Magnetic resonance studies of the deuteration effect on intersystem crossing in the anthracene molecule

The intersystem crossing decay constants from the ³B_2u state into the ground state of anthracene-d₁₀ in a phenazine crystal have been determined by magnetic resonance techniques at 1.5°K both at high magnetic field and, by a parameterization procedure, at zero magnetic field. A comparison of the anthracene-d₁₀ zero-field results with those for anthracene-h₁₀ show the effects of deuterium substitution to be largest for the in-plane spin levels of the anthracene triplet state.     

Exploiting radical-pair intersystem crossing for maximizing singlet oxygen quantum yields in pure organic fluorescent photosensitizers

Fluorescent photosensitizers (PSs) often encounter low singlet oxygen (¹O₂) quantum yields and fluorescence quenching in the aggregated state, mainly involving the intersystem crossing process. Herein, we successfully realize maximizing ¹O₂ quantum yields of fluorescent PSs through promoting radical-pair intersystem crossing (RP-ISC), which serves as a molecular symmetry-controlling strategy of donor–acceptor (D–A) motifs. The symmetric quadrupolar A–D–A molecule PTP exhibits an excellent ¹O₂ quantum yield of 97.0% with bright near-infrared fluorescence in the aggregated state. Theoretical and ultrafast spectroscopic studies suggested that the RP-ISC mechanism dominated the formation of the triplet for PTP, where effective charge separation and an ultralow singlet–triplet energy gap (0.01 eV) enhanced the ISC process to maximize ¹O₂ generation. Furthermore, in vitro and in vivo experiments demonstrated the dual function of PTP as a fluorescent imaging agent and an anti-cancer therapeutic, with promising potential applications in both diagnosis and theranostics.

Maximizing singlet oxygen quantum yields of a fluorescent photosensitizer for realizing approximately 100% utilization of excitons by precisely controlling the molecular symmetry.     

Time-dependent approaches for the calculation of intersystem crossing rates

We present three formulas for calculating intersystem crossing rates in the Condon approximation to the golden rule by means of a time-dependent approach: an expression using the full time correlation function which is exact for harmonic oscillators, a second-order cumulant expansion, and a short-time approximation of this expression. While the exact expression and the cumulant expansion require numerical integration of the time correlation function, the integration of the short-time expansion can be performed analytically. To ensure convergence in the presence of large oscillations of the correlation function, we use a Gaussian damping function. The strengths and weaknesses of these approaches as well as the dependence of the results on the choice of the technical parameters of the time integration are assessed on four test examples, i.e., the nonradiative S(1) ? T(1) transitions in thymine, phenalenone, flavone, and porphyrin. The obtained rate constants are compared with previous results of a time-independent approach. Very good agreement between the literature values and the integrals over the full time correlation functions are observed. Furthermore, the comparison suggests that the cumulant expansion approximates the exact expression very well while allowing the interval of the time integration to be significantly shorter. In cases with sufficiently high vibrational density of states also the short-time approximation yields rates in good agreement with the results of the exact formula. A great advantage of the time-dependent approach over the time-independent approach is its excellent computational efficiency making it the method of choice in cases of large energy gaps, large numbers of normal modes, and high densities of final vibrational states.     

Zn-containing porphyrin as a biomimetic light-harvesting molecule for biocatalyzed artificial photosynthesis

Among the porphyrin molecules with different metal insertion sites and functional ligands, Zn-porphyrin most efficiently regenerates NADH through photo-induced electron transfer in the presence of [Cp*Rh(bpy)H(2)O](2+), a rhodium-based electron mediator. Photochemical regeneration of NADH by Zn-porphyrin is successfully coupled with redox enzymatic synthesis under dark state conditions.     

On the intersystem crossing of pentacene in p-terphenyl

Applying methods developed for single molecule spectroscopy to small ensembles, we have recorded high-resolution fluorescence-excitation spectra for pentacene in all substitutional sites of a p-terphenyl single crystal. The difference in intersystem crossing efficiency for pentacene molecules in the various substitutional sites is discussed on the basis of these spectra and data from optically detected magnetic resonance experiments.     

Studies of intersystem crossing dynamics in acetylene

We report a new ab initio study of the acetylene T3 potential energy surface, which clarifies the nature of its energy minimum, and present computed equilibrium geometries and diabatic frequencies. This information enables the computation of harmonic vibrational overlap integrals of T3 vibrational levels with the S1 3nu3 state. The results of this calculation support the interpretation of two local perturbations of S1 3nu3, revealed in ultraviolet laser-induced fluorescence/surface electron ejection by laser excited metastables spectroscopy and Zeeman anticrossing measurements, respectively, as arising from two rotational submanifolds of a single T3 vibrational state. We present plausible assignments for this state as a guide for future experimental work.     

