超分子光化学的前景

近二十年来光化学研究取得了巨大进展.其基本状况可归纳为下列几个方面:一是大量的有机分子、配位化合物、金属有机化合物的光化学和光物理行为已被了解,并得到理论上的阐明,许多重要激发态在结构上、能量上以及动态学方面的研究也已相当深入和完善;另一方面,人们对自然界存在的某些重要的光生物过程也有了相当的认识,包括如光合作用,视觉过程等,但尚未完全弄清.     

推荐一组有机光化学实验

有机光化学是近十几年发展起来的一个化学分支。它的发展给现代理论有机和合成化学增添了新的内容和手段。在高等有机教材中也常列有篇章,而在实验方面,一些有机实验书里虽有所反映,但为数甚少。我们结合理论课的学习,参照有关文献、资料做了一组有机光化学实验,并对个别实验进行了一些充实和尝试。     

水相中POPs光化学降解研究进展

综述了近年来12种持久性有机污染物(POPs)在水体中光化学降解行为,从水体中POPs的光解途径、光解机理和定量结构-性质关系(QSPR)三个方面探讨了POPs在水体中的光化学行为,展望了水体中POPs光化学行为的研究前景.     

激光在分离中的应用

近十年来,随着激光技术的应用和发展,在物理和化学领域中出现一门崭新的边缘学科——激光化学。它和经典的光化学一样,是研究光子与物质相互作用过程中,物质激发态的产生、结构、性能及其相互转化的一门科学。然而,由于激光与普通光相比,具有亮度高、单色性好、相干性好和方向性好等突出优点,因而激     

芳烃与烷烃化合物参与的光化学与电化学硼化反应

有机硼化合物是重要的有机合成砌块,并被广泛应用于材料与医药领域.发展实用、简洁的硼化反应合成有机硼化合物一直是有机硼化学的核心课题之一.近年来,光化学和电化学硼化反应取得了快速发展,已成为合成有机硼化合物的重要方法.从能量来源及反应底物类型的角度出发,总结了芳烃与烷烃化合物参与的光化学、电化学和光电化学硼化反应的研究进展,同时也对今后光化学与电化学硼化反应的发展方向进行了展望.     

信息动态

有机光电功能材料作为一种新型功能材料,已应用于高科技领域和民用领域,故借2016年11月召开“2016年国际光致变色会议”之机出版主题专辑,内容主要涉及光致变色和荧光探针领域,希望可以为相关领域的研究人员提供一个展示成果的平台,推动包括光致变色等有机光电功能材料研究工作的深入开展. 此次国际光致变色会议主题之一的有机光致变色材料是光化学研究的重要内容之一,其种类繁多,反应机理也不尽相同,如何根据光物理和光化学原理设计出新型低背景颜色、抗疲劳性强、易于调控的分子,是有机光致变色材料研究的基础.本专辑中的综述文章介绍了不同体系的光致变色材料,包括萘并吡喃光致变色荧光体系(东北师范大学王广等)和二芳烯类光致变色体系(南昌大学蒲守智等)在分子开关器件的应用,还介绍了有机分子三重激发态的调控与应用(大连理工大学赵建章等),并特别感谢赵建章老师精心设计了专刊封面.这些光致变色体系和发光体系都是近年来国内外研究的重点工作.     

锌-镉还原-盐酸萘乙二胺分光光度法测定大气中NO2

1 引言 NO2是一种关键的大气化学组分,参与了多种重要的大气化学过程,如OH自由基、HO2自由基及有机过氧自由基RO2之间的光化学循环,光化学氧化剂及酸雨的形成等,对大气环境有重要影响.     

茂铁基多核配合物猝灭*Cr(bpy)3+3发光过程研究

在过去的十年内,过渡金属联吡啶配合物的光物理和光化学过程得到了迅速发展,激发态的形成及其决定因素在几类经典的配合物中得以很好的研究,尤其是对d~3组态Cr(bpy)_3~(3+)和d~6电子组态Ru(bpy)_3~(2+)的研究尤为突出.二茂铁及其衍生物一直是有机金属化学研究的重要对象.其对Cr(bpy)_3~(3+),Ru(bpy)_3~(2+)等发光剂猝灭作用对分子器件的基础研究具有重要意义.为此,本文合成了一系列含茂铁基多核配合物,并研究了其对Cr(bpy)_3~(3+)发光过程的猝灭作用.     

