ACTIVE INTERMEDIATES IN PHOTORADICAL AGING OF POLYMERS

The data referring to the mechanism and efficiency of electronically excited macroradical and radical anionreactions, the important role of photochemical chain reactions in polymers are presented, It was found that by varying photonenergy, temperature, photolysis time and competition between thermal and photochemical reactions, it is possible to change the functional composition and molecular weight distribution of polymers.     

Recent Advances and Challenges in the Design of Organic Photoacid and Photobase Generators for Polymerizations

Photopolymerization, or the use of light to trigger polymerization, is one of the most exciting technologies for advanced manufacturing of polymers. One of the key components in the photopolymerization processes is the photoactive compound that absorbs the light, generating the active species that promotes the polymerization and largely determines the final properties of the material. The field of photopolymerization has been dominated by photoradical generators to mediate radical reactions. In the last decade, to expand the number of polymers that can be prepared by photopolymerization, intensive research has been devoted to the synthesis and utilization of photoactive molecules that are able to generate a base or an acid upon irradiation. These organic compounds are known to promote not only the ring‐opening polymerization of various heterocyclic monomers such as lactones, carbonates, or epoxides but also to trigger the step‐growth synthesis of polyurethanes. This Minireview highlights the recent advances in the development of organic photobase and photoacid generators, with the aim of encouraging the wider application of these photoactive compounds in the photopolymerization area and to expand the use of these polymers in advanced manufacturing processes.     

Effect of diabatic correlation on the reactions of O(2 3P, 2 1D) with N2 O and CO2

Although correlation diagrams based upon the application of spin and angular momentum conservation have been shown to be a useful device in interpreting the chemistry of electronically excited atoms, experimental observations suggest that a more complete understanding of such chemical processes requires some insight into the electronic structure of the collision complex. In the absence of such information, it is possible to consider the role of diabatic correlations on the energetics of elementary processes with a view toward analyzing the behavior of the reactants along the reaction coordinate. Here, the aeronomically interesting reactions of ground state and electronically excited oxygen atoms with N₂ O and CO₂ are analyzed and the effects of low-lying molecular excited states on the reactivity of these molecules assessed.     

Proton-coupled electron transfer originating from excited states of luminescent transition-metal complexes

Proton-coupled electron transfer (PCET) is of fundamental importance for small-molecule activation processes, such as water splitting, CO(2)-reduction, or nitrogen fixation. Ideally, energy-rich molecules such as H(2), CH(3)OH, or NH(3) could be generated artificially using (solar) light as an energy input. In this context, PCETs originating directly from electronically excited states play a crucial role. A variety of transition-metal complexes have been used recently for fundamental investigations of this important class of reactions, and the key findings of these studies are reviewed in this article. The present minireview differs from other reviews on the subject of PCET in that it focuses specifically on reactions occurring directly from electronically excited states.     

氟原子与溴代甲烷反应化学发光研究

用光子计数技术系统地探测了F(^2P)原子与溴代甲烷等(CH~3Br、CH~2Br~2和CHBr~3)反应在各种压力下的可见区(300～900nm)化学发光,得到HF电子基态振动泛频跃迁及 Br~2(B)、BrF(B)、CHF(A)、CH(A) 等分子电子激发态跃迁的发射谱.求出HF(υ=3)转动温度为480K,计算机模拟光谱获得了Br~2(B)的振动布居.对比F与氯代甲烷反应的机理分析表明,初级反应主要是F提取形成HF,多级反应产生了电子激发态的产物分子.     

Dynamics and prototropic reactivity of electronically excited states in simple surfactant aggregates

Excitation of a molecule from the ground state to an electronically excited state can cause changes in its geometry, dipole moment, acidity or basicity, redox potentials and solvation. Bimolecular quenching of the excited state of the probe by other molecules present in the medium can be used to determine the mobilities of molecules and estimate microviscosities and encounter probabilities in the medium. Differences in excited state acidity or basicity relative to the ground state can be employed to investigate the dynamics of ultrafast proton transfer reactions. Three areas of current interest where fluorescent probes have served to elucidate important dynamic processes of molecules in simple self-aggregating surfactant systems such as aqueous micelles and reverse micelles are considered: (a) bimolecular quenching of excited states; (b) the dynamics of solvation of excited states and (c) ultrafast intermolecular excited state proton transfer (ESPT) reactions.     

