Anion–cation charge-transfer properties and spectral studies of [M(phen)3][Cd4(SPh)10] (M = Ru, Fe, and Ni)

Abstract

Three anion-cation compounds 1-3 with formula [M(phen)(3)][Cd(4)(SPh)(10)]·Sol (M = Ru(2+), Fe(2+), and Ni(2+), Sol = MeCN and H(2)O) have been synthesized and characterized by single-crystal analysis. Both the cations and anion are well-known ions, but the properties of the co-assembled compounds are interesting. Molecular structures and charge-transfer between the cations and anions in crystal and even in solution are discussed. These compounds are isomorphous and short inter-ion interactions are found in these crystals, such as π···π stacking and C-H···π contacts. Both spectroscopic and theoretical calculated results indicate that there is anion-cation charge-transfer (ACCT) between the Ru-phen complex dye and the Cd-SPh cluster, which plays an important role in their photophysical properties. The intensity of the fluorescent emission of the [Ru(phen)(3)](2+) is enhanced when the cation interacts with the [Cd(4)(SPh)(10)](2-) anion. The mechanism for the enhancement of photoluminescence has been proposed.

Ion pair charge-transfer thiogermanate salts [MV]2Ge4S10·xSol: solvent induced crystal transformation and photocurrent responsive properties

“…Metal-phenanthroline/ bipyridine cations as photoactive functional complexes have been integrated into chalcogenidometalates to obtain a good D-A charge transfer system. 5,6 Fluorescence enhancement, 7 solid-state crystal transformation, 8 and photochemical production of hydrogen 9 were achieved for these compounds or materials. The N,N′-dimethyl-4,4′-bipyridinium dication, also known as methylviologen or paraquat (abbreviated as MV 2+ hereafter), as a famous photo and electronically active organic electron acceptor, has been frequently used as the cation of charge transfer salts.…”

Synthesis and photocurrent responsive properties of CdS/Se clusters integrated with methylviologen

“…8a We have been interested in the organic functional group hybrid chalcogenides and a series of charge transfer chalcogenido compounds with [M(Phen/Bpy) 3 ] cations have been reported. 15,16 The aim of this work is to investigate the charge transfer properties and photoelectric activity of the larger cadmium chalcogenido clusters with methylviologen. Two new ion pair compounds with nano-sized C1 (Cd 17 ) CdQ (Q ¼ S, Se) anion clusters and organic functional cation MV 2+ are synthesized and their molecular structures are reported, MV [Cd 17 Se 4 (SPh) 24 Br 4 ] (1) and MV[Cd 17 S 4 (SPh) 24 Br 4 ] (2).…”

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…While the first such compounds were obtained from electrolysis of metal anodes in basic thiol solutions, [207,208] a simpler method involving reactions between chalcogenolate solutions and simple non-halide metal salts at mostly room temperature has subsenquently been used. [148,[209][210][211][212][213][214][215][216][217][218][219][220][221][222] In solution, Cd clusters can exchange chalcogenolates, including partial substitution with tellurium, to form mixed compounds [Cd4(ER)n(E´R´)10-n] 2− (in 320-368) by reacting them with R2E´2, or in equilibrium reactions with other similar clusters. [222] The latter strategy also works to form the mixed metal compound [Me4N][CdnZn4-n(SPh)10] (369-371).…”