Transition from Charge‐Transfer to Largely Locally Excited Exciplexes,from Structureless to Vibrationally Structured Emissions

Exciplexes of 9,10‐dicyanoanthracene (DCA) with alkylbenzene donors in cyclohexane show structureless emission spectra, typical of exciplexes with predominantly charge‐transfer (CT) character, when the donor has a relatively low oxidation potential (E_ox), e.g. hexamethylbenzene (HMB). With increasing E_ox and stronger mixing with a locally excited (LE) state, vibrational structure begins to appear with 1,2,3,5‐tetramethylbenzene and becomes prominent with p‐xylene (p‐Xy). A simple theoretical model reproduces the spectra and the radiative rate constants, and it reveals several surprises: Even in this nonpolar solvent, the fractional CT character of a highly mixed exciplex varies widely in response to fluctuations in the microscopic environment. Environments that favor the LE (or CT) state contribute more to the blue (or red) side of the overall spectrum. It is known that sparsely substituted benzene radical cations, e.g., p‐Xy^?+, are stabilized more in acetonitrile than the heavily substituted HMB^?+. Remarkably, ion pairing with DCA^?– in cyclohexane leads to even larger differences in the stabilization of these radical cations. The spectra of the low‐E_ox donors are almost identical except for displacements that approximately equal the differences in E_ox, even though the exciplexes have varying degrees of CT character. These similarities result from compensation among several nonobvious, but quantified factors.     

Photodissociation of pyrene dimer radical cation during the pulse radiolysis–laser flash photolysis combined method

Photodissociation of pyrene (Py) dimer radical cation (Py ₂ ^?+ ) giving pyrene radical cation (Py^?+) and Py and subsequent regeneration of Py ₂ ^?+ by association of Py^?+ and Py were directly observed during the pulse radiolysis–laser flash photolysis combined method at room temperature. When Py ₂ ^?+ was excited at the local excitation band with the 532-nm laser flash, the rapid growth and decay of monomeric Py^?+ were observed at 460 nm. The dissociation of Py ₂ ^?+ proceeded via a one-photon process to give the ground-state Py^?+(D₀) and Py in the quantum yield (Φ_diss) of (2.9 ± 0.9) × 10^?3. It was shown that Py^?+ decayed with a time constant of several tens of nanoseconds, indicating that the association of Py^?+ with Py regenerating Py ₂ ^?+ proceeds at a diffusion-controlled rate. The photodissociation proceeded from the lowest excited state of Py ₂ ^?+ , even when Py ₂ ^?+ was excited to the higher excited state. The difference between the Φ_diss value of Py ₂ ^?+ and that previously reported for naphthalene dimer radical cation (Np ₂ ^?+ ) is discussed.     

Oxygenation and chlorination of aromatic hydrocarbons with hydrochloric acid photosensitized by 9-mesityl-10-methylacridinium under visible light irradiation

Efficient photocatalytic oxygenation of toluene occurs under visible light irradiation of 9-mesityl-10-methylacridinium (Acr⁺–Mes) in oxygen-saturated acetonitrile containing toluene and aqueous hydrochloric acid with a xenon lamp for 15 h. The oxygenated products, benzoic acid (70 %) and benzaldehyde (30 %), were formed after the photoirradiation. The photocatalytic reaction is initiated by intramolecular photoinduced electron transfer from the mesitylene moiety to the singlet excited state of the Acr⁺ moiety of Acr⁺–Mes, which affords the electron-transfer state, Acr^?–Mes^?+. The Mes^?+ moiety can oxidize chloride ion (Cl^?) by electron transfer to produce chlorine radical (Cl^?), whereas the Acr^? moiety can reduce O₂ to O ₂ ^?? . The Cl^? radical produced abstracts a hydrogen from toluene to afford benzyl radical in competition with the bimolecular radical coupling of Cl^?. The benzyl radical reacts with O₂ rapidly to afford the peroxyl radical, leading to the oxygenated product, benzaldehyde. Benzaldehyde is readily further photooxygenated to yield benzoic acid with Acr^?–Mes^?+. In the case of an aromatic compound with electron-donating substituents, 1,3,5-trimethoxybenzene, photocatalytic chlorination occurred efficiently under the same photoirradiation conditions to yield a monochloro-substituted compound, 2,4,6-trimethoxychlorobenzene.     

