Bimolecular hydrogen abstraction from phenols by aromatic ketone triplets

Absolute rate constants for hydrogen abstraction from 4-methylphenol (para-cresol) by the lowest triplet states of 24 aromatic ketones have been determined in acetonitrile solution at 23 degrees C, and the results combined with previously reported data for roughly a dozen other compounds under identical conditions. The ketones studied include various ring-substituted benzophenones and acetophenones, alpha,alpha,alpha-trifluoroacetophenone and its 4-methoxy analog, 2-benzoylthiophene, 2-acetonaphthone, and various other polycyclic aromatic ketones such as fluorenone, xanthone and thioxanthone, and encompass n,pi*, pi,pi*(CT) and arenoid pi,pi* lowest triplets with (triplet) reduction potentials (E(red)*) varying from about -10 to -38 kcal mol(-1). The 4-methylphenoxyl radical is observed as the product of triplet quenching in almost every case, along with the corresponding hemipinacol radical in most instances. Hammett plots for the acetophenones and benzophenones are quite different, but plots of log k(Q) vs E(red)* reveal a common behavior for most of the compounds studied. The results are consistent with reaction via two mechanisms: a simple electron-transfer mechanism, which applies to the n,pi* triplet ketones and those pi,pi* triplets that possess particularly low reduction potentials, and a coupled electron-/proton-transfer mechanism involving the intermediacy of a hydrogen-bonded exciplex, which applies to the pi,pi* ketone triplets. Ketones with lowest charge-transfer pi,pi* states exhibit rate constants that vary only slightly with triplet reduction potential over the full range investigated; this is due to the compensating effect of substituents on triplet state basicity and reduction potential, which both play a role in quenching by the hydrogen-bonded exciplex mechanism. Ketones with arenoid pi,pi* states exhibit the fall-off in rate constant that is typical of photoinduced electron transfer reactions, but it occurs at a much higher potential than would be normally expected due to the effects of hydrogen-bonding on the rate of electron-transfer within the exciplex.     

Phosphorescence characteristics of acetophenone, benzophenone, p-aminobenzophenone and Michler's ketone in various environments

The phosphorescence characteristics (excitation and emission spectra and lifetimes) of acetophenone (AP), benzophenone (BP), p-aminobenzophenone (PABP) and Michler's ketone (MK) adsorbed on Whatman No. 1 filter paper were measured at various temperatures, and compared with the phosphorescence characteristics in different solvent glasses at 77 K. Both AP and BP phosphoresce on filter paper only at low temperature (208 K). The phosphorescence lifetimes of AP and BP are < 1 msec, indicating a (3)(n,pi(*)) lower triplet level for paper substrates. With PABP, the low lying triplet state in polar solvents is (3)(CT) and in non-polar solvents is (3)(n, pi(*)); PABP on filter paper results in spectral characteristics similar to those of PABP in polar solvents at 77 K. The lifetime of PABP is longer than that of BP, indicating a (3)(CT) low-lying triplet state. MK, like PABP, has strongly environment-dependent photophysical properties. MK, when adsorbed on filter paper, has an intense long-lived luminescence at room temperature, resulting in a limit of detection of 3 ng ml or 3 pg, and a linear dynamic range of over 3 orders of magnitude. MK appears to be strongly hydrogen-bonded to the filter paper. In studies in ethanol and other solvents, MK adsorbed on filter paper shows a dramatic change in its phosphorescence spectrum when the temperature is lowered from 298 K to 208 K; the phosphorescence peak moves to longer wavelengths and the intensity decreases. The temperature effect could arise from the presence of several conformers of MK or be due to different environmental sites or E-type delayed fluorescence. The low-lying triplet state of MK on filter paper is most likely a (3)(CT) state. Lowering the temperature appears to increase the phosphorescence intensity for ketones which phosphoresce in the (3)(n,pi(*)) triplet state, but affects it only slightly for analytes which phosphoresce in the (3)(pi,pi(*)) triplet state. Room-temperature phosphorescence seems to arise for aromatic ketones and aldehydes with low-lying (3)(pi, pi(*)) or (3)(CT) triplet states.     

Stereodifferentiation in the formation and decay of the encounter complex in bimolecular electron transfer with photoactivated acceptors

Experimental evidence has been obtained for the involvement of encounter complexes between both enantiomers of a pi,pi* triplet excited ketone and a chiral phenol or indole. Determination of the pre-equilibrium constants (K(EC)) and the intrinsic decay rate constants (kd) indicates a significant stereodifferentiation in both steps of the quenching process.     