Photophysical processes and the photodissociation of chemical bonds in polyatomic molecules

The main concepts of the nature of electronically excited states in polyatomic molecules and the intramolecular and intermolecular processes of their evolution are reported. The dependence of the probabilities of these processes on the electronic structure of the molecule is considered. Possible mechanisms of the dissociation of electronically excited molecules with bond cleavage are discussed, and the theoretical results of this consideration are given. The experimental data obtained by the authors are interpreted. In this case, attention is focused on C-H-bond photodissociation processes in a condensed phase, which are the best studied processes. The dissociation of other bonds is briefly discussed.     

LONG RANGE ELECTRON TUNNELING IN BIOLOGICAL AND MODEL SYSTEMS

Abstract— This review paper reports the data on the role of long range electron tunneling in photosynthetic and model systems. The main papers concerned with elucidation mechanisms and kinetical peculiarities of electron transfer in reaction centers of bacteria and green plants are considered. The paper reviews the articles on long range electron transfer in reactions of metalloporphyrins—synthetic analogs of the main natural pigment of photosynthesis, chlorophyll. Liquid and solid phase redox reactions of electronically excited porphyrin molecules, intramolecular and photosensitized electron transfer processes are considered.     

Autocatalytic processes during oxidation of lignin in alkaline media

Results are presented that characterize features of the oxidation of lignin in alkaline media. The prerequisites are considered and proofs are given of the appearance of autocatalytic reactions on the oxidation of lignin at the level of one-electron transfer between the phenoxyl radicals being formed and the initial fragments and between chromophores in triplet electronically excited states and other fragments and of the development of concerted oxidation reactions through the appearance of active forms of oxygen, and vibrationally excited states. The results obtained indicate that on the oxidation of lignin in alkaline media a network of chemical reactions bearing the autocatalytic nature of chain processes with degenerate energy branching is formed.Siberian Scientific Research Institute of Cellulose and Board, Bratsk. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 426–433, May–June, 1988.     

Excited state kinetics of the π*←n photochemistry of hexafluoroacetone

The π*←n excited state kinetics of hexafluoroacetone are reinvestigated in the presence of a vibrational relaxer and sufficient triplet state quencher so that only the reactions of the electronically excited upper singlet state are examined. From a Stern–Volmer type analysis it is concluded that vibrational relaxation of the initially formed vibrationally and electronically excited upper singlet state is via a multistage collisional mechanism. An activation energy of about 6 kcal/mole is reported for the unimolecular decomposition of the upper singlet state.     

Excited state proton transfer reactions of acridine studied by nanosecond fluorometry

Rate constants for excited state protonation reactions of acridine in aqueous solutions have been determined using fluorescence decay measurements. The value of the excited state pK derived from the rate constants is in full agreement with the one obtained from steady state fluorescence measurements. It is concluded that acridine follows a two states reaction scheme in its electronically excited state.     

Analysis of electronically nonadiabatic chemical reactions: An information theoretic approach

A practical procedure for the determination of branching ratios for reactions which lead to either excited or electronically ground state products is outlined. The method is applied to four reactions which could (on energetic grounds) produce an electronically excited iodine atom. No case of a complete inversion is found, but one reaction (F + HI) is predicted to yield a statistical, (one half), I^*(²P_1/2) to I(²P_3/2) ratio.     

En Route to Multisurface Chemistry

This article considers what happens when the energy required for a compound to react is supplied by an irradiation lamp instead of by a Bunsen burner. For this purpose real examples are selected from three typical groups of cases. The respective answers obtained should indicate significant moves in organic photochemistry which may be expected to affect the further development of chemistry as a whole in the near future. During this tour d'horizon particular attention is paid to photochemical processes in solids or solvent matrices, light-induced reactions are especially emphasized as key reactions in (natural product) syntheses, and a strong case is made for interpreting the reactions of electronically excited molecules in terms of Salem correlation diagrams.     

Theoretical analysis of reaction kinetics with singlet oxygen molecules

A comparative analysis of predictive ability of three approaches to estimate the rate constants of reactions of H(2), H, H(2)O and CH(4) with electronically excited O(2)(a(1)Δ(g)) and O(2)(b(1)Σ(g)(+)) molecules is conducted. The first approach is based on a detailed ab initio study of potential energy surfaces. The second one is known as the "bond energy-bond order" method, and the third approach is a modification of the updated method of vibronic terms that makes it possible to evaluate the activation energy of reactions involving electronically excited species. The comparison showed that the estimates of the energy barrier by the updated method of vibronic terms for some reactions can be in good agreement with ab initio calculations and available experimental data. It was revealed that reactions of O(2)(b(1)Σ(g)(+)) molecules with H(2), H(2)O and CH(4) molecules and with the H atom result in the formation of electronically excited species. The reactivity of O(2)(b(1)Σ(g)(+)) molecules is smaller than that of O(2)(a(1)Δ(g)) ones, but much higher as compared to the reactivity of ground state O(2) molecules. For each reaction under study involving oxygen molecules in the excited electronic states O(2)(a(1)Δ(g)) and O(2)(b(1)Σ(g)(+)) the recommended temperature-dependent rate constants are presented.     