Triplet excited states of nitronaphthalenes. III. 1,4-dinitronaphthalene

Nanosecond flash photolysis of 1,4-dinitronaphthalene (1,4-DNO₂N) in aerated and deaerated solvents shows a transient species with absorption maximum at 545 nm. The maximum of the transient absorption is independent of solvent polarity and its lifetime seems to be a function of the hydrogen donor efficiency of the solvent. The transient absorption is attributed to the lowest excited triplet state of 1,4-DNO₂N. The reactivity of this state for hydrogen abstraction from tributyl tin hydride (Bu₃SnH), K_q = 3.8 × 10⁸M^?1 sec, is almost equal to that of nitrobezene triplet state which has been characterized as an n → π* state. Based on spectroscopic and kinetic evidence obtained in the present work, the triplet state of 1,4-DNO₂N behaves as an n → π* state in nonpolar solvents, while in polar solvents the state is predominantly n → π* with a small amount of intramolecular charge transfer character.     

Determination of Sodium Hexametaphosphate in Beverages Based on the Fluorescence Quenching of Acridine Orange

Sodium hexametaphosphate was shown to form a complex with acridine orange by electrostatic interactions that induce fluorescence quenching. Analysis of fluorescence intensity showed that the process was dominated by static quenching, which was confirmed by absorption spectra and lifetime of the excited state. The decreased fluorescence intensity was directly proportional to the concentration of sodium hexametaphosphate between 8.0 × 10^?7 and 1.1 × 10^?5 mol L^?1 with a limit of detection of 5.3 × 10^?7 mol L^?1. Beverages were analyzed for sodium hexametaphosphate with recoveries between 91.7% and 108.3%.     

Low‐lying singlet excited states of isocyanogen

Recent photofragment fluorescence excitation (PHOFEX) spectroscopy experiments have observed the ùA″ singlet excited state of isocyanogen (CNCN) for the first time. The observed spectrum is not completely assigned and significant questions remain about the excited states of this system. To provide insight into the energetically accessible excited states of CNCN, optimized geometries, harmonic vibrational frequencies, and excitation energies for the first three singlet excited states are determined using equation‐of‐motion coupled‐cluster theory with singles and doubles (EOM‐CCSD) and correlation‐consistent basis sets. Additionally, excited state coupled‐cluster methods which approximate the contributions from triples (CC3) are utilized to estimate the effect of higher‐order correlation on the energy of each excited state. For the ùA″ state, our best estimate for T₀ is about 42,200 cm^?1, in agreement with the experimentally estimated upper limit for the zero‐point level of 42,523 cm^?1. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Interaction of Halogenoantimonates with Aromatic Compounds in organic solvents

The interaction of SbCl_nBr_6-n^? (n = 1—6) with various bπ-donors has been investigated by means of UV spectroscopy, conductometry, and polarography. The influence of the bπ-donor structure, of the corresponding cation, the ligands of the antimonates, and the solvent on the behaviour of complex formation is discussed. With increasing ionization potential of the bπ-donor the CT absorption shifts to higher energies. Derivatives of aminobenzene lead to the formation of radical cations. The influence of 18-crown-6 on the radical cation formation is also discussed. With increasing content of bromine in the antimonate the overall acceptor strength increases as well. The influence of the solvent on CT energy depends on both the specific solvation of the ground state of the electron donor-acceptor complex and the dielectric solvation of the excited state of the complex.     

Squaraine Rotaxane as a Reversible Optical Chloride Sensor

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.     

