共查询到20条相似文献,搜索用时 541 毫秒
1.
Alex S Basheer MC Arun KT Ramaiah D Das S 《The journal of physical chemistry. A》2007,111(17):3226-3230
The squaraine dye bis(2,4,6-trihydroxyphenyl)squaraine (SqH) was earlier reported to form J-type dimer aggregates in acetonitrile solutions at higher concentrations. Subsequent studies have suggested that concentration-dependent changes in the absorption spectrum of SqH in acetonitrile could be attributed to shifts in the acid-base equilibrium due to the presence of water as an impurity. In this work, we describe our studies on the effect of varying acid and dye concentration on the absorption spectra of the bromo and iodo substituted dyes, bis(3,5-dibromo-2,4,6-trihydroxyphenyl)squaraine (SqBr) and bis(3,5-diiodo-2,4,6-trihydroxyphenyl)squaraine (SqI). Analysis of the changes in the absorption spectra as a function of dye concentration and the nature of the solvent composition confirmed the formation of J-type dimer aggregates in aprotic solvents in this class of dyes. Further confirmation for the formation of the J-type dimer aggregates could be obtained by comparing the differences in the triplet excited state properties of the neutral and aggregated forms of the dyes using time-resolved spectroscopy. 相似文献
2.
Surat Hotchandani Das Suresh Thomas K. George George M. V. Kamat Prashant V. 《Research on Chemical Intermediates》1994,20(9):927-938
The role of bis(2,4,6-trihydroxyphenyl)squaraine, Sq, in sensitizing large bandgap semiconductors has been investigated in
the present study. The dye in its aggregate form readily interacts with the TiO2 colloids giving rise to a new charge transfer band in the red region. The apparent association constant for the dye aggregate
and TiO2 colloid as determined from a Benesi-Hildebrand plot is 1600 M-1. Nanocrystalline semiconductor films prepared from TiO2, ZnO, and SnO2 colloids have been modified with Sq to probe the photosensitization effects. Both dye monomers and aggregates were found
to participate in the charge injection process. An incident photon-to-photocurrent efficiency up to 0.7% has been observed. 相似文献
3.
Kulathinte M. Shafeekh Mohanannair S. Soumya Moochikkadavath A. Rahim Annie Abraham Suresh Das 《Photochemistry and photobiology》2014,90(3):585-595
Here, we report the synthesis, photophysical properties and photodynamic effects in DLA live cells of three water soluble squaraine dyes, viz. bisbenzothiazolium squaraine dyes SQMI and SQDI with iodine in one and both benzothiazolium units, respectively, and an unsymmetrical squaraine dye ASQI containing iodinated benzothiazolium and aniline substituents. The diiodinated SQDI showed an anomalous trend in both fluorescence and triplet quantum yields over the monoiodinated SQMI, with SQDI showing higher fluorescence and lower triplet quantum yields compared to SQMI. Nanosecond laser flash photolysis of SQDI and SQMI indicated the formation of triplet excited states with quantum yield of 0.19 and 0.26, respectively. On photoirradiation, both the SQDI and SQMI generate singlet oxygen and it was observed that both dyes undergoing oxidation reactions with the singlet oxygen generated. ASQI which exhibited a lower triplet quantum yield of 0.06 was, however, stable and did not react with the singlet oxygen generated. In vitro cytotoxicity studies of these dyes in DLA live cells were performed using Trypan blue dye exclusion method and it reflect an order of cytotoxicity of SQDI>SQMI>ASQI. Intracellular generation of the ROS was confirmed by dichlorofluorescein assay after the in vitro PDT. 相似文献
4.
