A diruthenium complex with a redox-active amine bridge has been designed, synthesized, and studied by single-crystal X-ray analysis and DFT and TDDFT calculations. It shows three well-separated redox processes with exclusive near-infrared (NIR) absorbance at each redox state. The electropolymerized film of a related vinyl-functionalized complex displays multistate NIR electrochromism with low operational potential, good contrast ratio, and long retention time. Flip-flop, flip-flap-flop, and ternary memories have been realized by using the obtained film (ca. 15-20 nm thick) with three electrochemical inputs and three NIR optical outputs that each displays three levels of signal intensity.
The synthesis, characterization, and temperature-responsive properties of two fluorescent organoplatinum(II) metallacycles are reported. Metallacycles M1 and M2 were prepared via the coordination-driven self-assembly of a 120° triarylamine ligand L1 and a 120° diplatinum(II) acceptor Pt-1 or 180° diplatinum(II) acceptor Pt-2, respectively. M1 and M2 are hexagonal metallacycles, comprising of three or six freely rotating anthracene pendants on their periphery, respectively. In response to the temperature variation between -20 and 60 °C, the ligand displays irregular emission changes, whereas both metallacycles show reversible absorption and emission spectral changes in THF. The changes in their green emission intensity also exhibit a linear correlation with the temperature variation, with an average sensitivity of -0.67% and -0.77% per °C for M1 and M2, respectively. Furthermore, in coordinating solvents, such as DMF and CHCN, M1 and M2 show different behaviors: in the lower temperature range, i.e., below 30 °C, their spectral changes are similar to those observed in THF; however, at a higher temperature the metallacycles were presumably destroyed by the solvents and displayed ratiometric fluorescent responses, including a cyan emission of the ligand L1.
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