Two 9-anthracenecarboxylate (9-AC) coordinated heterometallic TOC compounds, [Ln2Ti10O14(ClO4)2(O(i)Pr)14(9-AC)2(CH3CN)2]·2H2O, Ln = Nd 1() and Eu (2), along with two benzoate (bza) analogues, [Ln2Ti10O14(ClO4)2(O(i)Pr)14(bza)2(HO(i)Pr)2], Ln = Nd (3) and Eu (4), were prepared by one step in situ solvothermal synthesis, and characterized by single crystal analysis. To date, only about ten lanthanum-titanium oxo clusters have been reported. Except for two Ti28 clusters, the compounds are all small clusters (Ti ≤ 4). The cluster structures of 1-4 adopt a Ti10Ln2 core structure with pseudo-Ci symmetry, which is similar to the fundamental structure of Ti12 clusters. Furthermore, except for their structures, the properties of lanthanum-titanium oxo clusters have never been studied. Herein, the fluorescence properties of these compounds are studied in detail. The metal centered emission of Eu(III) is completely quenched by 9-AC due to the lower triplet energy of the coordinated ligand. Enhanced ligand centered fluorescence is found for 2 in comparison with that of 1.
As most of the chalcogenidometalate anions are well-known electron-rich systems, design and preparation of ion pair compounds, by integrating an organic acceptor (A) with an inorganic chalcogenidometalate donor (D), are an attractive strategy to obtain new functional materials. We report herein the single-crystal structures and properties of three new ion pair charge-transfer (IPCT) compounds by incorporating thiogermanates with methylviologen (MV(2+), N,N'-dimethyl-4,4'-bipyridinium dication), [MV]2Ge4S10·xSol (Sol = solvent). Sharp and fast solvent-induced color changes and switchable fluorescence emission are observed for the compounds. The weak interactions that relate to the solvent and ions in the structures are likely the key points to modulate the cation-anion charge-transfer. A photocurrent response is observed for the photoelectric system of the IPCT compound upon repetitive switching of light on and off.
Recently, discrete large Tn clusters have become particularly attractive because they can be used as starting materials not only for constructing porous chalcogenides but also for solution processing of semiconductor film materials with electronic and optical properties. However, the discrete large clusters of main-group metal chalcogenides are difficult to stabilize because of their high negative charge. We report herein a new crystal compound co-assembled by discrete T4 [Cu 4 In 16 S 35 H 4 ] 14− and cubic [Cu 12 S 8 ] 4− clusters. It is uncommon that the negatively charged CuS cluster acts as a template to sustain a hexagonal cavity formed by negatively charged T4 clusters. Its degeneration product shows an excellent near-infrared absorption property and photocurrent responsive properties.
Different from the dominating supertetrahedral structure of InSe clusters, co-assembled nano-scale In33Se60 triangular ring clusters and wheel-shaped In18Se30 clusters have been found. The unusual second-sphere coordination templating effect of the Mn(dach) complexes and the central Mn(2+) ion is responsible for the formation of the triangular ring. The optical and electronic properties are discussed.
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