Synthesis and Photophysics of BF2‐Rigidified Partially Closed Chain Bromotetrapyrroles: Near Infrared Emitters and Photosensitizers
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En Dai Weidong Pang Prof. Dr. Xian‐Fu Zhang Xudong Yang Ting Jiang Ping Zhang Changjiang Yu Prof. Dr. Erhong Hao Yun Wei Xiaolong Mu Prof. Dr. Lijuan Jiao 《化学:亚洲杂志》2015,10(6):1327-1334
We report the synthesis, crystallographic, optical, and triplet and singlet oxygen generation properties of a series of BF2‐rigidified partially closed chain bromotetrapyrroles as near infrared emitters and photosensitizers. These novel dyes were efficiently synthesized from a nucleophilic substitution reaction between pyrroles and the 3,5‐bromo‐substituents on the tetra‐ and hexabromoBODIPYs and absorb in the near‐infrared region (681–754 nm) with high molar extinction coefficients. Their fluorescent emission (708–818 nm) and singlet oxygen generation properties are significantly affected by alkyl substitutions on the two uncoordinated pyrrole units of these dyes and the polarity of solvents. Among them, dyes 4 ca and 4 da show good singlet oxygen generation efficiency and good NIR fluorescence emission (fluorescence quantum yields of 0.14–0.43 in different solvents studied). 相似文献
5.
F. Elisei G. G. Aloisi F. Dall'Acqua L. Latterini F. Masetti P. Rodighiero 《Photochemistry and photobiology》1998,68(2):164-172
The decay processes of the lowest excited singlet and triplet states of five methylated angelicins (4,6,4′-trimethyl-angelicin, MA, and four methylated thioangelicins, MTA; see Scheme 1) were investigated in live solvents by stationary and pulsed fluorometric and flash photolytic techniques. In particular, the solvent effects on absorption, fluorescence, quantum yields of fluorescence (φF) and triplet formation (φT), lifetimes of fluorescence (τF) and the triplet state (τT) and the quantum yields of singlet oxygen production (φΔ) were investigated. Semiempirical (ZINDO/S-CI) calculations were carried out to obtain information (transition probabilities and nature) on the lowest excited singlet and triplet states. The quantum mechanical calculations and the solvent effect on the photophysical properties showed that the lowest excited singlet state (S1) is a partially allowed π,π* state, while the close-lying S2 state is n,π* in nature. The efficiencies of fluorescence, S1→T1 intersystem crossing (ISC) and S1→ S0 internal conversion (IC) strongly depend on the energy gap between S1, and S2 and are explained in terms of the so-called proximity effect. In fact, for MA in cyclohexane, only the S1→ S0 internal conversion is operative, while in acetonitrile and ethanol, where the n.π* state is shifted to higher energy, the efficiencies of fluorescence and ISC increase significantly. The energy gap between S1 and S2 increases in MTA, where the furanic oxygen is replaced by a sulfur atom. Consequently, the solvent effect on the photophysical parameters of MTA is less marked than for MA; e.g. fluorescence and triplet-triplet absorption are also detectable in the nonpolar cyclohexane. The lowest excited singlet state of molecular oxygen O2(1Dg) was produced efficiently in polar solvents by energy transfer from the T1 state of MA and MTA. 相似文献
6.
PHOTOPHYSICAL AND PHOTOSENSITIZING PROPERTIES OF BENZOPORPHYRIN DERIVATIVE MONOACID RING A (BPD-MA)*
The photophysical properties of benzoporphyrin derivative monoacid ring A (BPD-MA), a second-generation photosensitizer currently in phase II clinical trials, were investigated in homogeneous solution. Absorption, fluorescence, triplet-state, singlet oxygen (O2(1Δg)) sensitization studies and photobleaching experiments are reported. The ground state of this chlorin-type molecule shows a strong absorbance in the red (λ≈ 688 nm, ?≈ 33 000 M?1 cm?1 in organic solvents). For the singlet excited state the following data were determined in methanol: energy level, Es= 42.1 kcal mol?1, lifetime, Φf= 5.2 ns and fluorescence quantum yield, Φf= 0.05 in air-saturated solution. The triplet state of BPD-MA has a lifetime, τf >. 25 ns, an energy level, ET= 26.9 kcal mol?1 and the molar absorption coefficient is ?T= 26 650 M?1 cm?1 at 720 nm. A dramatic effect of oxygen on the fluorescence (φf) and intersystem crossing (φT) quantum yields has been observed. The BPD-MA presents rather high triplet (φT= 0.68 under N2-saturated conditions) and singlet oxygen (φΔ= 0.78) quantum yields. On the other hand, the presence of oxygen does not significantly modify the photobleaching of this photostable compound, the photodegradation quantum yield (φPb) of which was found to be on the order of 5 × 10?5 in organic solvents. 相似文献
7.