Mechanism of collision-induced intersystem crossing in CO

We have studied inert-gas pressure effects on the fluorescence decay in CO selectively excited to the υ = 0 to 7 vibronic levels of the A ¹Π electronic state. It is shown that the dependence of the quenching cross section σ_isc on the average value of the ST mixing coefficient (β²) has a quasi-logarithmic form. A simple two-level model describing semiquantitatively this behavior is proposed.     

Reduced equations of motion for collision-induced intersystem crossing

A model is proposed for collision-induced intersystem crossing in “intermediate case” and small molecules. The collisions are assumed to cause dephasing (T₂) among the zero order singlet and triplet molecular states. The combined effect of the intramolecular spin-orbit coupling (μ) and the collisional dephasing, results in the experimentally observable relaxation of populations (T₁). The basic assumption of the present model is that the duration of a collision τ_c is short compared to the intramolecular coupling (μτ_c ? 1). Reduced equations of motion for the molecular density matrix are derived and conditions for observing nonexponential relaxations are discussed. The model demonstrates the equivalence of T₁ and T₂ processes, depending on our choice of a basis set.     

Inverse deuterium isotope effect in the intersystem crossing of diphenylcarbene

The singlet-to-triplet intersystem crossing rate (k_st) of diphenylcarbene (DPC) is found to exhibit an inverse isotope effect in various solvents. An off-resonance coupling model between the initial singlet state and a sparse triplet vibronic manifold accounts for k_ST showing both an inverse isotope effect in a given solvent as well as an inverse energy gap effect in a solvent series.     

Zeeman effect of the PMDR signal and the mechanism of the intersystem crossing process in pyrazine at 1.6 K

The observed change in the 10.38 GHz PMDR signal of pyrazine in durene at 1.6 K upon the application of a magnetic field of 0–500 G cannot be explained by the direct S₁(n, π^*)

T₁(n, π^*) intersystem crossing process. The observed results can be computer fitted if the crossing is assumed to involve an intermediate triplet state with zero-field parameters similar to those of the lowest π, π^* state of substituted benzene. The relative probability of the direct to the indirect crossing to the different spin levels is concluded. The limitations of the method are discussed.     

The nature of internal conversion and intersystem crossing in exciplexes

Experimental data obtained by the authors themselves and other published data on the dependence of the rate constants of internal conversion and intersystem crossing in exciplexes (back electron transfer) on the value of energy gap were critically revisited. The conclusion that these processes occur according to the mechanism of radiationless diabatic quantum transitions, rather than the preceding thermally activated solvent and reactant reorganizations was substantiated.Translated from Khimiya Vysokikh Energii, Vol. 39, No. 2, 2005, pp. 114–125.Original Russian Text Copyright © 2005 by Kuzmin, Soboleva, Dolotova, Dogadkin.This revised version was published online in April 2005 with a corrected cover date.     

Accessing the triplet state of perylenediimide by radical-enhanced intersystem crossing

Owing to their exceptional photophysical properties and high photostability, perylene diimide (PDI) chromophores have found various applications as building blocks of materials for organic electronics. In many light-induced processes in PDI derivatives, chromophore excited states with high spin multiplicities, such as triplet or quintet states, have been revealed as key intermediates. The exploration of their properties and formation conditions is thus expected to provide invaluable insight into their underlying photophysics and promises to reveal strategies for increasing the performance of optoelectronic devices. However, accessing these high-multiplicity excited states of PDI to increase our mechanistic understanding remains a difficult task, due to the fact that the lowest excited singlet state of PDI decays with near-unity quantum yield to its ground state. Here we make use of radical-enhanced intersystem crossing (EISC) to generate the PDI triplet state in high yield. One or two 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) stable radicals were covalently attached to the imide position of PDI chromophores with and without p-tert-butylphenoxy core substituents. By combining femtosecond UV-vis transient absorption and transient electron paramagnetic resonance spectroscopies, we demonstrate strong magnetic exchange coupling between the PDI triplet state and TEMPO, resulting in the formation of excited quartet or quintet states. Important differences in the S₁ state deactivation rate constants and triplet yields are observed for compounds bearing PDI moieties with different core substitution patterns. We show that these differences can be rationalized by considering the varying importance of competitive excited state decay processes, such as electron and excitation energy transfer. The comparison of the results obtained for different PDI–TEMPO derivatives leads us to propose design guidelines for optimizing the efficiency of triplet sensitization in molecular assemblies by EISC.

The triplet state of PDI can be sensitized efficiently by radical-enhanced intersystem crossing. A detailed study of several related structures allows us to propose new strategies to optimize triplet formation in materials for optoelectronic devices.     