Geometrical effects on the intramolecular quenching of pi,pi* aromatic ketones by phenols and indoles

Laser flash photolysis of a series of bichromophoric compounds 1-12 containing the 2-benzoylthiophene (BT) and phenol (PhOH) or indole (InH) moieties has been used to determine the possible geometrical effects in the intramolecular quenching of triplet excited ketones, resulting in formal hydrogen abstraction. The results are compared with those obtained in the intermolecular process. In both cases, substitution either at the thienyl or the phenyl moiety has a marked influence on the photoreactivity. Time-resolved experiments showed that the rate constants for bimolecular quenching by phenol and indole of 2-benzoylthiophene substituted at the thienyl 5-position were lower than those for BT substituted at the phenyl p-position, which agrees with the higher energy found for the excited triplet state of the latter compounds. However, the rate constant for hydrogen abstraction in the bichromophoric compounds by the pi,pi* triplet state of the derivatives with the spacer linked to the thienyl 5-position are higher than those of their regioisomers. These results indicate a possible geometry-dependence in the intramolecular quenching process. Theoretical DFT studies have been carried out in order to estimate the optimum conformation for hydrogen abstraction in two pairs of phenolic and indolic bichromophoric regioisomers. The energy profile for photoactivation/deactivation of the aromatic ketone and the structures of the triplet states and biradicals involved in the process have been determined. The observed regiodifferentiation in the experimental studies is consistent with a dependence of the rate constant on orbital overlap between the carbonyl oxygen and the X-H bonds.     

Are antiaromatic rings stacked face-to-face aromatic?

The stacking of 4n pi electron hydrocarbon rings into superphane structures can eliminate their antiaromaticity and result in through-space three-dimensional aromatic character. This is demonstrated by the bond length equalized geometries and diatropic NICS values of the methano-bridged superphane series with interacting three- to nine-membered 4n pi electron rings. Along with triplet and M?bius strategies, stacking is the third way to achieve aromatic ring systems with 4n pi electrons.     

Change in spin state and enhancement of redox reactivity of photoexcited states of aromatic carbonyl compounds by complexation with metal ion salts acting as Lewis acids. Lewis acid-catalyzed photoaddition of benzyltrimethylsilane and tetramethyltin via photoinduced electron transfer

The lowest excited state of aromatic carbonyl compounds (naphthaldehydes, acetonaphthones, and 10-methylacridone) is changed from the n,pi triplet to the pi,pi singlet which becomes lower in energy than the n,pi triplet by the complexation with metal ions such as Mg(ClO(4))(2) and Sc(OTf)(3) (OTf = triflate), which act as Lewis acids. Remarkable positive shifts of the one-electron reduction potentials of the singlet excited states of the Lewis acid-carbonyl complexes (e.g., 1.3 V for the 1-naphthaldehyde-Sc(OTf)(3) complex) as compared to those of the triplet excited states of uncomplexed carbonyl compounds result in a significant increase in the redox reactivity of the Lewis acid complexes vs uncomplexed carbonyl compounds in the photoinduced electron-transfer reactions. Such enhancement of the redox reactivity of the Lewis acid complexes leads to the efficient C-C bond formation between benzyltrimethylsilane and aromatic carbonyl compounds via the Lewis-acid-promoted photoinduced electron transfer. The quantum yield determinations, the fluorescence quenching, and direct detection of the reaction intermediates by means of laser flash photolysis experiments indicate that the Lewis acid-catalyzed photoaddition reactions proceed via photoinduced electron transfer from benzyltrimethylsilane to the singlet excited states of Lewis acid-carbonyl complexes.     

Effect of meta electron-donating groups on the electronic structure of substituted phenyl nitrenium ions

Density functional theory (UB3LYP/6-31G(d,p)) was used to determine substituent effects on the singlet-triplet-state energy gap for 21 meta-substituted phenylnitrenium ions. It was found that strongly electron-donating substituents stabilize the triplet state relative to the singlet state. With sufficiently strong meta electron donors (e.g., m,m'-diaminophenylnitrenium ion) the triplet is predicted to be the ground state. Analysis of equilibrium geometries, Kohn-Sham orbital distributions, and Mulliken spin densities for the triplet states of this series of nitrenium ions leads to the conclusion that there are two spatially distinct types of low-energy triplet states. Simple arylnitrenium ions such as phenylnitrenium ions as well as those having electron-withdrawing or weakly donating meta substituents have lowest-energy triplet states that are n,pi in nature. That is, one singly occupied molecular orbital is orthogonal to the plane of the phenyl ring and one is coplanar. These n,pi triplets are generally characterized by large ArNH bond angles (ca. 130-132 degrees ) and an NH bond that is perpendicular to the plane of the phenyl ring. In contrast, meta donor arylnitrenium ions have a lowest-energy triplet state best described as pi,pi. That is, both singly occupied molecular orbitals are orthogonal to the aromatic ring. Such pi,pi states are characterized by NH bonds that are coplanar with the phenyl ring and have ArNH bond angles that are more acute (ca. 110-111 degrees ). These triplet nitrenium ions have electronic structures analogous to those of meta-benzoquinodimethane derivatives.     

