The diverse structures of molybdate anions significantly provide new opportunities to design various nanostructures of MoO x -based organic-inorganic hybrids with prominent catalytic, electrochemical and photo/electrochromic properties. In this paper, the one-dimensional (1D) growth originating from anisotropic molybdate anions is successfully introduced to prepare a series of hybrid nanowires of Mo 3 O 10 (C 6 H 8 N) 2 $2H 2 O (anilinium trimolybdate), Mo 3 O 10 (C 2 H 10 N 2 ) (ethylenediamine trimolybdate) and Mo 3 O 10 (C 5 H 6 N) 2 $H 2 O (pyridium trimolybdate). Taking Mo 3 O 10 (C 6 H 8 N) 2 $2H 2 O for example, the 1D growth is proved to be associated with the chain-like structure of Mo 3 O 10 2À anions by both experiments and quantum chemical calculations. Meanwhile, the synthesis parameters, e.g., reacting time, pH conditions and feeding ratio, show obvious influences on product morphologies based on different molybdate anions, further validating the growth mechanism. More importantly, the asobtained MoO x /amine nanostructures remarkably exhibit tunable photochromic properties depending on their 1D structures and hybrid composites, which presents the potential to design well-tailored functional optical nanodevices.

Quantum chemical calculations were carried out on CO oxidation catalyzed by a single gold atom. To investigate the performance of density functional theory (DFT) methods, 42 DFT functionals have been evaluated and compared with high-level wavefunction based methods. It was found that in order to obtain accurate results the functionals used must treat long range interaction well. The double-hybrid mPW2PLYP and B2PLYP functionals are the two functionals with best overall performance. CAM-B3LYP, a long range corrected hybrid GGA functional, also performs well. On the other hand, the popular B3LYP, PW91, and PBE functionals do not show good performance and the performance of the latter two are even at the bottom of the 42 functionals. Our accurate results calculated at the CCSD(T)/aug-cc-pVTZ//mPW2PLYP/aug-cc-pVTZ level of theory indicate that Au atom is a good catalysis for CO oxidation. The reaction follows the following mechanism where CO and O(2) adsorb on Au atom forming an Au(OCOO) intermediate and subsequently O(2) transfer one oxygen atom to CO to form CO(2) and AuO. Then AuO reacts with CO to form another CO(2) to complete the catalytic cycle. The overall energy barrier at 0 K for the first CO oxidation step (Au + CO + O(2)→ AuO + CO(2)) is just 4.8 kcal mol(-1), and that for the second CO oxidation step (AuO + CO → Au + CO(2)) is just 1.6 kcal mol(-1).

This paper reports for the first time that under ammonia atmosphere, ammonia borane (AB) reversibly absorbs up to at least 6 equiv of NH(3), forming liquid AB(NH(3))(n) (n = 1-6) complexes at 0 °C. Reasonable structures for AB(NH(3))(n) were identified via density functional theory calculations, which indicate that the strong classical hydrogen bond formed between the lone pair of NH(3) and the -NH(3) of AB is the driving force for the absorption of ammonia by AB. By use of the van't Hoff equation, the enthalpy change (ΔH) for AB to absorb one NH(3) was determined to be -2.24 kcal/mol, which is in good agreement with the theoretical calculations. Other organic amines were screened to further confirm the role of the N lone pair; only 1,4-diazabicyclo[2.2.2]octane (DABCO) formed a stable adduct, which X-ray structural analysis showed was the DABCO-BH(3) species. Finally, Raman spectra of AB(NH(3))(n) were collected, and its unique spectral features are also discussed.

Liquefaction of Solid-State BH 3 NH 3 by Gaseous NH 3 . -Under 1-4 bar ammonia, H3NBH3 (AB) reversibly absorbs up to 6 equivalents of NH3 forming liquid AB(NH3)n (n = 1-6) complexes at 0°C. The structures of these complexes are characterized by DFT calculations and Raman spectroscopy. The new phenomena displayed by reversible ammonia absorption/desorption of ammonia borane may be of value for some potential applications, for example, separation and purification technologies for ammonia borane, loading into multiple-pore materials, and pressure sensitive materials for ammonia storage. -(GAO, L.; FANG, H.; LI, Z.; YU*, X.; FAN, K.; Inorg. Chem. 50 (2011) 10, 4301-4306, http://dx.