Electronic structures of octahedral cluster halides of transition metals [M6X8]n+, [M6X12]n+ and their interstitial compounds [M6X12Z]

We report herein the synthesis, characterization, and coordination chemistry of a free N-aluminylene, namely a carbazolylaluminylene 2b. This species is prepared via a reduction reaction of the corresponding carbazolyl aluminium diiodide. The coordination behavior of 2b towards transition metal centers (W, Cr) is shown to afford a series of novel aluminylene complexes 3-6 with diverse coordination modes. We demonstrate that the Al center in 2b can behave as: 1. a σ-donating and doubly π-accepting ligand; 2. a σ-donating, σ-accepting and π-accepting ligand; and 3. a σ-donating and doubly σ-accepting ligand. Additionally, we show ligand exchange at the aluminylene center providing access to the modulation of electronic properties of transition metals without changing the coordinated atoms. Investigations of 2b with IDippCuCl (IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) show an unprecedented aluminylene-alumanyl transformation leading to a rare terminal Cu-alumanyl complex 8. The electronic structures of such complexes and the mechanism of the aluminylene-alumanyl transformation are investigated through density functional theory (DFT) calculations.

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Chemistry and optical properties of 4d and 5d transition metals. III. Chemistry and electronic structures of ruthenium acidonitrosylammines, [Ru(NH3)4(NO)(L)]q+1a

Inorganic Chemistry ◽

10.1021/ic50110a047 ◽

1972 ◽

Vol 11 (4) ◽

pp. 880-888 ◽

Cited By ~ 51

Author(s):

A. F. Schreiner ◽

S. W. Lin ◽

P. J. Hauser ◽

E. A. Hopcus ◽

D. J. Hamm ◽

...

Keyword(s):

Optical Properties ◽

Transition Metals ◽

Electronic Structures

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Stable Geometric and Electronic Structures of Gold-Coated Nanoparticles M@Au12(M = 5d Transition Metals, from Hf to Hg):IhorOh?

The Journal of Physical Chemistry C ◽

10.1021/jp8033006 ◽

2008 ◽

Vol 112 (33) ◽

pp. 12646-12652 ◽

Cited By ~ 23

Author(s):

Juan Long ◽

Yi-Xiang Qiu ◽

Xian-Yang Chen ◽

Shu-Guang Wang

Keyword(s):

Transition Metals ◽

Electronic Structures ◽

Coated Nanoparticles

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Enhancement of third-order nonlinear optical properties of HMTA stabilized pure and doped ZnS nanoparticles and their electronic structures

Journal of Nonlinear Optical Physics & Materials ◽

10.1142/s0218863518500169 ◽

2018 ◽

Vol 27 (02) ◽

pp. 1850016 ◽

Cited By ~ 6

Author(s):

K. Vijai Anand ◽

G. Vinitha ◽

Sanjeev Gautam ◽

K. H. Chae ◽

R. Mohan ◽

...

Keyword(s):

Transition Metals ◽

Electronic Structures ◽

Nonlinear Optical ◽

Zns Nanoparticles ◽

Third Order ◽

Tetrahedral Symmetry ◽

Nonlinear Optical Susceptibility ◽

Nlo Properties ◽

The Third ◽

Mn Doped

This study reports the third-order nonlinear optical (NLO) properties of hexamethylenetetramine (HMTA) stabilized pure and transition metals (Cu, Co and Mn) doped ZnS nanoparticles (NPs) and their electronic structures. The third-order NLO properties of pure and transition metals (Cu, Co and Mn) doped ZnS NPs were measured by [Formula: see text]-scan technique. From these measurements, the pure and doped ZnS samples exhibit negative nonlinearity i.e., self-defocusing. The open aperture [Formula: see text]-scan measurement shows saturated absorption within the medium. The prepared pure and doped ZnS samples exhibit nonlinear refractive index of the order of 10[Formula: see text][Formula: see text](cm2/W), nonlinear absorption (NLA) coefficient of the order of 10[Formula: see text][Formula: see text]cm/W and nonlinear optical susceptibility of the order of 10[Formula: see text][Formula: see text]esu. The electronic structures of these ZnS NPs were investigated using near edge X-ray absorption fine structure (NEXAFS) measurements at the C K-, N K- and Co L[Formula: see text]-edges. The C K- and N K-edges XANES spectra reveal the appearance of several spectral features in the range 285–290[Formula: see text]eV and 390–430[Formula: see text]eV respectively. The Co L[Formula: see text]-edge NEXAFS spectrum exhibits multiplet absorption lines similar to those of Co[Formula: see text] ions coordinated in tetrahedral symmetry with four sulfur nearest neighbors. These results clearly demonstrate that divalent Co ions substitute Zn sites. From the Raman spectra, the appearance of multiple resonance Raman peaks indicates that the prepared ZnS samples have good optical quality.

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