In recent years squarines received attention as fluorescent labels. Their very promising spectral properties such as long wavelength absorption and emission, high extinction coefficients and quantum yields could lead novel sensing technologies. In this work newly synthesized fluoroinophores named bis[4-N-(1-aza-4,7,10,13-tetraoxacyclopentadecyl)-3,5-dihydroxyphenyl]squaraine, azacrown-1 and 2 bis[4-N-(1-aza-4,7,10,13,16-pentaoxacyclooctadecyl)-3,5-dihydroxyphenyl]squaraine, azacrown-2 have been used for sodium and potassium sensing in plasticized PVC matrix. The squaraine derivatives exhibited fluorescence emission based optical responses to sodium and potassium with a detection limit of 1.10(-9) M. The sensor compositions exhibited wide response ranges between 10(-9) and 10(-5) M Na(+)or K(+), and, therefore, may be an alternative method to flame emission spectroscopy. The sensor is fully reversible within the dynamic range and the response time is 3 min under batch conditions. Cross sensitivity to pH is negligible in the pH range of 6.2-7.3. Throughout fiber optic based studies a relative signal change of 54-56% has been achieved. The azacrown dyes have the advantage that they can be excited with long wavelength light and, are, therefore, LED compatible. The cross sensitivity of azacrown-1 and -2 to Ba(2+), Ca(2+) and NH(4)(+)were also tested in separate solutions. 相似文献
8.
Dr. Jing Chen Prof. Dr. Rainer F. Winter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(34):10733-10741
The bis(vinyl ruthenium)‐modified squaraine dye 1 was synthesized by treatment of [RuHCl(CO)(PiPr3)2] with bis(ethynyl)‐substituted squaraine 8 . Spectroscopic and electrochemical measurements on 1 and its organic precursors 6 – 8 were performed to study the effect of the vinyl ruthenium “substituents,” particularly with respect to (poly)electrochromism. Attachment of the vinyl ruthenium moieties endows metal–organic squaraine 1 with two additional oxidation waves and lowers the first two oxidation potentials by approximately 300 mV with respect to its organic precursors. Squaraines 6 , 7 , 8 , and 1 strongly absorb at 648, 663, 656, or 709 nm. Although organic dyes 6 , 7 , and 8 fluoresce, no room‐temperature emission is observed for 1 . The radical cations and anions of 6 , 7 , 8 , and 1 as well as the doubly oxidized dications have been studied by IR and UV/Vis/NIR spectroelectrochemistry, and the ?/0/+/2+ redox sequences were found to be reversible in each case. Our results indicate that the 12?/?/0/+/2+ redox system constitutes a polyelectrochromic switch in which absorption in the visible or the near‐infrared range is reversibly turned off or shifted deep into the NIR. They also show that radical cation 1.+ is an intrinsically delocalized system with only little contribution from the outer vinyl ruthenium tags to the oxidation process. Dication 12+ constitutes a class‐II mixed‐valent system with two electronically different vinyl ruthenium moieties and has an open‐shell singlet electronic ground‐state structure. ESR and NMR spectra of chemically prepared 1.+ and 12+ corroborate these results. It has also emerged that reduction involves an orbital that is strongly delocalized across the entire squaraine π system and strongly affects the peripheral vinyl ruthenium sites. 相似文献
9.
