Comparative Bonding and Photophysical Properties of 2,2'-Bipyridine and 2,2'-Bipyrazine in Tetracyano Complexes Containing Ruthenium and Osmium

Luminescent Cyanoruthenate(II)Diimine and Cyanoruthenium(II)Diimine Complexes

“…In addition to their unique bonding features, the lone‐pair of electrons on the nitrogen atoms of the cyanide ligands, which can interact with solvent molecules or electron acceptors, also gives rise to highly environmentally sensitive photophysical properties in luminescent cyanometalates 2b. f, 3 These properties have been extensively studied in the most‐popular cyanoruthenate system, that is, [Ru(CN) 4 ($\widehat{NN}$ )] 2− ,2f, 3a–g and they have been found to be useful in the development of luminescent chemosensors, probes, and stimuli‐responsive devices 2g. 4 Although luminescent cyanometalates possess many intriguing and favorable properties, modification of their properties is challenging when the only modifiable diimine ligand is functionalized for various applications.…”

“…Replacing the metal center is one possible strategy for tuning the properties of cyanometalates and does not require the redesign of the functionalized diimine ligand 2f. 3g, h, i In this context, we recently developed a new family of cyanorhenatediimine complexes 3i. Although luminescent cyanometalates with different metal centers, such as Os, Ir, and Re, have been explored, the emission quantum yields and lifetimes of many of these complexes remain unsatisfactory 2f.…”

The Nature of Charge-Transfer Excited States in Transition Metal Complexes Pertinent to Energy Conversion and Chemical Sensing

“…It should be noted that emission and absorption properties of cyano-ruthenium complexes are extremely solvent-dependent due to strong interactions of the cyanide co-ligands with solvents of different acceptor numbers; therefore, the nature of the involved electronic states can also be modulated by solvent changes. 27 For a reasonable explanation of the absorption and emission properties of ( 9) and its reduced and protonated form (9H2), quantum mechanical calculations were carried out. The MO's diagrams of (9), and (9H2) -built with DFT calculations -are shown in Figures 18 and 19, together with the contributions of each group.…”

Structural and photophysical properties of luminescent cyanometallates [M(diimine)(CN)4]2− and their supramolecular assemblies

“…A single report form 1995 described synthesis of [Os(bipy)(CN) 4 ] 2and compared its spectroscopic and redox properties to those of [Ru(bipy)(CN) 4 ] 2-. 35 Accordingly we prepared a more extensive series of complexes of this type using the published method from Na 4 [Os(CN) 6 ] and the appropriate diimine ligands. 36 Structural characterisation of many of the resulting complexes revealed coordination networks similar to those observed between [Ru(bipy)(CN) 4 ] 2and group 1A or 2A metal cations, based on coordination of cyanide lone pairs to Na + cations and the presence of water molecules which hydrogen-bond to the otherwise unoccupied cyanide groups.…”