Selective formation of triplet alkyl nitrenes from photolysis of beta-azido-propiophenone and their reactivity

Photolysis of beta-azido propiophenone derivatives, 1, with built-in sensitizer units, leads to selective formation of triplet alkyl nitrenes 2 that were detected directly with laser flash photolysis (lambdamax = 325 nm, tau = 27 ms) and ESR spectroscopy (|D/hc| = 1.64 cm-1, |E/hc| = 0.004 cm-1). Nitrenes 2 were further characterized with argon matrix isolation, isotope labeling, and molecular modeling. The triplet alkyl nitrenes are persistent intermediates that do not abstract H-atoms from the solvent but do decay by dimerizing with another triplet nitrene to form azo products, rather than reacting with an azide precursor. The azo dimer tautomerizes and rearranges to form heterocyclic compound 3. Nitrene 2a, with an n,pi* configuration as the lowest triplet excited state of the its ketone sensitizer moiety, undergoes intramolecular 1,4-H-atom abstraction to form biradical 6, which was identified by argon matrix isolation, isotope labeling, and molecular modeling. beta-Azido-p-methoxy-propiophenone, with a pi,pi* lowest excited state of its triplet sensitizer moiety, does not undergo any secondary photoreactions but selectively yields only triplet alkyl nitrene intermediates that dimerize to form 3b.     

B4CO2: a new,observable sigma-pi diradical

A new sigma-pi diradical, B4(CO)2, prepared in matrix isolation, was characterized unambiguously by isotopic-substitution infrared spectroscopy and by theoretical computations. Both open-shell singlet and triplet states have three pi electrons but are aromatic with moderately large NICS values. Quantum chemical calculations at various levels indicate that the open-shell singlet is slightly more stable than the triplet state. However, the singlet and triplet are computed to have very similar IR features which do not allow experimental differentiation.     

Electronic structure of the lowest excited triplet state of 5,12-naphthacenequinone

Continuous-wave time-resolved EPR (cw-TREPR) and pulsed electron nuclear double resonance (ENDOR) studies have been carried out to clarify the electronic structure of the lowest excited triplet (Tl) state of 5,12-naphthacenequinone (5,12-NpQ) as well as 1,4-anthraquinone (1,4-AQ) and 6,13-pentacenequinone (6,13-PeQ). The Tl energy level and the D value of the zero-field splitting (ZFS) parameters only slightly decreased with the increasing pi-conjugated system. The Tl states of these linear para-acenequinones were assigned to the pi pi* character. In triplet 5,12-naphthacenequinone, more than 80% of the unpaired electron spins are localized on the naphthalene aromatic sub-system.     

On the interaction mechanism of radical photoinitiators with monomers

Rate constants of quenching of triplet excited ketones by several monomers were determined through time‐resolved laser spectroscopy or culled from the literature. The semi‐empirical calculation method PM3 allows the quenching mechanisms to be refined and can be used to predict the reactivity of aromatic ketones toward monomers. It is apparent from both experimental results and theoretical calculations that the rate constant (k_q ) measured for the bimolecular quenching between the triplet state of a given aromatic ketone and both electron‐rich as well as electron‐poor monomers, depends linearly on the free enthalpy of formation of the regioselectively favored 1,4‐biradical, which is the primary reaction step of the ketone/monomer interaction. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1785–1794, 2000     

Competition between alpha-cleavage and energy transfer in alpha-azidoacetophenones