Structure and Reactivity of the Distonic and Aromatic Radical Cations of Tryptophan

In this work, we regiospecifically generate and compare the gas-phase properties of two isomeric forms of tryptophan radical cations—a distonic indolyl N-radical (H₃N⁺ - TrpN^?) and a canonical aromatic π (Trp^?+) radical cation. The distonic radical cation was generated by nitrosylating the indole nitrogen of tryptophan in solution followed by collision-induced dissociation (CID) of the resulting protonated N-nitroso tryptophan. The π-radical cation was produced via CID of the ternary [Cu^II(terpy)(Trp)] ^?2+ complex. CID spectra of the two isomeric species were found to be very different, suggesting no interconversion between the isomers. In gas-phase ion-molecule reactions, the distonic radical cation was unreactive towards n-propylsulfide, whereas the π radical cation reacted by hydrogen atom abstraction. DFT calculations revealed that the distonic indolyl radical cation is about 82 kJ/mol higher in energy than the π radical cation of tryptophan. The low reactivity of the distonic nitrogen radical cation was explained by spin delocalization of the radical over the aromatic ring and the remote, localized charge (at the amino nitrogen). The lack of interconversion between the isomers under both trapping and CID conditions was explained by the high rearrangement barrier of ca.137 kJ/mol. Finally, the two isomers were characterized by infrared multiple-photon dissociation (IRMPD) spectroscopy in the ~1000–1800 cm^–1 region. It was found that some of the main experimental IR features overlap between the two species, making their distinction by IRMPD spectroscopy in this region problematic. In addition, DFT theoretical calculations showed that the IR spectra are strongly conformation-dependent.      

Ultrafast Photoinduced Charge Separation Leading to High‐Energy Radical Ion‐Pairs in Directly Linked Corrole–C60 and Triphenylamine–Corrole‐C60 Donor–Acceptor Conjugates

Closely positioned donor–acceptor pairs facilitate electron‐ and energy‐transfer events, relevant to light energy conversion. Here, a triad system TPACor‐C₆₀ , possessing a free‐base corrole as central unit that linked the energy donor triphenylamine ( TPA ) at the meso position and an electron acceptor fullerene (C₆₀) at the β‐pyrrole position was newly synthesized, as were the component dyads TPA‐Cor and Cor‐C₆₀ . Spectroscopic, electrochemical, and DFT studies confirmed the molecular integrity and existence of a moderate level of intramolecular interactions between the components. Steady‐state fluorescence studies showed efficient energy transfer from ¹ TPA* to the corrole and subsequent electron transfer from ¹corrole* to fullerene. Further studies involving femtosecond and nanosecond laser flash photolysis confirmed electron transfer to be the quenching mechanism of corrole emission, in which the electron‐transfer products, the corrole radical cation ( Cor^?+ in Cor‐C₆₀ and TPA‐Cor^?+ in TPACor‐C₆₀ ) and fullerene radical anion (C₆₀^??), could be spectrally characterized. Owing to the close proximity of the donor and acceptor entities in the dyad and triad, the rate of charge separation, k_CS, was found to be about 10¹¹ s^?1, suggesting the occurrence of an ultrafast charge‐separation process. Interestingly, although an order of magnitude slower than k_CS, the rate of charge recombination, k_CR, was also found to be rapid (k_CR≈10¹⁰ s^?1), and both processes followed the solvent polarity trend DMF>benzonitrile>THF>toluene. The charge‐separated species relaxed directly to the ground state in polar solvents while in toluene, formation of ³corrole* was observed, thus implying that the energy of the charge‐separated state in a nonpolar solvent is higher than the energy of ³corrole* being about 1.52 eV. That is, ultrafast formation of a high‐energy charge‐separated state in toluene has been achieved in these closely spaced corrole–fullerene donor–acceptor conjugates.     

Emission spectroscopy and excited-state dynamics of chromyl-chloride vapor

A tunable dye laser has been used to excite single vibronic features in the low-pressure vapor of CrO₂Cl₂. The fluorescence spectrum, fluorescence excitation spectrum and time-resolved fluorescence decay are discussed. It is shown that the active ν′₄ and ν″₄ modes are the same frequency in the gas phase, thus collapsing the sequence congestion normally observed in gas-phase spectra. This degeneracy makes impossible the excitation of single vibronic levels. It is shown that the fluorescence lifetime of the excited state in all except the vibrationally cold level is severely shortened by unimolecular radiationless decay. This radiationless rate is strongly dependent upon the partitioning of energy into various excited-state modes. The radiative lifetime of the vibrationally cold excited state is (1.34 ± 0.08) μs and the apparent bimolecular quenching rate is (5.9 ± 0.2) × 10^?10 cm³/molecules. No evidence of emission from the lowest-energy excited electronic state recently reported by Spoliti [J. Mol. Spectrosc. 52 (1973) 146] is observed.     

