Light driven photoswitches: three classes of molecular systems that result in a single photoproduct a conical intersection and an exothermic reverse reaction.

A common feature of molecular photoswitches is the selectivity of their photo-processes. The photoswitching model must combine a selective photochemical direct route and a thermal reverse reaction from the product back to the parent reactant. The conical intersection model is an appropriate approach to this problem. Valence bond analysis of the ground state reactions between the photoswitching isomers provides a chemically oriented approach to locate the conical intersection and to define its two coordinates. Three different classes of molecular photoswitches have been identified:(1) A reactant and product are connected by two distinct reaction routes with two different transition states. The conical intersection is situated inside this phase-inverting loop. An example of this class of photoswitches is an isomerization around a polar double CC, CN or NN bond. The capacity to store energy is indicated by the energy gap between the reactant and product. However, this can also result in the destabilisation of the product. For instance, the addition of bulky substituents can disrupt the planar fragment around the double bond, leading to the loss of π-conjugation. Two non-equivalent isomers with different contributions of polar and biradical forms can exhibit a highly distorted conical intersection topology. (2) The photoreaction leading to two photoproducts is a regular case. However, this case could be a "quasi single product", if two products or the parent reactant and one of the products are equivalent isomers. This is the second type of photoswitch. (3) If one of the two products is at a higher energy level than both the reactant and the main product, then this is also a possible molecular photoswitching mechanism. The second high energy product is likely to be unstable and it is close to conical intersection. The norbornadiene-quadricyclane pair is an example of this type of photoswitch.