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Intermolecular Dynamics and Exciplex Formation of van der Waals Complexes

范德华配合物的分子间动力学和激基复合物形成

基本信息

批准号：
61470004
负责人：
ITOH Michiya
金额：
$ 4.29万
依托单位：
Kanazawa University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1986
资助国家：
日本
起止时间：
1986 至 1987
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-61470004/
关键词：
van der Waals complex Supersonic jet Exciplex Excimer Fluorescence Transformation of van der Waals complex to Exciplex ファンデアワールス錯体エクサイマー時間分解蛍光スペクトル

项目摘要

1. The exciplex formation dynamics of the 1-cyanonaphthalene/triethylamine van der Waals complex upon excitation has been examined under collision free condition. Mode-specificity has been found in the excitation of a combination band between intra- and intermolecular vibrational modes in the S_1 state of the vdW complex to promote the exciplex formation reaction.The fluorescence decays of the S1 and exciplex states have been measured as a function of excess energy above the S1 origdn. The observed decay rate constants have been discussed using a simple kinetic model.2. Upon excitation of the van der Waals dimer and heterodimer of fluorene and 9-ethylfluorene generated in a supersonic expansion, the excimer and exciplex fluorescence spectra and decay times were obtained, The spectral maximum and decay time of the exciplex are almost intermediate between two excimers of fluorene and 9-ethylfluorene. The transformation of vdW heterodimer to the exciplex takes place from the excited state of the heterodimer corresponding to the locally excited state of 9-ethylfluorene.3. Two types of van der Waals complexes between 1-cyano-4-methylnaphthalene and triethylamine were obvserved in the supersonic free jet. Upon excitation of neraly origin bands of these complexes, the dispersed exciplex fluorescence was observed from one of the complexes, while no significnat exciplex fluorescence was detected from the other complex. However, the fluorescence excitation spectra demonstrate that the transformation to the exciplex proceeds in the excitation to the uper vibrational state of these complexes. The exciplex fromation from the vdW complex was also indicated by the determination of fluorescence decay times of these jet cooled species.

1. 在无碰撞条件下，研究了1-氰萘/三乙胺范德华配合物在激发时的激络合物形成动力学。在vdW配合物的S_1状态下，激发分子内和分子间振动模式之间的组合带，促进外络合物形成反应，发现了模式特异性。S1和外复合体态的荧光衰减已被测量为S1原点以上多余能量的函数。用一个简单的动力学模型讨论了观测到的衰变速率常数。对超声速膨胀产生的芴和9-乙基芴的范德华二聚体和异二聚体进行激发，得到了准分子和外络合物的荧光光谱和衰减时间，外络合物的光谱最大值和衰减时间几乎介于芴和9-乙基芴两个准分子之间。vdW异源二聚体向外络合物的转化发生在异源二聚体的激发态对应于9-乙基芴的局域激发态。在超声速自由射流中观察到1-氰基-4-甲基萘与三乙胺之间的两种范德华配合物。当激发这些配合物的同源条带时，在其中一个配合物中观察到分散的激复数荧光，而在另一个配合物中没有检测到明显的激复数荧光。然而，荧光激发光谱表明，在激发到这些配合物的高振动状态时，向外络合物的转变是进行的。通过测定这些射流冷却的物质的荧光衰减时间，也表明了vdW配合物的外络合物形成。