Structural Studies of Novel Metal Complexes Produced by Laser Ablation of Metals

金属激光烧蚀产生的新型金属配合物的结构研究

• 批准号: 07102009
• 负责人: SATO Hiroyasu
• 金额: $ 92.16万
• 依托单位: Mie University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Specially Promoted Research
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07102009/
• 关键词: laser; ablation; metal complex ions; mass spectrometer; rare gas matrix; Fourier-transform spectroscopy; mid-IR laser; difference frequency generation; フーリエ赤外分光; レーザーアブレーション; 金属イオン; 一価金属イオン; 金属錯体; 分子構造

1. A variety of novel organometallic compounds and inorganic metal complexes can be prepared by the "laser ablation-molecular beam (LAMB)" method developed by us. Their molecular structures are very interesting. The main goal of the present research is to study their molecular structures.2. Reactions of M^+=Mg^+, Al^+, Mn^+ and with ammonia/water binary clusters (NH3)p(H2O)a to form adistribution of product complex ions M^+(NH_3)m(H_2O)n were studied. Structures of the complex ions can be inferred from the pattern of their distribution : selective, mon-selective and magic number-like. Kinetic simulation based on the Kiots' evaporative ensemble model reproduced the essential feature of the distribution.3. Density functional calculations were made on the optimized structures and energetics of mixed-metal binuclearcarbonyl ions [MCr(CO)_n]^+, n 4-6, obtained experimentally by the reaction of M^+ with Cr(CO)_6.4. The products of M^++Cr(CO)_6, and M^+^+benzene reactions were studied in Ar matrix at 10-15 K using a Fourier-transform infrared spectrometer.5. A tunable ns infrared laser light was obtained by difference frequency generation of dye laser light and the 2nd harmonic of a Nd : YAG laser. It was used to obtain spectra of ammonia and methanol cluster ions.6. A tunable CW infrared laser light in the mid-IR (7-10mum) region was obtained by difference frequency generation with a AgGaS_2 crystal using two ring dye/titanium sapphire lasers.7. A triple quadrupole mass spectrometer equipped with an ion trap was designed and constructed. Predissociation action spectra of benzene dimer ion (C_6H_6)_2^+ and its derivatives (C6ll5X)2^+ were measured, and their molecular structures were discussed.8. A cavity ring down spectrometer in the visible region (Nd : YAG laser pumped dye laser-based and CW ring dye laser-based) was constructed, and its performance was tested using J2.

1.激光烧蚀-分子束（LAMB）法可以制备多种新型的金属有机化合物和无机金属配合物。它们的分子结构非常有趣。本研究的主要目的是研究它们的分子结构.本文研究了M^+=Mg^+，Al^+，Mn^+与氨/水二元团簇（NH_3）p（H_2O）a反应生成产物配离子M^+（NH_3）m（H_2O）n的分布。从配离子的分布模式可以推断出配离子的结构：选择性配离子、非选择性配离子和类幻数配离子。基于Kiots蒸发系综模型的动力学模拟再现了这种分布的基本特征.用密度泛函方法计算了混合金属双核羰基离子[MCr（CO）_n]^+（n = 4-6）的优化结构和能量。利用傅里叶变换红外光谱仪研究了10-15 K下Ar基质中M^++Cr（CO）_6和M^+^+苯反应的产物.利用染料激光与Nd：YAG激光的二次谐波差频产生可调谐的纳秒红外激光。它被用来获得氨和甲醇簇离子的光谱。采用两个环形染料/钛蓝宝石激光器，用AgGaS_2晶体差频产生中红外（7- 10 μ m）连续可调谐红外激光.设计并研制了一台带有离子阱的三重四极质谱计。测量了苯二聚体离子（C_6H_6）_2^+及其衍生物（C_6115X）_2 ^+的预解离作用光谱，并讨论了它们的分子结构.搭建了一台基于Nd：YAG激光泵浦染料激光器和连续环形染料激光器的可见光区腔衰荡光谱仪，并利用J2.

项目成果

Takao Wada et al.: "Optimized Structures of Cr_2(CO)_6^+ with Three Different Symmetries by Density Functional Calculation" Applied Organometallic Chemistry. 12(6). 419-426 (1998)

Takao Wada 等人：“通过密度泛函计算优化具有三种不同对称性的 Cr_2(CO)_6^ 结构”应用有机金属化学。

S.Nishio et al.: "Preparation of Amorphous Organic Semiconductor Thin Films with Polyperinaphtalene Structure on Temperature-controlled Substrates by Excimer Laser Ablation of 3,4,9,10-Perylenetetracarboxylic Dianhydride" Applied Surface Science. 127-129.

S.Nishio 等人：“通过准分子激光烧蚀 3,4,9,10-苝四甲酸二酐在温控基板上制备具有聚萘二烯结构的非晶有机半导体薄膜”应用表面科学。

Hiroyasu Sato et al.: "Laser Ablation-Molecular Beam (LAMB) Method : Coordination (Solvation) Chemistry of Monopositive Metal Ions in the Gas Phase" Journal of Photochemistry and Photobiology, A Chemistry. 92. 17-24 (1995)

Hiroyasu Sato 等人：“激光烧蚀分子束（LAMB）方法：气相中单正金属离子的配位（溶剂化）化学”光化学和光生物学杂志，化学。

T.Wada et al.: "Optimized Structures of Cr_2(CO)_6^+ with Three Different Symmetries by Density Functional Calculation" Applied Organometallic Chemistry. 12(in press). (1998)

T.Wada 等人：“通过密度泛函计算优化具有三种不同对称性的 Cr_2(CO)_6^ 结构”应用有机金属化学。

H.Sato et al.: "Limited Coordination Number and Competitive Coordination in Ammonia-Water Mixed-Ligand Complexes of Monopositive Metal lons" Journal of Chemical Physics. 108(in press). (1998)

H.Sato 等人：“单正金属氨水混合配体配合物中的有限配位数和竞争性配位”化学物理杂志。