Direct observation of the formation of a cyclic poly(alkyl sorbate) via chain-growth polymerization by an N-heterocyclic carbene initiator and ring-closing without extreme dilution

1,3-Di-tert-butylimidazol-2-ylidene (NHCtBu), which is one of the typical N-heterocyclic carbene (NHC), was found to initiate the anionic chain-growth polymerization of methyl sorbate (MS) in toluene at −20°C. The polymerization was accelerated by an aluminum Lewis acid, that is, methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (MAD), to afford cyclic poly(MS)s. Subsequently, thiol-ene click reactions of poly(MS)s with two different alkanethiols were performed using a photoradical initiator to obtain graft-like polymers, which was for the microscopic observation of the chains directly by transmittance electron microscope (TEM). The contamination of linear polymers was hardly observed. This means that the polymers synthesized by our synthetic strategy were indeed cyclic polymers. We also compared the theoretical and experimental chain diameter and width for the graft-like cyclic polymers, where these values were dependent on the molecular weight of the cyclic polymers regulated by the feed monomer/initiator ratio and length of the alkanethiols, respectively.     

ENZYMATIC GENERATION OF ELECTRONICALLY EXCITED STATES BY ELECTRON TRANSFER

Abstract— The catechol oxidase promoted oxidation of catechols produces electronically excited states readily detected by chlorophyll sensitized fluorescence. Both the chemiexcitation step and the transfer step are efficient. The use of chlorophyll has confirmed that the peroxidase catalyzed oxidation of dihydroxyfumarate also generates electronically excited species. It is concluded that efficient enzymatic generation of electronic energy can occur not only through the dioxetane/dioxetanone route, but also via electron transfer processes.     

The mercury-sensitized oxidation of carbon monoxide

The mercury-photosensitized oxidation of CO was studied at 275°C over a wide range of [O₂]/[CO] ratios in the absence and presence of the oxygen atom scavenger 2-trifluoromethylpropene (TMP) and at 25°C at low [O₂]/[CO] ratios in the presence of TMP. By following the quantum yield of CO₂ production, Φ {CO₂}, as a function of the [O₂]/[CO] ratio, the reactions of vibrationally excited CO (v υ 9) and electronically excited O₂, probably in the c¹Σ^?_u state, were studied. At low [O₂]/[CO] ratios the predominant reactions are of vibrationally excited CO (v υ 9). Relative rate constants for chemical reaction versus deactivation of CO (v υ 9) were obtained. At higher [O₂]/[CO] ratios, the principal reactions are of electronically excited O₂. Relative rate constants for chemical reactions and deactivation of this electronically excited O₂ with CO, O₂, and TMP were obtained. From the effect of total pressure on Φ {CO₂}, it is proposed that an intermediate CO₃ is formed in the reaction of electronically excited O₂ with CO.     

Stereochemistry as a probe for photochemical reaction mechanisms

In this publication we have reviewed examples derived from our photochemical investigations where stereochemistry provides information allowing elucidation of the mechanistic details of electronically excited state transformations. The reactions discussed include unimolecular rearrangements of both singlet and triplet excited state species.     

Photochemical Rearrangements and Fragmentations of Alkenes and Polyenes

This article presents a systematic analysis of the numerous intramolecular reactions of electronically excited alkenes categorized according to substance class and reaction type. The rearrangements and fragmentations observed in simple alkenes are usually rediscovered in non-conjugated and conjugated dienes and polyenes, where they are accompanied by reaction types such as rearrangements involving several double bonds, cyclizations, and intramolecular cycloadditions. Geometrical factors largely determine which reaction of a series of energetically feasible competing processes actually takes place. The industrial syntheses of vitamin D utilize many of the reaction types to be discussed.     

Reaction between electronically excited species: O(1D2)+NO2→NO(A)+O2

The high-intensity laser permits the study of reactions between electronically excited species. The laser irradiation of NO₂ generated NO₂ by one-photon excitation and O(¹D) by two-photon dissociation. These two species react with each other, producing electronically excited NO(A). The product energy distribution was nearly statistical, indicating the possible presence of a long-lived collision complex.