Dalton Transactions

doi: 10.1039/c8dt90041hpmid: N/A

doi: 10.1039/C8DT90041Hpmid: N/A

doi: 10.1039/c8dt90042fpmid: N/A

doi: 10.1039/C8DT90042Fpmid: N/A

doi: 10.1039/c8dt90043dpmid: N/A

doi: 10.1039/C8DT90043Dpmid: N/A

Belik, Alexei A.

doi: 10.1039/c7dt04490apmid: 29384532

A-site-ordered AA′3B4O12 quadruple perovskites (with twelve-fold coordinated A and square-planar coordinated A′ sites) were discovered in 1967. Since then, there have been considerable research efforts to synthesize and characterize new members of such perovskites. These efforts have led to the discoveries of many interesting physical and chemical properties, such as inter-site charge transfer and disproportionation, giant dielectric constant, multiferroic properties, reentrant structural transitions and high catalytic activity. The first member of A-site columnar-ordered A2A′A′′B4O12 quadruple perovskites (with ten-fold coordinated A, square-planar coordinated A′ and tetrahedrally coordinated A′′ sites), CaFeTi2O6, was discovered in 1995, and for 19 years it was the only representative of this family. In the last few years, A2A′A′′B4O12 perovskites have experienced rapid growth. Herein, we present a brief overview of the recent developments in this field and highlight an under-investigated status and great potential of A2A′A′′B4O12, which can be prepared mainly at high pressure and high temperature. The presence of the A′′ site gives an additional degree of freedom in designing such perovskites. The A2A′A′′B4O12 perovskites are discussed in comparison with well-known AA′3B4O12 perovskites.

Xu, Xian; Luo, Ben-long; Wang, Lu-Lu; Xu, Li

doi: 10.1039/c7dt04309kpmid: 29411007

The solvothermal oxidation of [Mo3O2(O2CCH3)6(H2O)3]·ZnCl4 has been established as a general route toward [Mo4+3O4]-incorporated polyoxomolybdates (MoIV-POMs). Two unprecedented family members: the first Mo4+–Mo5+–Mo6+ nanocage cluster, Na[MoIV12MoV4MoVI3O43(OH)Py12]·11H2O (1) and the first heterometallic hybrid, [MoIV3MoVI10Zn(PO4)4(OH)2O31py3]·2(C5H6N)·3(C5H5N)·2H2O (2) have been prepared and characterized by X-ray crystallography, elemental and DFT theoretical analyses, XPS, mass spectroscopy, cyclic voltammetry, and IR spectroscopy.

Frischhut, Sabine; Fässler, Thomas F.

doi: 10.1039/c8dt00321apmid: 29411846

The first alkenyl-functionalized, uncharged deltahedral germanium clusters [{Si(SiMe3)3}3Ge9(CH2)nCHCH2] (n = 1 or 3) comprising five Ge0 atoms are presented. All compounds were NMR-spectroscopically and mass-spectrometrically characterized. [{Si(SiMe3)3}3Ge9(CH2)3CHCH2] was further characterized by X-ray structure analysis and Raman spectroscopy. Temperature-dependent NMR studies reveal dynamic behavior for both compounds in solution at room temperature. The propenyl derivative [{Si(SiMe3)3}3Ge9CH2CHCH2] undergoes fast decomposition in solution. The possibility of the comparatively stable pentenyl-substituted Ge9 cluster as a candidate for follow-up reactions is highlighted.

Zhang, Yingying; Hu, Dandan; Xue, Chaozhuang; Yang, Huajun; Wang, Xiang; Wu, Tao

doi: 10.1039/c7dt04891bpmid: 29423493

Herein we report a new 3D neutral chalcogenide framework constructed by using a supertetrahedral T3 cluster ([Mn2Ga4Sn4S20]) as the building unit and a metal complex ([Mn(dach)2], dach = 1,2-diaminocyclohexane) as the linker. Significantly, the obtained material exhibits high-efficiency electrocatalytic oxygen reduction activity with quasi-four-electron transfer and a small Tafel slope, much better than that of commercial Pt/C (10 wt%).