Jeremiah J. Gassensmith Dr. Sarah Matthys Jung‐Jae Lee Dr. Aleksandra Wojcik Dr. Prashant V. Kamat Prof. Dr. Bradley D. Smith Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(9):2916-2921
A mechanically interlocked squaraine rotaxane is comprised of a deep‐red fluorescent squaraine dye inside a tetralactam macrocycle. NMR studies show that Cl? binding to the rotaxane induces macrocycle translocation away from the central squaraine station, a process that is completely reversed when the Cl? is removed from the solution. Steady‐state fluorescence and excited‐state lifetime measurements show that this reversible machine‐like motion modulates several technically useful optical properties, including a three‐fold increase in deep‐red fluorescence emission that is observable to the naked eye. The excited states were characterized quantitatively by time‐correlated single photon counting, femtosecond transient absorption spectroscopy, and nanosecond laser flash photolysis. Cl? binding to the rotaxane increases the squaraine excited singlet state lifetime from 1.5 to 3.1 ns, and decreases the excited triplet state lifetime from >200 to 44 μs. Apparently, the surrounding macrocycle quenches the excited singlet state of the encapsulated squaraine dye and stabilizes the excited triplet state. Prototype dipsticks were prepared by adsorbing the lipophilic rotaxane onto the ends of narrow, C18‐coated, reverse‐phase silica gel plates. The fluorescence intensity of a dipstick increased eighteen‐fold upon dipping in an aqueous solution of tetrabutylammonium chloride (300 mM ) and was subsequently reversed by washing with pure water. It is possible to develop the dipsticks for colorimetric determination of Cl? levels by the naked eye. After dipping into aqueous tetrabutylammonium chloride, a dipstick’s color slowly fades at a rate that depends on the amount of Cl? in the aqueous solution. The fading process is due primarily to hydrolytic bleaching of the squaraine chromophore within the rotaxane. That is, association of Cl? to immobilized rotaxane induces macrocycle translocation and exposure of the electrophilic C4O2 core of the squaraine station, which is in turn attacked by the ambient moisture to produce a bleached product. 相似文献
10.
Nagappanpillai Adarsh Madhesh Shanmugasundaram Dr. Rekha R. Avirah Dr. Danaboyina Ramaiah 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(40):12655-12662
A new series of aza‐BODIPY derivatives ( 4 a – 4 c , 5 a , c , and 6 b , c ) were synthesized and their excited‐state properties, such as their triplet excited state and the yield of singlet‐oxygen generation, were tuned by substituting with heavy atoms, such as bromine and iodine. The effect of substitution has been studied in detail by varying the position of halogenation. The core‐substituted dyes showed high yields of the triplet excited state and high efficiencies of singlet‐oxygen generation when compared to the peripheral‐substituted systems. The dye 6 c , which was substituted with six iodine atoms on the core and peripheral phenyl ring, showed the highest quantum yields of the triplet excited state (ΦT=0.86) and of the efficiency of singlet‐oxygen generation (ΦΔ=0.80). Interestingly, these dyes were highly efficient as photooxygenation catalysts under artificial light, as well as under normal sunlight conditions. The uniqueness of these aza‐BODIPY systems is that they are stable under irradiation conditions, possess strong red‐light absorption (620–680 nm), exhibit high yields of singlet‐oxygen generation, and act as efficient and sustainable catalysts for photooxygenation reactions. 相似文献
11.
Salvatore Sortino Giancarlo Marconi Salvatore Giuffrida Guido De Guidi Sandra Monti 《Photochemistry and photobiology》1999,70(5):731-736
The photophysical properties of rufloxacin, 9-fluoro-2r3-dihydro-10-(4-methyl-l-pyrazinyl)-7-oxo-7-H-pyri-do[l,2,3-de]-l,4-benzothiazin-6-carboxylic acid, a fluoroquinolone antibacterial drug exhibiting photosensitizing action toward biological substrates, were studied in aqueous solutions at neutral pH. The lowest excited electronic states of the zwitterion were characterized by both experimental techniques and theoretical methods. Steady-state and time-resolved emission, triplet-state absorption and singlet oxygen production were investigated. The results indicate that the lowest excited singlet is a fluorescent, relatively long-lived state (φr= 0.075, Tr? 4.5 ns) with an efficient intersystem crossing to the triplet manifold (φisc? 0-7)- The lowest triplet is a long-lived state (TT? 10 μs at 295 K in 0.01 M phosphate buffer), with properties that make it a good candidate for being the precursor of the photodecarboxylation of the drug. It is quenched by oxygen at a rate of 1.7 times 109M-1 s-1 and singlet oxygen is formed with a quantum yield of 0.32 in air-saturated solutions. 相似文献
12.
