Is it possible to ”simply” predict the photoejection of a cation? Example of azacrown-substituted [(bpy)Re(CO)<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline" id="d1e2405" altimg="si94.svg"><mml:msub><mml:mrow /><mml:mrow><mml:mn>3</mml:mn></mml:mrow></mml:msub></mml:math>L]<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline" id="d1e2413" altimg="si17.svg"><mml:msup><mml:mrow /><mml:mrow><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math> complexes

In the context of designing efficient photocontrolled ion-release systems, we propose a ”simple” computational strategy able to predict cation photoejection. Our is based on TD-DFT calculations and analysis charge transfer (CT) parameters excited states that can be populated for given excitation wavelength, in Franck–Condon region. With help CT descriptors (the variation electronic density, so-called DCT index natural population NPA charges), aim identify presenting depletion density complexation site after excitation. If loss large enough binding site, such state should first step mechanism leading photorelease. We test this ReAZBAP+-Mn+ (Mn+ = Li+, Na+, Mg2+, Ca2＋, Ba2+) ReAZAT+-Ba2+ series complexes synthesized studied by Moore co-workers [Lewis et al. (2004)]. show our first-order approach does not take into account complex excited-state decay routes, correctly photorelease properties with success rate ca. 80 percent. This method thus considered as valuable tool framework silico design light-controlled ion release.