Molecular modeling demonstrates that the first excited state of the triplet ketone (T1K) in azide 1b has a (pi,pi*) configuration with an energy that is 66 kcal/mol above its ground state and its second excited state (T2K) is 10 kcal/mol higher in energy and has a (n,pi*) configuration. In comparison, T1K and T2K of azide 1a are almost degenerate at 74 and 77 kcal/mol above the ground state with a (n,pi*) and (pi,pi*) configuration, respectively. Laser flash photolysis (308 nm) of azide 1b in methanol yields a transient absorption (lambdamax=450 nm) due to formation of T1K, which decays with a rate of 2.1 x 105 s-1 to form triplet alkylnitrene 2b (lambdamax=320 nm). The lifetime of nitrene 2b was measured to be 16 ms. In contrast, laser flash photolysis (308 nm) of azide 1a produced transient absorption spectra due to formation of nitrene 2a (lambdamax=320 nm) and benzoyl radical 3a (lambdamax=370 nm). The decay of 3a is 2 x 105 s-1 in methanol, whereas nitrene 2a decays with a rate of approximately 91 s-1. Thus, T1K (pi,pi*) in azide 1b leads to energy transfer to form nitrene 2b; however, alpha-cleavage is not observed since the energy of T2K (n,pi*) is 10 kcal/mol higher in energy than T1K, and therefore, T2K is not populated. In azide 1a both alpha-cleavage and energy transfer are observed from T1K (n,pi*) and T2K (pi,pi*), respectively, since these triplet states are almost degenerate. Photolysis of azide 1a yields mainly product 4, which must arise from recombination of benzoyl radicals 3a with nitrenes 2a. However, products studies for azide 1b also yield 4b as the major product, even though laser flash photolysis of azide 1b does not indicate formation of benzoyl radical 3b. Thus, we hypothesize that benzoyl radicals 3 can also be formed from nitrenes 2. More specifically, nitrene 2 does undergo alpha-photocleavage to form benzoyl radicals and iminyl radicals. The secondary photolysis of nitrenes 2 is further supported with molecular modeling and product studies.     

Time-resolved spectroscopy of sulfur- and carboxy-substituted N-alkylphthalimides

The photophysical and photochemical properties of N-phthaloyl-methionine (1), S-methyl-N-phthaloyl-cysteine methyl ester (2) and N-phthaloyltranexamic acid (3) were studied by time-resolved UV/Vis spectroscopy, using laser pulses at 248 or 308 nm. The quantum yield of fluorescence is low (phi(f)< 10(-2)) for 1-3 in fluid and glassy media, whereas that of phosphorescence is large (0.3-0.5) in ethanol at - 196 degrees C. The triplet properties were examined in several solvents, at room temperature and below. The spectra and decay kinetics are similar, but the population of the pi(pi*) triplet state, as measured by T-T absorption, is much lower for 1 and 2 than for 3 or N-methyltrimellitimide (5') at ambient temperatures. The quantum yield (phi(delta)) of singlet molecular oxygen O2(1deltag) formation is substantial for 3 and 5' in several air- or oxygen-saturated solvents at room temperature, but small for 2 and 1. The quantum yield of decomposition is substantial (0.2-0.5) for 3 and small (<0.05) for 2 and 1. It is postulated that photoinduced charge separation in the spectroscopically undetectable 3n,pi* state may account for the cyclization products of 1 and 2. In aqueous solution, this also applies for 3, whereas in organic solvents cyclization involves mainly the lower lying 3pi,(pi*) state. Triplet acetone, acetophenone and xanthone are quenched by 1-3 in acetonitrile; the rate constant is close to the diffusion-controlled limit, but smaller for benzophenone. While the energy transfer from the triplet ketone occurs for 3, a major contribution of electron transfer to the N-phthalimide derivative is suggested for 1 and 2, where the radical anion of benzophenone or 4-carboxybenzophenone is observed in alkaline aqueous solution.     

The aromaticity and Möbius characteristics of carbeno[8]heteroannulenes and triplet state annulenes

Two types of annulene which may show significant M?bius aromatic character and bond and twist delocalisation are proposed; triplet states with 4n + 2 occupancy of the p pi array of atomic orbitals and a novel 8-pi carbeno[8]heteroannulene ring system 1 where the Hückel highly antiaromatic nature as a planar system can be attenuated or even reversed by the C2 symmetric M?bius distortion.     

A theory of nonvertical triplet energy transfer in terms of accurate potential energy surfaces: the transfer reaction from pi,pi* triplet donors to 1,3,5,7-cyclooctatetraene

Triplet energy transfer (TET) from aromatic donors to 1,3,5,7-cyclooctatetraene (COT) is an extreme case of "nonvertical" behavior, where the transfer rate for low-energy donors is considerably faster than that predicted for a thermally activated (Arrhenius) process. To explain the anomalous TET of COT and other molecules, a new theoretical model based on transition state theory for nonadiabatic processes is proposed here, which makes use of the adiabatic potential energy surfaces (PES) of reactants and products, as computed from high-level quantum mechanical methods, and a nonadiabatic transfer rate constant. It is shown that the rate of transfer depends on a geometrical distortion parameter gamma=(2g(2)/kappa(1))(1/2) in which g stands for the norm of the energy gradient in the PES of the acceptor triplet state and kappa(1) is a combination of vibrational force constants of the ground-state acceptor in the gradient direction. The application of the model to existing experimental data for the triplet energy transfer reaction to COT from a series of pi,pi(*) triplet donors, provides a detailed interpretation of the parameters that determine the transfer rate constant. In addition, the model shows that the observed decrease of the acceptor electronic excitation energy is due to thermal activation of C=C bond stretchings and C-C bond torsions, which collectively change the ground-state COT bent conformation (D(2d)) toward a planar triplet state (D(8h)).     