The low-lying singlet and triplet states of H2CBe and HCBeH are examined using ab inito molecular orbital theory. In agreement with earlier results, the lowest-lying structure of H2CBe has C2v symmetry and is a triplet with one π electron (3 B1). The results presented here suggest that the lowest-energy singlet structure is the (1B1) open-shell singlet, also with C2v symmetry, at least 2.5 kcal/mol higher in energy. The singlet C2v structure with two π electrons (1A1) is 15.9 kcal/mol higher than 3B1. All of these structures are bound with respect to the ground state of methylene and the beryllium atom. In HCBeH, linear equilibrium geometries are found for the triplet (3Σ) and singlet (1Δ) states. The triplet is more stable than the singlet (1Δ) by 35.4 kcal/mol, and is only 2.9 kcal/mol higher in energy than triplet H2 CBe. Since the transition structure connecting these two triplet molecules is found to be 50.2 kcal/mol higher in energy than H2 CBe, both triplet equilibrium species might exist independently. The harmonic vibrational frequencies of all structures are also reported. 相似文献
13.
Prof. Dr. Curt Wentrup Dr. Michèle J. Regimbald‐Krnel Dr. Dennis Müller Prof. Dr. Peter Comba 《Angewandte Chemie (International ed. in English)》2016,55(47):14600-14605
Variable‐temperature NMR and ESR spectroscopic studies reveal that bis(dibenzo[a,i]fluorenylidene) 1 possesses a singlet ground state, 1 (S0), while the 90° twisted triplet 1 (T1) is populated to a small extent already at room temperature. Analysis of the increasing amount of paramagnetic 1 (T1) at temperatures between 300 and 500 K yields the exchange interaction Jex/h c=3351 cm?1 and a singlet–triplet energy splitting of 9.6 kcal mol?1, which is in excellent agreement with calculations (9.3 kcal mol?1 at the UKS BP86/B3LYP/revPBE level of theory). In contrast, the zero‐field splitting parameter D is very small (calculated value ?0.018 cm?1) and unmeasurable. 相似文献
14.
Water‐Soluble Luminescent Cyclometalated Gold(III) Complexes with cis‐Chelating Bis(N‐Heterocyclic Carbene) Ligands: Synthesis and Photophysical Properties
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Faan‐Fung Hung Dr. Wai‐Pong To Dr. Jing‐Jing Zhang Dr. Chensheng Ma Prof. Dr. Wai‐Yeung Wong Prof. Dr. Chi‐Ming Che 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(28):8604-8614
A new class of cyclometalated AuIII complexes containing various bidentate C‐deprotonated C^N and cis‐chelating bis(N‐heterocyclic carbene) (bis‐NHC) ligands has been synthesized and characterized. These are the first examples of AuIII complexes supported by cis‐chelating bis‐NHC ligands. [Au(C^N)(bis‐NHC)] complexes display emission in solutions under degassed condition at room temperature with emission maxima (λmax) at 498–633 nm and emission quantum yields of up to 10.1 %. The emissions are assigned to triplet intraligand (IL) π→π* transitions of C^N ligands. The AuIII complex containing a C^N (C‐deprotonated naphthalene‐substituted quinoline) ligand with extended π‐conjugation exhibits prompt fluorescence and phosphorescence of comparable intensity with λmax at 454 and 611 nm respectively. With sulfonate‐functionalized bis‐NHC ligand, four water‐soluble luminescent AuIII complexes, including those displaying both fluorescence and phosphorescence, were prepared. They show similar photophysical properties in water when compared with their counterparts in acetonitrile. The long phosphorescence lifetime of the water‐soluble AuIII complex with C‐deprotonated naphthalene‐substituted quinoline ligand renders it to function as ratiometric sensor for oxygen. Inhibitory activity of one of these water‐soluble AuIII complexes towards deubiquitinase (DUB) UCHL3 has been investigated; this complex also displayed a significant inhibitory activity with IC50 value of 0.15 μM . 相似文献
15.
