Dalton Transactions

doi: 10.1039/c4dt90149epmid: N/A

doi: 10.1039/c4dt90150apmid: N/A

doi: 10.1039/c4dt90151gpmid: N/A

Rabuffetti, Federico A.; Brutchey, Richard L.

doi: 10.1039/c4dt01376jpmid: 25154461

This Perspective reviews our recent efforts towards the low-temperature synthesis of complex perovskite oxide ABO3 (A = Sr, Ba; B = Ti, Zr) nanocrystals using the vapor diffusion sol–gel method and the determination of their room-temperature crystal structure. From a synthetic standpoint, emphasis is placed on demonstrating the ability of the vapor diffusion sol–gel approach to yield compositionally complex nanocrystals at low temperatures and atmospheric pressure without the need for postsynthetic heat treatment to achieve a crystalline and phase-pure oxide product. The ability to successfully achieve this is illustrated using Ba1−xSrxTi1−yZryO3 (0 ≤ x ≤ 1, 0 ≤ y ≤ 1) and Eu3+-doped Ba(Ti,Zr)O3 nanocrystals as examples. From the standpoint of the structural analysis, emphasis is placed on highlighting how multiple and complementary spectroscopic techniques that probe atomic correlations in short (≤1 nm), intermediate (∼1–3 nm), and long (≥3 nm) length scales can be employed to gain insight into the atomic structure of the resulting nanocrystals. Examples that clearly illustrate this strategy of structural characterization are the investigation of the size- and composition-dependence of the structure of polar nanoregions in sub-10 nm BaTiO3 and sub-20 nm Ba1−xSrxTiO3 and BaTi1−yZryO3 nanocrystals, and the investigation of the distribution of rare earth dopants in sub-15 nm Eu3+:BaTiO3 nanocrystals.

Hector, Andrew L.; Jolleys, Andrew; Levason, William; Pugh, David; Reid, Gillian

doi: 10.1039/c4dt02265cpmid: 25138586

The new binary mixed-valence fluoride of germanium, Ge3F8, has been obtained by heating GeF4 with powdered Ge in an autoclave (390 K/4 bar/48 h). The structure contains pyramidal GeIIF3 and octahedral GeIVF6 units, linked by fluoride bridges. The new compound is the missing member of the series (GeF2)n·GeF4 (n = 2, 4, or 6). Sublimation of (GeF2)n·GeF4in vacuo provides a convenient source of GeF2 in ca. 30% overall yield.

Bichler, Bernhard; Glatz, Mathias; Stöger, Berthold; Mereiter, Kurt; Veiros, Luis F.; Kirchner, Karl

doi: 10.1039/c4dt01933dpmid: 25138445

Treatment of anhydrous FeCl2 with 2 equiv. of the pincer ligand PNP-Ph afforded the diamagnetic cationic octahedral complex [Fe(κ3-P,N,P-PNP)(κ2-P,N-PNP)Cl]+ featuring a κ2-P,N-bound PNP ligand. Preliminary reactivity studies revealed that the κ2-P,N-bound PNP ligand is labile reacting with CO to afford trans-[Fe(PNP-Ph)(CO)2Cl]+.

Dermitzaki, Despina; Raptopoulou, Catherine P.; Psycharis, Vassilis; Escuer, Albert; Perlepes, Spyros P.; Stamatatos, Theocharis C.

doi: 10.1039/c4dt02204apmid: 25140887

The initial ‘accidental’, metal ion-assisted hydrolysis of PF6− to PO3F2− has been evolved in a systematic investigation of the bridging affinity of the latter group in NiII/oximate chemistry; mono-, di- and trinuclear complexes have been prepared and confirmed both the rich reactivity of PO3F2− and its potential for further use as bridging ligand in high-nuclearity 3d-metal cluster chemistry.

Hasegawa, Toru; Yamane, Hisanori

doi: 10.1039/c4dt01670jpmid: 25141342

The crystal structure of Li2B3PO8 was determined by X-ray diffraction of a single crystal prepared by slow cooling from 943 K to 873 K. Li2B3PO8 crystallizes in a triclinic cell (space group P1̄, Z = 8). The sheets of ∞2[B3PO8]2− formed by the linkage of triangular BO3 and tetrahedral BO4 and PO4 groups stack along the b-axis direction.

García-Rodríguez, Raúl; Wright, Dominic S.

doi: 10.1039/c4dt02216epmid: 25142824

The in situ reaction of the tripodal anion [EtAl(MePy)3]− (MePy = 6-Me-2-py) with SnCl2 gives the Janus-head ligand (MePy)3Sn–Sn(MePy)3, containing a Sn–Sn bond, through a novel, one-pot reaction involving a combination of pyridyl transfer and metal-oxidation.

André Ohlin, C.; Rustad, James R.; Casey, William H.

doi: 10.1039/c4dt01763cpmid: 25144328

Electronic-structure calculations show that the ε-isomer of the polyoxoaluminate ion in the Keggin structure [AlO4-(Al(OH)2(H2O))12]7+ is the thermodynamically favoured one. Direct interconversion between the ε- and δ-isomers via cap rotation has a prohibitively high energy barrier in vacuo, suggesting that isomerisation in solution either proceeds via a dissolution–precipitation pathway, or that solvation and/or coordination to counterions reduces the barrier significantly. The implications for the formation of the [Al2O8Al28(OH)56(H2O)26]18+ ion are discussed.