An efficient intersystem crossing mechanism revealed by a large temperature effect on the photochemical reactions of 9-α-Bromopropionylanthracene

A significant temperature effect on the new photochemical reactions of 9-α-bromopropionylanthracene has been noted. In comparison to the temperature effect on the fluorescence intensity of 9-propionylanthracene, it was suggested that the rotation of the carbonyl group on photo-excitation might operate as an enhancing factor in the intersystem crossing process.     

Intersystem crossing versus electron transfer in porphyrin-based donor-bridge-acceptor systems: influence of a paramagnetic species

We have investigated how the spin state of an acceptor influences the photophysical processes in a donor-bridge-acceptor (D-B-A) system. The system of choice has zinc porphyrin as the electron donor and high- or low-spin iron(III) porphyrin as the acceptor. The spin state of the acceptor porphyrin is switched simply by coordinating imidazole ligands to the metal center. The D-A center-center distance is 26 A, and the bridging chromophore varies from pi-conjugated to a sigma-bonded system. The presence of a high-spin iron(III) porphyrin in such systems has previously been shown to significantly enhance intersystem crossing in the remote zinc porphyrin donor, whereas no significant electron transfer to the iron porphyrin acceptor was observed, even though the thermodynamics would allow for photoinduced electron transfer. Here, we demonstrate that by switching the acceptor to a low-spin state, the dominating photophysical process is drastically changed; the low-spin system shows long-range electron transfer on the picosecond time-scale, and intersystem crossing occurs at its "normal" rate.     

Direct measurement of ultrafast intersystem crossing time for the PtIVBr62− complex

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Enhanced intersystem crossing via a high energy charge transfer state in a perylenediimide-perylenemonoimide dyad

The electronic relaxation processes of a photoexcited linear perylenediimide-perylenemonoimide (PDI-PMI) acceptor-donor dyad were studied. PDI-PMI serves as a model compound for donor-acceptor systems in photovoltaic devices and has been designed to have a high-energy PDI (-*)-PMI (+*) charge transfer (CT) state. Our study focuses on the minimal Gibbs free energy (Delta G ET) required to achieve quantitative CT and on establishing the role of charge recombination to a triplet state. We used time-resolved photoluminescence and picosecond photoinduced absorption (PIA) to investigate excited singlet (S 1) and CT states and complemented these experiments with singlet oxygen ( (1)Delta g) luminescence and PIA measurements on longer timescales to study the population of triplet excited states (T 1). In an apolar solvent like cyclohexene (CHX), photoinduced electron transfer does not occur, but in more polar solvents such as toluene (TOL) and chlorobenzene (CB), photoexcitation is followed by a fast electron transfer, populating the PDI (-*)-PMI (+*) CT state. We extract rate constants for electron transfer (ET; S 1-->CT), back electron transfer (BET; S 1<--CT), and charge recombination (CR) to lower-energy states (CT-->S 0 and CT-->T 1). Temperature-dependent measurements yield the barriers for the transfer reactions. For ET and BET, these correspond to predictions from Marcus-Jortner theory and show that efficient, near quantitative electron transfer ( k ET/ k BET >or= 100) can be obtained when Delta G ET approximately -120 meV. With respect to triplet state formation, we find a relatively low triplet quantum yield (Phi T < 25%) in CHX but much higher values (Phi T = 30-98%) in TOL and CB. We identify the PDI (-*)-PMI (+*) state as a precursor to the T 1 state. Recombination to T 1, rather than to the ground-state S 0, is required to rationalize the experimental barrier for CR. Finally, we discuss the relevance of these results for electron donor-acceptor films in photovoltaic devices.     

Spin–orbit coupling in the intersystem crossing of the ring-opened oxirane biradical

The intersystem crossing (ISC ) between the lowest triplet and singlet states occurring in the reaction of atomic oxygen with ethylene was studied. The importance of spin–orbit coupling (SOC ) in oxirane biradicals (?R′R″—CRR*—?) is stressed through calculations where the spin–orbit matrix elements over the full Breit–Pauli SOC operator has been obtained in the singlet–triplet crossing region. The calculations are performed with a multiconfigurational linear response approach, in which the spin–orbit couplings are obtained from triplet response functions using differently correlated singlet-reference-state wave functions. Computational results confirm earlier semiempirical predictions of the spin–orbit coupling as an important mechanism behind the ring opening of oxiranes and addition of oxygen O(³P) atoms to alkenes. © 1995 John Wiley & Sons, Inc.     

Picosecond time-resolved spectroscopy and the intersystem crossing rates of anthrone and fluorenone

The rise time of the T_n ← T₁ absorption of anthrone in benzene is determined to be 70 ps. The mechanism of efficient intersystem crossing of anthrone has been discussed and is compared with that of benzophenene. The rise time of fluorenone has been found to be sensitive to solvent, changing from 140 ps in cyclohexane to 12 ns in acetone. This tendency is explained in terms of the change in the character of the lowest excited singlet state of fluorenone from ππ^* in acetone to nπ^* in cyclohexane.