Mo (W,V)_Cu (Ag)_S(Se) cluster compounds

Facile Syntheses and Tunable Non‐Linear Optical Properties of Heterothiometallic Clusters with [MS4Ag2] Units (M=Mo, W)

“…

Heterothiometallic clusters are of significant interest for their intriguing structures and topologies, [1][2][3][4][5][6] as well as their potential applications as non-linear optical (NLO) materials [7] and as the active sites of various metalloenzymes and catalytic reactions. [1] However, a dearth of facile preparative routes has proven a major impediment to the design and synthesis of these functionalised molecular materials.

…”

“…[3] The crystal engineering of M/S/Ag clusters [5, 6] (M = Mo, W), in particular, has proven significantly more challenging for both control of complexity and diversity of structures than that of the Cu-containing counterparts. [2][3][4] 7] Most of the known 1D polymeric M/S/Ag clusters have been synthesised by following a single protocol, namely, the reaction of [NH 4 ] 2 This methodology is not broadly applicable because it has several clear disadvantages: 1) AgNO 3 reacts readily with [MS 4 ] 2À , resulting in a Ag 2 S precipitate that is very difficult to react with further [MS 4 ] 2À moieties; 2) only S atoms from [MS 4 ] 2À moieties serve as the bridge to build M/S/Ag 1D chain clusters-no other linking atoms or units participate; 3) the solvent-coordinated rare-earth cations are trivalent and usually induce trivalent repeat units in the anionic chains, reducing the diversity and novelty of polymeric M/S/Ag clusters; 4) the known 1D M/S/Ag clusters synthesised by this method are formed in very low yields, which is a significant disadvantage with respect to applications as precursors for functional materials. [6] Herein, we report a new synthetic method for constructing M/S/Ag clusters in high yields, structural studies that reveal an unusual discrete octanuclear planar "open" square-like skeleton for [SrA ][W 2 S 8 Ag 4 I 2 ]} n (3), NLO studies that demonstrate strong third-order non-linear refraction, absorption and a large optical limiting (OL) capability, tuning of non-linearity by conceptual replacement of Mo by W, and time-dependent density functional theory (TD-DFT) studies that provide insight into the electronic transitions and spectral characterisation of these functionalised NLO molecular materials.In our new procedure, Sr 2 + cations and AgI take the roles of the directing cations and Ag + source, respectively, for synthesising M/S/Ag clusters.…”

“…[3] The crystal engineering of M/S/Ag clusters [5,6] (M = Mo, W), in particular, has proven significantly more challenging for both control of complexity and diversity of structures than that of the Cu-containing counterparts. [2][3][4]7] Most of the known 1D polymeric M/S/Ag clusters have been synthesised by following a single protocol, namely, the reaction of [NH 4 ] 2 A C H T U N G T R E N N U N G [MS 4 ] with AgNO 3 (or Ag 2 S) and LnA C H T U N G T R E N N U N G (NO 3 ) 3 . [6] This methodology is not broadly applicable because it has several clear disadvantages: 1) AgNO 3 reacts readily with [MS 4 ] 2À , resulting in a Ag 2 S precipitate that is very difficult to react with further [MS 4 ] 2À moieties; 2) only S atoms from [MS 4 ] 2À moieties serve as the bridge to build M/S/Ag 1D chain clusters-no other linking atoms or units participate; 3) the solvent-coordinated rare-earth cations are trivalent and usually induce trivalent repeat units in the anionic chains, reducing the diversity and novelty of polymeric M/S/Ag clusters; 4) the known 1D M/S/Ag clusters synthesised by this method are formed in very low yields, which is a significant disadvantage with respect to applications as precursors for functional materials.…”

Synthesis, crystal structure, and properties of a binuclear Zn(II) macroheterocyclic complex based on ferrocene-thiocarbazide ligand

“…In the complex the absorption at 474 cm À1 is attributed to M-S vibration [27]. Absorptions in the 1302-1225 cm À1 region shift to shorter wavenumbers and a new strong band at 1652 cm À1 is observed in the complex [28], perhaps the N-C vibration.…”

Synthesis, crystal structure and electrochemical properties of a novel tetranuclear silver(I) cluster based on 1,1′-bis[(2-hydroxybenzylidene)thiocarbonohydrazono-1-ethyl] ferrocene (FcL)

“…IR spectra of 1 indicate that the peak at 467 cm À1 is due to the M-S vibration [18], all other peaks in 1 shift to shorter wave numbers compared with the ligand IR spectra, the peaks in the range 1561-1532 cm À1 suggest that the new bonds in the structure of 1 are formed [19]. In the UV-Vis spectrum, two broad bands center at 307 and 335 nm are noted for the ligand, and attributed to a p-p* transition of the benzene ring and azomethine chromophore, respectively [20,21].…”