铱配合物在磷光化学传感器中的应用

由于在生物领域和物联网领域的广泛应用,化学传感器在近期发展迅速.相比于纯有机分子的荧光化学传感器,基于重金属配合物的磷光化学传感器由于发光寿命长,斯托克斯位移大等优点越来越引起人们的广泛关注.重金属铱配合物三线态寿命短,发光效率高而且配合物的发射波长容易受配体的改变而发生变化,因此成为最好的磷光传感器材料之一.本文介绍了铱配合物在磷光化学传感器领域中的应用,具体包括:阳离子传感器、阴离子传感器、氧分子传感器、氨基酸传感器、pH传感器等,并指出了相比于其它磷光化学传感器,基于铱配合物的磷光化学传感器的优势以及目前所存在的问题,最后,对基于铱配合物的磷光化学传感器的研究和发展方向进行了展望.     

第二届全国光化学学术会议简讯

中国科学院于1982年12月8日至13日在杭州召开了第二届全国光化学学术会议。高等院校、工业部门、国防单位和科学院所属研究所等57个单位的171名代表参加了会议。会议邀请了中国科学院学部委员、北京大学冯新德同志做“烯类单体的电荷转移络合光聚合”,中国科学院化学研究所朱秀昌同志做“有机金属化合物光生伏特性”,中国科学院感光化学研究所蒋丽金同志做“生物光化学”,任新民同志做“光化学成象过程的几个问题”的综合性学术报告.     

Chemically Produced Excited States

Electronically excited states of organic molecules are formed in many chemical reactions. Such chemically produced excited states are (with one exception) identical to light produced excited states, and they undergo the molecular transformations expected of such states (“photochemistry without light”). The excited states can also be used in energy transfer experiments. This review covers the generation of chemically produced excited states, the chemical reactions they undergo, and the possible role of chemically produced excited states in biology.     

Comments about the representation of Rydberg and ionic excited states and their photochemistry

This paper discusses the conditions for representing Rydberg and ionic excited states of molecules. It especially shows the intrinsic difficulties of MO methods to treat the weak resonances between strongly polarized situations in highly polarizable symmetric systems; such situations occur in the long distance region for Rydberg excited states of homonuclear molecules, and for the 90 ° twisted singlet excited states of polyenes. The valence/Rydberg mixing is discussed, and some principles for the understanding of Rydberg photochemistry are proprosed, based on a few examples. The present knowledge of the photochemistry of zwitterionic excited states of polyenes is summarized.     

Mechanistic Organic Photochemistry

Organic photochemical reactions can be understood as transformations of the electronically excited states of the reactant molecules. By considering Lewis structure or molecular orbital representations of these excited states it is possible to outline the several possible reactions available in the case of a given reactant. A number of different types of photochemical transformations are now reasonably well understood. In these cases one finds the same common controlling feature, namely the tendency for an excited state species to follow mechanistic pathways of minimum energy and the requirement for continuous electron redistribution in following these pathways. These preferred transformations can often be selected by inspection of relative bond orders for different types of bonding, by comparison of the potential energy surfaces available to the excited state molecules, and by use of correlation diagrams. The reactions derive from both singlet and triplet states, and one of the more reliable methods now available for identifying excited states reacting is termed the “fingerprint method”. Examples of the author's mechanistic approach are given both for ketone and for hydrocarbon photochemistry.     

Inorganic Photochemistry:Past,Present, and Future

Transition metal complex, in its electronic excited state, has intriguing photophysical and photochemical properties that are substantially different from its ground state, Indeed, electronically excited metal complex can be viewed as hot chemical species that is readily synthesized by photo-excitation with UV-visible light. If the energy of excited metal complex can be properly manipulated, it may be possible to devise new catalytic system for converting light to chemical energy. In the context of energy conversion reactions and chemical sensing, it is important for biomolecular reactions at room temperature. Among the photochemical bimolecular reactions, the following three have the widest applications in photocatalysis, and these are (1) bimolecular outer-sphere electron transfer reactions, (2) bimoleculat inner-sphere atom transfer/abstract reactions, and (3) exciplex formation involving electronic excited state. The past of inorganic photochemistry has demonstrated the success of[Ru(bpy)₃]²⁺ as a powerful reagent for light-induced electron transfer reactions. Much of the current photochemistry research focus on coordinative unsaturated metal complexes, that are strongly photoluminescent and readily undergo substrate binding reactions in their excited states. In this lecture, I will review some of the past successful stories of[Ru(bpy)₃]²⁺ and discuss our current research on the luminescent metal-complexes prepared in my laboratory. I will end my lecture by proposing a clue for achieving light-induced multi-electron transfer reactions, which remains a challenge in photochemistry research.     