The triplet state of 4-nitro-N,N-dimethynaphthylamine

Nanosecond laser photolytic studies of 4-nitro-N,N-dimethylnaphthylamine (4-NDMNA) in nonpolar and polar solvents at room temperature show a transient species with an absorption maximum in the 500-510-nm range. This species is assigned to the lowest triplet excited state of 4-NDMNA. The absorption maximum of this state is independent of solvent polarity, and its lifetime is a function of the hydrogen donor efficiency of the solvent. In n-hexane the lifetime 1/k of the triplet state is 9.1 × 10^?6 sec, while in acetonitrile 1/k is 2.0 × 10^?7 sec. The hydrogen abstraction rate constant k_H of the triplet state with tributyl tin hydride (Bu₃SnH) in n-hexane is 1.7 × 10⁷M^?1·sec^?1, while in the case of isopropyl alcohol as hydrogen donor, k_H is 4.0 × 10⁷M^?1·sec^?1. The activation energy for the hydrogen abstraction by the triplet state from Bu₃SnH in deaerated n-hexane is 0.6 kcal/mol. The lack of spectral shift with increasing solvent polarity, and the appreciable hydrogen abstraction reactivity of the triplet state, also independent of solvent polarity, seem to indicate that this excited state is an n-π* state which retains its n-π* character even in polar media.     

Reactive intermediates in the initiation step of the photo‐oxidation of MDMO‐PPV

Because oxygen cannot be fully eliminated from organic solar cells, the occurrence of oxidative photo‐degradation of the device in operating conditions has to be considered. Polyphenylene‐vinylene‐based photovoltaic devices have a short lifetime that currently limits their applications. In this article, we focus on various transient species that are potentially involved in the initiation step of the photo‐oxidation of poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylenevinylene] (MDMO‐PPV). The role of the transient species was investigated by a combination of quenching and sensitization experiments. Complementary information was obtained by transient absorption spectroscopy. Results evidenced the fact that ¹O₂ was not the principal reactive intermediate involved in the photo‐oxidation of MDMO‐PPV. This result was in contradiction with previous reports. It was shown that the MDMO‐PPV^?+ radical cation was generated after excitation. The presence of oxygen and the photo‐aging favored the formation of the radical cation, suggesting that oxygen and photoproducts act as electron acceptors. The charged radicals formed are likely to evolve and give radicals that initiate the oxidation of the polymer by abstraction of the labile hydrogen in α position of the ether function and by addition on the double bonds. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6044–6052, 2009     

Photodissociation of Co3: Evidence for a long-lived excited state

Energy analysis of the photofragment O^? ions produced in the photodissociation reaction CO₃^? + hv »- O^? + CO₂ identifies two dinstict O^? production mechanisms: a two-photon absorption via an intermediate bound electronic state, and a collision-assisted single-photon process via a long-lived excited state. This species has a radiative lifetime exceeding one microsecond. and a collisional dissociation cross section measurably higher than that of the ground state.     

