A Molecular Platform for Multistate Near‐Infrared Electrochromism and Flip‐Flop, Flip‐Flap‐Flop, and Ternary Memory

Abstract

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.

Polypyridyl-imidazole based smart Ru(II) complex mimicking advanced Boolean and Fuzzy logic functions

“…In contrast to mimicking the functions of basic logic gates as well as their simple combinations, the molecular systems capable of demonstrating sequential logic operations as required in circuits, molecular keypad locks [28][29][30], and memory devices are relative few in the literature [8,[31][32][33][34]. Moreover, there is huge scarcity of coordination complex-based molecular systems with versatile geometry and excellent optoelectronic properties compared with their organic counterparts in exhibiting sequential advanced logic functions [35][36][37]. To this end, we designed and structurally characterized the title Ru(II) complex (1) derived from heteroditopic terpyridyl-imidazole ligand (Chart 1).…”

Improving Memory Performances by Adjusting the Symmetry and Polarity of O‐Fluoroazobenzene‐Based Molecules

“…[1][2][3][4][5][6][7][8] Amongt he variety of organic materials used, small molecules show the meritso fw ell-definedm olecular structures, reproducible preparation,f acile purification, and easy functionalization. [12][13][14][15][16][17] Several kinds of molecular dyes have been reported for applications in electronic memory. [12][13][14][15][16][17] Several kinds of molecular dyes have been reported for applications in electronic memory.…”

Transition from a Metal‐Localized Mixed‐Valence Compound to a Fully Delocalized and Bridge‐Biased Electrophore in a Ruthenium–Amine–Ruthenium Tricenter System

“…[2][3][4][5][6][7][8][9][10][11][12] Furthermore, these redox-active complexes are useful molecular materials for applications such as molecular electronics, [13] near-infrared electrochromism, [14] redox switches, [15] and molecular logic gates and memories. [16] Mixed-valence diruthenium complexes are normally treated as two-center systems. However, when a redox-active or -noninnocent bridge is used, [17][18][19] a three-center diruthenium complex is obtained.…”

“…Complexes 6(PF 6 ) 2 and 7(PF 6 ) 2 have previously been reported by us regarding their applications as molecular logic gates. [16] Complex 3(PF 6 ) 3 was isolated as the one-electron-oxidized form owing to its low oxidation potential. Furthermore, some monoruthenium complexes were prepared for the purpose of comparison (see details in the Supporting Information).…”

“…Each redox state of these complexes shows significantly different absorption spectra, which makes them useful in sophisticated logic gates. [16] We are particularly interested in the electronic structure and charge delocalization of the one-electron-oxidized state of these complexes (1 3 + -7 3 + ). It is surprising and interesting that these open-shell complexes show a set of absorption spectra in the near infrared (NIR) region with significant difference in energy, shape, and intensity ( Figure [27] The EPR signals of 4 3 + and 5 3 + at 77 K are much broader with respect to those at room temperature.…”