The photochemistry of 1,3-butadiene rationalized by means of theoretical resonance structures and their weights

A complete active-space self-consistent-field wave function for the pi-electron part of s-trans-1,3-butadiene has been expanded into a set of localized bonding schemes and their weights. These bonding schemes are close to the resonance structures used in organic chemistry. The expansion technique has been applied to both the electronic ground state and the electronically first-excited singlet and triplet pi,pi* states. The manifolds of large-weight bonding schemes represent approximate resonance hybrids for the ground and the singlet and triplet pi,pi* states of s-trans-1,3-butadiene. These resonance hybrids, obtained by theory alone, permit a qualitative rationalization of a significant part of the known singlet and triplet photochemistry.     

Photochemistry and photophysics of thienocarbazoles

Two methylated thienocarbazoles and two of their synthetic nitro-precursors have been examined by absorption, luminescence, laser flash photolysis and photoacoustic techniques. Their spectroscopic and photophysical characterization involves fluorescence spectra, fluorescence quantum yields and lifetimes, and phosphorescence spectra and phosphorescence lifetimes for all the compounds. Triplet-singlet difference absorption spectra, triplet molar absorption coefficients, triplet lifetimes, intersystem crossing S1 --> T1 and singlet molecular oxygen yields were obtained for the thienocarbazoles. In the case of the thienocarbazoles it was found that the lowest-lying singlet and triplet excited states, S1 and T1, are of pi,pi* origin, whereas for their precursors S1 is n,pi*, and T1 is pi,pi*. In both thienocarbazoles it appears that the thianaphthene ring dictates the S1 --> T1 yield, albeit there is less predominance of that ring in the triplet state of the linear thienocarbazole, which leads to a decrease in the observed phiT value.     

A laser flash photolysis study of fenofibric acid in aqueous buffered media: unexpected triplet state inversion in a derivative of 4-alkoxybenzophenone

Laser excitation of aqueous solutions of fenofibric acid (FA) at pH 7.4 show the formation of two reaction intermediates, the triplet state and the hydrated electron. The former is longer lived in water than in acetonitrile; its anionic form decays irreversibly by decarboxylation to give a carbanion that protonates before or after rearrangement. Several spectroscopic and quenching studies suggest that in aqueous media the triplet state of FA has a pi,pi* character, in comparison with an n,pi* character in organic media. Further, the known chemistry of the triplet, including decarboxylation and hydrogen abstraction, occurs predominantly from the n,pi* state, and as a consequence, activation energies are higher when the lowest triplet has a pi,pi* character. Photoionization is more important in aqueous than in organic media and involves a biphotonic process. Hydrated electrons are trapped by FA, leading to the corresponding ketyl radical after protonation.     

Triplet state properties and triplet-state-oxygen interactions of some linear and angular furocoumarins

Linear and angular furocoumarins with conjugated external carbonyl substituents show higher triplet and singlet oxygen yields than the corresponding unsubstituted molecules. The efficiency of the oxygen quenching process to yield singlet oxygen is also higher for these substituted molecules. These changes are interpreted in terms of the "proximity effect" associated with two nearly degenerate n pi* and pi pi* excited states, and variations in the excess energy following furocoumarin triplet quenching by ground state triplet oxygen to yield singlet oxygen.     

Photophysical properties of 2,5-diphenyl-1,6,6a-trithiapentalene revealed by time-resolved spectroscopy

The fluorescence decay from S2(pi, pi*) state of 2,5-diphenyl-1,6,6a-trithiapentalene (DP-TTP) in cyclohexane, tetrahydrofuran and acetonitrile solutions of a quantum yield of approximately 0.02-0.04 were measured. The results indicate that, the dominant process of radiationless deactivation of the S2 state, is internal conversion to the S1 state. Upon laser pulse excitation (lambda(ex) = 532 nm) from the S1(pi, pi*) state, DP-TTP in deoxygenated benzonitrile, acetonitrile, ethanol and tetrahydrofuran solutions give rise to transient triplet triplet absorption (lambdaTmax = 700-720 nm). Kinetic data are presented for intrinsic triplet lifetimes, self-quenching and quenching by oxygen.