The role of copper(II) ions in the oxidation of 5-hydroxy-6-methyluracil in the ground and electronically excited states with molecular oxygen in aqueous solutions

A spectral fluorescence study of photoinduced reactions in aqueous solutions has been carried out in order to examine the mechanisms of the oxidation of 5-hydroxy-6-methyluracil (I) in the ground and electronically excited states by molecular oxygen in the presence of copper(II) chloride. It has been found that 5,5,6-trihydroxy-6-methylpyrimidine-2,4-dione (II) is formed upon the photolysis of I. The spectral parameters (λ_max) and the quantum yields (φ) of fluorescence (FL) of compounds I (φ = 8 × 10^–4; λ_max = 362 nm) and II (φ = 17 × 10^–4; λ_max = 306, 330 nm) have been determined. A reaction scheme was proposed, according to which the photooxidation of I occurs through the steps of the generation of the radical cation I ^?+ and the superoxide anion О ₂ ^?- with the subsequent formation of 5,5,6-trihydroxy-6-methylpyrimidine-2,4-dione. The catalytic and inhibitory effects of Cu(II) ions on the oxidation of 5-hydroxy-6-methyluracil in the ground and electronically excited states, respectively, by the oxygen radical anion О ₂ ^?- have been revealed.     

Photoreactions of aromatic compounds—XXIX : Pathway and intermediates of the photoreactions of 3,5-dinitroanisole with nucleophiles

The photoreactions of 3,5-dinitroanisole with nucleophiles (mostly hydroxide ion) have been studied by sensitization and quenching as well as by flash photolysis experiments. The photosubstitution starts mainly from the π-π* triplet excited state (λ_max ～ 475 nm; τ 5·10^?8s or shorter depending on the concentration of nucleophile). The formation of substitution product is completed within ～ 10^?6s. The occurrence of the radical anion (λ_max ～ 550 nm; τ ～ 10^?2-10^?4s depending on the nature of the nucleophile) could be established. This cannot be intermediate in the photosubstitution reaction but is so in the formation of reduction products. The radical anion and, probably also, the substitution product seem to originate from a complex (λ_max ～ 410 nm; τ ～ 5·10^?7s) between the triplet excited aromatic compound and its nucleophilic reaction partner. The formation of this complex is a very fast process.     

On the structural change of some TCNB complexes in the excited singlet state

The absorption spectra of the TCNB-toluene complex in the fluorescent state at 4.2°K were observed. On the basis of the results of excited singlet-singlet absorption spectra of some TCNB complexes at various temperatures, available fluorescence spectral data were re-interpreted. Instead of the model of so-called structural change, an alternative explanation in terms of the triple complex (D₂⁺A^?) in the excited state is proposed.     

Laser-Induced Fluorescence and Photoelectron-Photon Coincidence Studies of 3,5-Octadiyne Cation

3,5-Octadiyne cation in its lowest excited state has been studied in the gas phase by laser-induced fluorescence and photoelectron-photon coincidence techniques. The excitation spectrum of the ò″←²A″ transition has been obtained and yields vibrational frequencies of some of the fundamentals for the excited cationic state. The fluorescence quantum yields and lifetimes at selected energies within the òA″ state have been determined from the coincidence measurements. This provides quantitative data for the discussion of the relaxation behaviour of such an excited open-shell cation.     

Dynamics of excited <Emphasis Type="Italic">m</Emphasis>-dichlorobenzene

Dynamics of excited m-dichlorobenzene is investigated in real time by femtosecond pump-probe method, combined with time-of-flight mass spectrometric detection in a supersonic molecular beam. The yields of the parent ion and daughter ion C₆H₄Cl⁺ are examined as a function of the delay between the 270 and 810 nm femtosecond laser pulses, respectively. The lifetime of the first singlet excited state S₁ of m-dichlorobenzene is measured. The origin of this daughter ion C₆H₄Cl⁺ is discussed. The ladder mechanism is proposed to form the fragment ion. In addition, our experimental results exhibit a rapid damped sinusoidal oscillation over intermediate time delays, which is due to quantum beat effects.     

Excited-state relaxation of protonated adenine.

The excited state dynamics of protonated adenine in the gas phase were investigated by femtosecond pump-probe transient mass spectroscopy. Adenine was protonated in an electrospray ionization source and transferred to a Paul trap. Two femtosecond laser pulses at 266 nm and 800 nm excited the lowest electronic pipi* state and probed the excited-state dynamics by monitoring ion fragment formation. The measured excited state decay is monoexponential with a lifetime shorter than 161 fs. This agrees with a theoretical prediction of very fast internal conversion via a conical intersection with the ground state.