环的芳香单元也负责壁塌缩/竖起的形状切换机制。