Eight differently substituted title dye compounds have been investigated regarding intersystem crossing, triplet state, fluorescence and singlet excited state pKa properties. In general, non-halogenated oxazines and thiazines as well as a mono bromooxazine show very low triplet quantum yields, phi tau (less than 0.03) and relatively long triplet lifetimes (approximately 40 microseconds) in acidic methanol. The phi tau data correlate well with known singlet oxygen yields. In basic methanol no triplet transient is observed but a significant yield of a ground state transient protonated (base dye) form is produced with a short lifetime, approximately 400 ns. Fluorescence can be seen simultaneously from both the excited base and the protonated base dye forms in basic methanol. For iodinated oxazine or thiazines, the triplet yield increases and can be as high as 0.5 (diiodo case) in acidic methanol. The triplet lifetimes are further shortened to approximately 10 microseconds compared to the non-iodinated derivatives above. The triplet yields of the iodo compounds are higher or equal to known singlet oxygen yields. In basic methanol triplet yields up to 0.2 can be seen, the triplet lifetime are shortened still further to 1 microsecond but no observable protonated form is produced (in distinction to the non-iodinated cases). Consideration is given to the correlation of triplet and singlet oxygen yields, ground and excited pKa properties, spin-orbit coupling and internal conversion properties, solvent effects, and phototherapeutic activity of these dyes. 相似文献
16.
Curt Wentrup Michle J. Regimbald‐Krnel Dennis Müller Peter Comba 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2016,128(47):14820-14825
Variable‐temperature NMR and ESR spectroscopic studies reveal that bis(dibenzo[a,i]fluorenylidene) 1 possesses a singlet ground state, 1 (S0), while the 90° twisted triplet 1 (T1) is populated to a small extent already at room temperature. Analysis of the increasing amount of paramagnetic 1 (T1) at temperatures between 300 and 500 K yields the exchange interaction Jex/h c=3351 cm−1 and a singlet–triplet energy splitting of 9.6 kcal mol−1, which is in excellent agreement with calculations (9.3 kcal mol−1 at the UKS BP86/B3LYP/revPBE level of theory). In contrast, the zero‐field splitting parameter D is very small (calculated value −0.018 cm−1) and unmeasurable. 相似文献
17.
An unusual infrared chemiluminescence emission (8130Å) of methylene blue, and other thiazine dyes, sensitized by singlet molecular oxygen is reported. This chemiluminescence does not correspond to the ordinary fluorescence of the dye and cannot be explained by previously proposed mechanisms for singlet oxygen sensitized emissions of dyes. From energetic considerations singlet molecular oxygen in its 1Σg+ state is postulated as the sensitizing agent for the thiazine dye chemiluminescences. Schemes in which 1Σg+ oxygen transfers electronic excitation energy (a) to the lowest triplet state of the dye, (b) to a combined multiplicity state of the lowest triplet state of the dye, and triplet molecular oxygen, or (c) to a charge-transfer state between the dye and oxygen, are compared. The chemiluminescence of methylene blue in aqueous solution may be used as a luminescent probe for 1Σg+ oxygen. 相似文献
18.
