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、我们开发的“激光烧蚀-分子束（LAMB）”方法可以制备多种新型有机金属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其分子结构。 2． M^+=Mg^+、Al^+、Mn^+ 与氨/水二元团簇 (NH3)p(H2O)a 反应形成产物络离子 M^+(NH_3)m(H_2O)n 的分布被研究了。复合离子的结构可以从其分布模式推断：选择性、单选择性和幻数状。基于Kiots蒸发系综模型的动力学模拟再现了分布的本质特征。 3．对通过M^+与Cr(CO)_6.4反应实验获得的混合金属双核羰基离子[MCr(CO)_n]^+, n 4-6的优化结构和能量学进行了密度泛函计算。利用傅里叶变换红外光谱仪研究了Ar基体中10-15 K下M^++Cr(CO)_6与M^+^+苯反应的产物。 5．通过染料激光和 Nd:YAG 激光器的二次谐波的差频产生获得了可调谐 ns 红外激光。用于获得氨和甲醇簇离子的谱图。 6．采用两个环形染料/钛蓝宝石激光器，通过AgGaS_2晶体差频产生，获得了中红外（7-10mum）区域的可调谐连续红外激光。7．设计并构建了配备离子阱的三重四极杆质谱仪。测量了苯二聚体离子(C_6H_6)_2^+及其衍生物(C6ll5X)2^+的预解离作用谱，并讨论了它们的分子结构。 8．搭建了可见光区腔衰荡光谱仪（基于Nd：YAG激光泵浦染料激光器和基于CW环染料激光器），并使用J2测试了其性能。

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。

Osamu Ito et al.: "Laser Ablation-Molecular Beam Method:A Simple and Versatile Diagosis to Study Chemistry of Monopositive Metal ions in the Gas Phase" Appl.Surf.Sci.106. 90-93 (1996)

Osamu Ito 等人：“激光烧蚀分子束法：研究气相单正金属离子化学的简单而多功能的诊断”Appl.Surf.Sci.106。

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。

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。