[Nb@Ge13/14 ]3- : New Family Members of Ge-Based Intermetalloid Clusters.

During the past two decades, single-atom-centered medium-sized germanium clusters [M@Gen ] (M=transition metals, n>12) have been extensively explored, both from theoretical perspectives and experimental gas-phase syntheses. However, the actual structural arrangements of the Ge13 and Ge14 endohedral cages are still ambiguous and have long remained an unresolved problem for experimental implementation. In this work, we successfully synthesize 13-/14-vertex Ge clusters [Nb@Ge13 ]3- (1) and [Nb@Ge14 ]3- (2), which are structurally characterized and exhibit unprecedented topologies, neither classical deltahedra nor 3-connected polyhedral structures. Theoretical analysis indicates that the major stabilization of the Ge backbones arises due to the substantial interaction of Ge 4p-AOs with the endohedral Nb 4d-AOs through three/four-center two-electron bonds with an enhanced electron density accumulated over the shortest Nb-Ge13 contact in 1. Low occupancies of the direct two-center two-electron (2c-2e) Nb-Ge and Ge-Ge σ bonds point to a considerable degree of electron delocalization over the Ge cages revealing their electron deficiency.

Open Shells in Endohedral Clusters: Structure and Bonding in the [Fe2@Ge16]4- Anion and Comparison to Isostructural [Co2@Ge16]4.

The anionic cluster [Fe2@Ge16]4- has been characterized and shown to be isostructural to the known D2h-symmetric α isomer of the cobalt analogue [Co2@Ge16]4-. Together with the known pair of compounds [Co@Ge10]3- and [Fe@Ge10]3-, the title compound completes a set of four closely related germanium clusters that allow us to explore how the metal-metal and metal-cage interactions evolve as a function of size and of the identity of the metal. The results of spin-unrestricted density functional theory (DFT) and multiconfigurational self-consistent field (MC-SCF) calculations present a consistent picture of the electronic structure where transfer of electron density from the metal to the cage is significant, particularly in the Fe clusters where the exchange stabilization of unpaired spin density is an important driving force.

A passive wireless hydrogen surface acoustic wave sensor based on Pt-coated ZnO nanorods.

Using a passive wireless sensor to detect hydrogen can reach the goals of reducing cost and increasing the lifetime since the sensor can work without batteries. In this paper, a passive wireless hydrogen SAW sensor operating at room temperature has been achieved by combining a SAW tag and a resistive hydrogen sensor. The SAW tag is fabricated on a 128 degrees YX-LiNbO(3) substrate and its central frequency is 433 MHz. The resistive hydrogen sensor with the Pt-coated ZnO nanorods as the sensing film has the advantages of high stability, good repeatability and simple fabrication. The ZnO nanorods are synthesized by using the aqueous solution method and the Pt coating is employed as a catalyst for the hydrogen detection. The property of the resistive hydrogen sensor is examined before combining with the SAW tag. Results show that the resistance changes caused by the variations of relative humidity and temperature are negligible. Finally, the hydrogen SAW sensor is configured and measured wirelessly for various hydrogen concentrations at room temperature. The difference of the relative return loss caused by the hydrogen concentration variation is obvious and recognizable. All responses show that the proposed hydrogen sensor not only has good repeatability and high sensitivity but is capable of passive wireless detection.