Elena Reddi Michael A. J. Rodgers John D. Spikes Giulio Jori 《Photochemistry and photobiology》1984,40(4):415-421
Abstract The 83 μM hematoporphyrin (HP)-sensitized photooxidation of 0.1 mM tryptophan in aqueous solution buffered at pH 7.4 or in binary mixtures of phosphate buffer and organic solvents of higher (formamide) or lower (N,N-dimethylformamide, methanol, ethanol, tetrahydrofuran) polarity proceeds by a pure singlet oxygen (1O2) mechanism as suggested by azide quenching experiments, the rate-enhancing action of deuterated solvents, and the lack of any significant reaction between triplet HP and tryptophan. Both the first-order rate constant of the photoprocess and the photooxidation quantum yield (φ= 0.011 in phosphate buffer at pH 7.4) increase when the medium polarity is increased (e.g. φ= 0.024 in 90% formamide); this results mainly from the greater quantum yield of 1O2 generation and the longer lifetime of 1O2. The intrinsic reactivity of 1O2 with tryptophan is independent of formamide concentration. A moderate decrease in the medium polarity (e.g. in the range 0-30% methanol) enhances the efficiency of tryptophan photooxidation (φ= 0.014 in 30% methanol) as a result of the enhanced quantum yields of triplet HP and 1O2 formation. In contrast, the overall photooxidation rate is depressed at high concentrations of low-polarity organic solvents (e.g. φ= 0.0039 in 90% methanol) due to a 5.5-fold drop of the rate constant for the 1O2-tryptophan reaction which counteracts the enhancement of the lifetime and quantum yield of triplet HP and 1O2. The solvent composition also affects the equilibria between monomeric and multimeric forms of HP. However, under our experimental conditions, the aggregation state of HP appears to exert only a minor influence on the efficiency of tryptophan photooxidation. 相似文献
19.
Density functional theory calculations with the B3LYP functional are used to study the structure and stabilities of C5H2 isomers and possible isomerization mechanisms on the triplet and singlet potential energy surfaces.Calculated results show that isomerization of C5H2 is likely to occur on the triplet potential energy surface while direct conversions of the singlet C5H2 isoers via 1,3-hydrogen migration transitions of the singlet C5H2 isomers via 1,3-hydrogen migration transition states are extremely difficult dynamically.In such isomerization processes,the hydrogen transfer processes in carbon chains are the rate-determining steps.The triplet species except the linear ground state X^3∑g^- are rather less stable than their singlet forms,although the singlet and triplet species haver similar geometries. 相似文献
20.
Alexei V. Trofimov‡ Rostislav F. Vasil'ev Karsten Mielke Waldemar Adam 《Photochemistry and photobiology》1995,62(1):35-43
Abstract— The thermal generation of singlet and triplet excited states from silyloxyaryl-substituted spiroadamantyl dioxetanes lab and the adamantylidineadamantane dioxetane (1c) was investigated by direct and enhanced chemiluminescence (CL). 9,10-Diphenylanthracene (DPA) and 9-fluorenone were used as energy acceptors in the singlet-singlet (S-S), naphthalene and europium chelate Eu(TTA)3Phen (TTA = thenoyltrifluoroacetone, Phen = 1,10-phenanthroline) in the triplet-triplet (T-T) and 9,10-di-bromoanthracene (DBA) in triplet-singlet (T-S) energy transfer experiments. The direct chemiluminescence observed in the thermolysis of dioxetanes lab consisted of fluorescence derived from the singlet-excited adamantanones 2a,b. In the presence of naphthalene, selective T-S energy transfer with DBA (napthalene as quencher) displayed the adamantanone triplets 2a,b and with Eu(TTA)3Phen (naphthalene as mediator) also the silyloxyaryl ester 3 triplets. From the Stern-Volmer constants (kTNTT0) the triplet lifetimes t0t of these triplet state products were assessed. By using the Hastings-Weber standard, the total triplet excitation yield (φt) was estimated to be ca 20%. The energies of the first excited singlet and triplet states of the adamantanones 2a,b and the silyloxyaryl ester 3, the products of the thermally induced decomposition of dioxetanes la-c , were determined by semiempirical calculations (AMI-based configuration interaction), which included explicitly solvent effects on the excitation energies in terms of a self-consistent reaction field approach. The calculations revealed that the first excited singlet and triplet states of the adamantanones 2a,b are expectedly n,π*-type excitations while the silyloxyaryl ester 3 possesses π,π* character. The semiempirical computations suggest that excitation of the adamantanones 2a,b as well as the silyloxyaryl ester 3 is feasible in the thermolysis of the spiroadamantyl dioxetanes lab , which has been confirmed by the experimental energy transfer studies. 相似文献