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Laser photolysis studies of endothermic triplet energy transfer in solution

溶液中吸热三线态能量转移的激光光解研究

基本信息

批准号：
15550004
负责人：
YAMAJI Minoru
金额：
$ 1.79万
依托单位：
Gunma University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

项目摘要

A bimolecular rate constant (κ_q) and an efficiency (α_<TET>) of an endoergonic triplet energy transfer from triplet α-naphthyl phenyl ketone(NPK) to α-naphthylmethyl phenyl sulfide(NMPS) in solution, where the energy difference (ΔE_T) is 1.7 kcal mol^<-1>, have been determined by means of nanosecond laser flash photolysis. Base on the Arrhenius plots of the κ_q value for the NPK-NMPS system, an activation energy (ΔE_a) for the endoergonic triplet energy transfer is found to be 2.6 kcal mol^<-1>, which is larger than the endothermic energy gap (ΔE_T=1.7 kcal mol^<-1>). The endoergonic triplet energy transfer in solution is demonstrated to proceed with the aid of thermal activation for the first time.The triplet-sensitized photoreactions of the title biplanophane system 6, the photoisomer of a 2.11-diaza[3,3](9,10)anthracenoparacyclophane derivative 5, were investigated by stationary and laser flash photolyses using xanthone(XT) and benzophenone(BP) as triplet sensitizers. Upon XT-sensi … More tized irradiation of the photoisomer 6, a cyclophane 5 and a novel polycyclic product 7 were obtained via an adiabatic cycloreversion and a formal [2πa+2πa+ 2σs] rearrangement. The maximum quantum yield for formation of the cyclophane 5 (0.69) and the upper-limit efficiency for formation of the polycycle 7 (0.31) were determined by laser photolysis techniques. For BP-sensitized photolysis of the photoisomer 6, an oxetane 8 was formed via a Paterno-Buchi reaction in addition to cyclophane 5 and polycycle 7. Quenching rate constant (κ_q) of the triplet sensitizers by photoisomer 6 was smaller by one order of magnitude for BP (3.4x 10^8 dm^3 mol^<-1> s^<-1>) than for XT (5.0x10^9 dm^3 mol^<-1> s^<-1>) and the triplet energy level of photoisomer 6 was estimated as 71 kcal mol^<-1> based on the relationship between κ_q and triplet donor-acceptor energy gap. The photochemical and the photophysical processes involved in the sensitized photolyses are summarized in an energetic reaction diagram and discussed in detail. Less

本文<TET>用纳秒激光闪光光解法测定了溶液中三重态α-萘基苯基酮（NPK）与α-萘甲基苯基硫醚（NMPS）的三重态能量转移的双分子速率常数（κ q）和效率（α_），其中能量差（ΔE_T）为1.7kcal·mol ~<-1>（-1）。根据NPK-NMPS体系κ_q的Arrhenius图，求得三重态能量转移的活化能（ΔE_a）为2.6 kcal mol ~（-1）<-1>，大于吸热能隙（ΔE_T=1.7 kcal mol ~（-1）<-1>）。本文首次证明了溶液中的三重态能量转移是在热活化的辅助下进行的，并以氧杂蒽酮（XT）和二苯甲酮（BP）为三重态敏化剂，通过静态和激光闪光光解研究了标题双平面萘烷体系6（2.11-二氮[3，3]（9，10）蒽并对环芳烷衍生物5的光异构体）的三重态敏化光反应。在XT-sensi上 ...更多信息光致异构体6、环蕃5和新的多环产物7经绝热环化反转和形式[2πa+2πa+ 2σs]重排反应得到。通过激光光解技术确定了形成环蕃5的最大量子产率（0.69）和形成多环7的上限效率（0.31）。对于光异构体6的BP敏化光解，除了环蕃5和多环7之外，还通过Paterno-Buchi反应形成氧杂环丁烷8。光异构体6对三重态敏化剂的猝灭速率常数（κ_q），BP（3.4 × 10^8 dm^3 mol^<-1>s^<-1>）比XT（5.0 × 10^9 dm^3 mol ^<-1>s^<-1>）小一个数量级，根据κ_q与三重态给体-受体能隙的关系，估算光异构体6的三重态能级为71 kcal mol^<-1>。在敏化光解所涉及的光化学和光物理过程中总结了一个充满活力的反应图，并详细讨论。少

项目成果

期刊论文数量（32）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Photochemical reactions of triplet p-phenylbenzyl derivatives studied by using laser flash triplet-sensitization techniques.