Analytical time-dependent density functional derivative methods within the RI-J approximation, an approach to excited states of large molecules

Time-dependent density functional theory (TDDFT) is now well established as an efficient method for molecular excited state treatments. In this work, we introduce the resolution of the identity approximation for the Coulomb energy (RI-J) to excited state gradient calculations. In combination with nonhybrid functionals, the RI-J approximation leads to speed ups in total timings of an order of magnitude compared to the conventional method; this is demonstrated for oligothiophenes with up to 40 monomeric units and adamantane clusters. We assess the accuracy of the computed adiabatic excitation energies, excited state structures, and vibrational frequencies on a set of 36 excited states. The error introduced by the RI-J approximation is found to be negligible compared to deficiencies of standard basis sets and functionals. Auxiliary basis sets optimized for ground states are suitable for excited state calculations with small modifications. In conclusion, the RI-J approximation significantly extends the scope of applications of analytical TDDFT derivative methods in photophysics and photochemistry.     

Wavelength dependence of nitrate radical quantum yield from peroxyacetyl nitrate photolysis: experimental and theoretical studies

The photolysis wavelength dependence of the nitrate radical quantum yield for peroxyacetyl nitrate (CH(3)C(O)OONO(2), PAN) is investigated. The wavelength range used in this work is between 289 and 312 nm, which mimics the overlap of the solar flux available in the atmosphere and PAN's absorption cross section. We find the nitrate radical quantum yield from PAN photolysis to be essentially invariant; Phi(NO3)(PAN) = 0.30 +/- 0.07 (+/-2sigma) in this region. The excited states involved in PAN photolysis are also investigated using ab initio calculations. In addition to PAN, calculations on peroxy nitric acid (HOONO(2), PNA) are performed to examine general photochemical properties of the -OONO(2) chromophore. Equation of motion coupled cluster calculations (EOM-CCSD) are used to examine excited state energy gradients for the internal coordinates, oscillator strengths, and transition energies for the n --> pi* transitions responsible for the photolysis of both PNA and PAN. We find in both molecules, photodissociation of both O-O and O-N bonds occurs via excitation to predissociative electronic excited states and subsequent redistribution of that energy as opposed to directly dissociative excitations. Comparison and contrast between experimental and theoretical studies of HOONO(2) and PAN photochemistry from this and other work provide unique insight on the photochemistry of these species in the atmosphere.     

CHEMIENERGIZED SPECIES IN PEROXIDASE SYSTEMS

Abstract— Several hemeprotein-catalyzed reactions generate products of the type expected from the cleavage of a high energy intermediate. For some systems, the formation, in high yield, of a carbonyl compound in its excited triplet state has been firmly established on the basis of (i) equivalence of the chemiluminescence and phosphorescence spectra of the expected products; (ii) energy transfer to sensitizers containing heavy atoms and (iii) occurrence of photoproducts. The excited species appears to be generated within the enzyme and shielded from quenching by oxygen. It may be quenched, however, via long-range triplet-singlet energy transfer.
This work strongly supports our hypothesis that excited electronic states are also formed in biological systems which are not necessarily bioluminescent. One of the functions which peroxidases may thus fulfill might be the utilization of the potential of photochemistry in the absence of light.     

Excited-state kinetics in the photolysis of azoethane and hexafluoroazomethane at 366 nm,up to one atmosphere pressure,and from room temperature to 150°C

The photochemistry of azoethane and hexafluoroazomethane at 366 nm has been reinvestigated up to 1 atm pressure, and over a range of temperature from 27 to 150°C. The Stern-Volmer type quenching plots primarily demonstrate the decomposition of a single electronic and vibrationally excited state for azoethane, but competitive photodissociation from two different electronic and vibrationally excited states, which was previously postulated for hexafluoroazomethane and azoisopropane, is confirmed for hexafluoroazomethane. It is concluded, however, that two different electronic and vibrationally excited photodissociating states are present in azoethane photolysis, but that one of them is difficult to detect, at least by the present approach Photosensitization with biacetyl at 436 nm also causes the dissociation of azoethane, and this is probably from the vibrationally equilibrated first triplet state. The energy barrier for this process was found to be 5.0 kcal/mol.     

Rydberg states in chemistry

The excited states of molecules can be divided into three categories: valence-shell, Rydberg, and intermediate. Reasons are given why this classification is important for photochemistry. The photolytic primary steps should be different for excited states falling into these different categories. Rydberg states should be taken into account when the photochemical reaction path is interpreted in terms of orbital symmetry conservation or diradical intermediates. They might play a role in certain photobiological events.     

High intensity,argon ion laser-jet photochemistry

A new technique for the study of high intensity solution photochemistry has been developed. With this laser-jet technique, a high velocity microjet is irradiated with the focussed output of an argon ion laser. Under these extremely high intensity conditions, photochemically generated transient species with suitable absorption properties are excited further and produce relatively large amounts of photoproducts which are not observed under low intensity conditions. The application of this laser-jet technique in the study of the photochemistry of radicals, biradicals, photoenols and the higher excited states of carbonyl and polycyclic aromatic compounds is described.