Anion and Temperature Responsive Molecular Switches Based on Trimetallic Complexes of Ru(II) and Os(II) That Demonstrate Advanced Boolean and Fuzzy Logic Functions

Anion- and temperature-induced alteration of the photoredox behaviors of our recently reported trimetallic complexes was carried out to fabricate potential molecular switches. The triads [(phen)2Ru(d-HIm-t)M(t-HIm-d)Ru(phen)2]6+ (phen = 1,10-phenanthroline, d-HIm-t = heterotopic bipyridine-terpyridne type bridging ligand, and M = RuII and OsII) possess two acidic imidazole NH protons that upon interaction with anions give rise to considerable changes in their photophysical and electrochemical behaviors. Red-shifts of the absorption and emission maximum and a decrease in the M3+/M2+ potential occur when the triads are treated with basic anions. In fact, the triads can function as triple-channel sensors for F-, AcO-, CN-, OH-, and H2PO4- in acetonitrile and as selective probes for CN- and SCN- in water. The equilibrium constants for the receptor-anion interaction are on the order of 106 M-1, while the limit of detection was on the order of 10-9 M. Temperature plays a key role in the luminescence properties of the triads by adjusting the energy barrier between the emitting triplet metal-to-ligand charge transfer and non-emitting triplet metal-centered levels. A decrease in temperature leads to increases in the emission intensity and lifetime of the triads displaying the "on state", whereas an increase in temperature leads to a decrease in their emission characteristics and thus indicates the "off state" and that the process is fully reversible. In essence, the triads could function as potential switches on the basis of the reversible change in their spectral and redox behaviors under the influence of anion, acid, and temperature. The most important outcome of this study is mimicking several advanced Boolean and fuzzy logic functions by utilizing the spectral response of the triads upon the action of said external stimuli.