使用激光闪光三重态敏化技术研究三重态对苯基苄基衍生物的光化学反应。

DOI：
发表时间：
2005
期刊：
Photochem.Photobiol.Sci. 4
影响因子：
0
作者：
M.Yamaji;M.Yamaji;M.Yamaji.et al.;M.Yamaji.et al.
通讯作者：
M.Yamaji.et al.

A New-Type Photoreaction of A Carbonyl Compound ; Part 2. Photoinduced ω-bond Dissociation in p-Halomethylbenzophenone Studied by Time-Resolved EPR Technique and Laser Flash Photolysis

羰基化合物的新型光反应；第 2 部分：通过时间分辨 EPR 技术和激光闪光光解研究对卤代甲基二苯甲酮中的光诱导 ω 键解离

DOI：
发表时间：
2005
期刊：
J.Photochem.Photobiol.A : Chem. 170
影响因子：
0
作者：
M.Yamaji
通讯作者：
M.Yamaji

A new-type photoreaction of a carbonyl compound Part 1. Photoinduced ω-bond dissociation in p-mercaptomethylbenzophenone studied by time-resolved EPR technique and laser flash photolysis

羰基化合物的新型光反应第1部分：通过时间分辨EPR技术和激光闪光光解研究对巯基甲基二苯甲酮中的光诱导ω键解离

DOI：
发表时间：
2004
期刊：
J.Photochem.Photobiol.A : Chem. 368
影响因子：
0
作者：
M.Yamaji;M.Yamaji;M.Yamaji.et al.;M.Yamaji.et al.;M.Yamaji;M.Yamaji;M.Yamaji;H.Okamoto;M.Yamaji.et al.;H.Okamoto et al.;M.Yamaji
通讯作者：
M.Yamaji

Triplet-Sensitized Photolysis of the Photoisomer of a 2,11-Diaza[3,3](9,10)anthracenophane : An Adiabatic Cycloreversion and a [2πa+2πa+ 2σs]Rearrangement in a Triplet State of the Biplanophane System.

2,11-二氮杂[3,3](9,10)蒽芬光异构体的三重态敏化光解：双平面系统三重态中的绝热环回复和[2πa+2πa+ 2σs]重排。

DOI：
发表时间：
2004
期刊：
J.Org.Chem. 39
影响因子：
0
作者：
M.Yamaji;M.Yamaji;M.Yamaji.et al.;M.Yamaji.et al.;M.Yamaji;M.Yamaji;M.Yamaji;H.Okamoto;M.Yamaji.et al.;H.Okamoto et al.
通讯作者：
H.Okamoto et al.

Triplet-Sensitized Photolysis of the Photoisomer of a 2,11-Diaza[3,3](9,10)anthracenophane : An Adiabatic Cycloreversion and a [2πa + 2πa + 2σs] Rearrangement in a Triplet State of the Biplanophane System

2,11-二氮杂[3,3](9,10)蒽芬光异构体的三重态敏化光解：双平面系统三重态中的绝热环回复和 [2πa + 2πa + 2σs] 重排

DOI：
发表时间：
2004
期刊：
J.Org.Chem. 69
影响因子：
0
作者：
M.Yamaji;M.Yamaji;M.Yamaji.et al.;M.Yamaji.et al.;M.Yamaji;M.Yamaji;M.Yamaji;H.Okamoto;M.Yamaji.et al.;H.Okamoto et al.;M.Yamaji;H.Okamoto
通讯作者：
H.Okamoto