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Photoelectron spectroscopic and computational studies of the Pt@Pb???¹ and Pt@Pb??¹?/²? anions.

ABSTRACT: A combination of anion photoelectron spectroscopy and density functional theory calculations has elucidated the geometric and electronic structure of gas-phase endohedral Pt/Pb cage cluster anions. The anions, Pt@Pb???¹ and Pt@Pb??¹? were prepared from "preassembled" clusters generated from crystalline samples of [K(2,2,2-crypt)]?[Pt@Pb??] that were brought into the gas phase using a unique infrared desorption/photoemission anion source. The use of crystalline [K(2,2,2-crypt)]?[Pt@Pb??] also provided access to K[Pt@Pb(n)](-) anions in the gas phase (i.e., the K? salts of the Pt@Pb(n)²? anions). Anion photoelectron spectra of Pt@Pb???¹, Pt@Pb??¹?, and K[Pt@Pb??]¹? are presented. Extensive density functional theory calculations on Pt@Pb??³?/²?/¹?/? and Pt@Pb??²?/¹? provided candidate structures and anion photoelectron spectra for Pt@Pb???¹ and Pt@Pb??¹?. Together, the calculated and measured photoelectron spectra show that Pt@Pb???¹ and Pt@Pb??²?/¹? endohedral complexes maintain their respective D(4d) and slightly distorted I(h) symmetries in the gas phase even for the charge states with open shell character. Aside from the fullerenes, the Pt@Pb??²? endohedral complex is the only bare cluster that has been structurally characterized in the solid state, solution, and the gas phase.

SUBMITTER: Grubisic A

PROVIDER: S-EPMC3169158 | biostudies-literature | 2011 Sep

REPOSITORIES: biostudies-literature

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Photoelectron spectroscopic and computational studies of the Pt@Pb₁₀⁻¹ and Pt@Pb₁₂¹⁻/²⁻ anions.

Grubisic Andrej A Wang Haopeng H Li Xiang X Ko Yeon-Jae YJ Kocak F Sanem FS Pederson Mark R MR Bowen Kit H KH Eichhorn Bryan W BW

Proceedings of the National Academy of Sciences of the United States of America 20110826 36

A combination of anion photoelectron spectroscopy and density functional theory calculations has elucidated the geometric and electronic structure of gas-phase endohedral Pt/Pb cage cluster anions. The anions, Pt@Pb₁₀⁻¹ and Pt@Pb₁₂¹⁻ were prepared from "preassembled" clusters generated from crystalline samples of [K(2,2,2-crypt)]₂[Pt@Pb₁₂] that were brought into the gas phase using a unique infrared desorption/photoemission anion source. The use of crystalline [K(2,2,2-crypt)]₂[Pt@Pb₁₂] also pro ...[more]

PMID: 21876183

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Project description:The benzoylcyanoxime, NC-C(=N-OH)-C(O)-C6H5 (later H(BCO)), represents a new ampolydentate ligand that received attention in the light of useful biological properties of its coordination compounds. Colorless H(BCO), upon deprotonation, gains color that depends on the counter-cation and the system in general. Five derivatives of H(BCO), with colorless organic and inorganic mono-cations - Cs, Tl, Ag, N(CH3)4 and As(C6H5)4 - were synthesized and characterized by the X-ray analysis, vibrational and electronic spectroscopy. Compounds exhibited unexpected and significant differences in color, both in solid state and in solutions, that were challenging to explain, thereby warranting detailed investigation including high-level DFT/TDFT computations. It was found that the BCO- anion demonstrates negative solvatochromic in polar protic ROH (R = H, CH3, C2H5, C3H7, C4H9) solvents, and appears yellow in color, as tetraalkylammonium or alkali metal salts. In polar aprotic solvents, such as CH3CN, DMF, and DMSO, solutions of the BCO- anion are red. The color originates from n→π* transition in the anion. Solid state structures evidenced a considerable dependence on planarity of the BCO- anion on its color, as well as on the character of bonding in the C-N-O fragment: yellow color is associated with an oxime (bond length C-N is shorter than N-O), while red color is due to the nitroso character (bond length C-N is longer than the N-O). An addition of ethanol to red solutions of the BCO-containing salts leads to the color change to yellow, which is the result of the formation of an H-bond between the C-N-O fragment of cyanoxime and the solvent, also leading to the flattening of the structure. An explanation for this new color-changing effect was offered, based on experimental evidence and TD/DFT calculations. Glossary: H(BCO) is 1-cyano-1-oximino-acetophenone, or benzoylcyanoxime; BCO- is anion of the benzoylcyanoxime; AsPh4 + is tetraphenylarsonium cation; MMe4 + is tetramethyammonium cation; ROH - alcohols; DMF - dimethylformamide; DMSO - dimethylsulfoxide; AN - acetonitrile; DFT -Density Functional Theory; TDDFT - Time-Dependent Density Functional Theory.

Dataset Information

Photoelectron spectroscopic and computational studies of the Pt@Pb???¹ and Pt@Pb??¹?/²? anions.

Publications

Photoelectron spectroscopic and computational studies of the Pt@Pb₁₀⁻¹ and Pt@Pb₁₂¹⁻/²⁻ anions.

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