Kasha-Vavilov Rule Research Articles

Singlet oxygen generation on a superhydrophobic surface: Effect of photosensitizer coating and incident wavelength on 1O2 yields.

Photochemical generation of singlet oxygen (1O2) often relies on homogenous systems; however, a dissolved photosensitizer (PS) may be unsuitable for some applications because it is difficult to recover, expensive to replenish, and hazardous to the environment. Isolation of the PS onto a solid support can overcome these limitations, but implementation faces other challenges, including agglomeration of the solid PS, physical quenching of 1O2 by the support, photooxidation of the PS, and hypoxic environments. Here, we explore a superhydrophobic polydimethylsiloxane (SH-PDMS) support coated with the photosensitizer 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphyrin (TFPP). This approach seeks to address the challenges of a heterogeneous system by using a support that exhibits low 1O2 physical quenching rates, a fluorinated PS that is chemically resistant to photooxidation, and a superhydrophobic surface that entraps a layer of air, thus preventing hypoxia. Absorbance and fluorescence spectroscopy reveal the monomeric arrangement of TFPP on SH-PDMS surfaces, a surprising but favorable characteristic for a solid-phase PS on 1O2 yields. We also investigated the effect of incident wavelength on 1O2 yields for TFPP in aqueous solution and immobilized on SH-PDMS and found overall yields to be dependent on the absorption coefficient, while the yield per absorbed photon exhibited wavelength independence, in accordance with Kasha-Vavilov's rule.

Anti-Kasha Fluorescence in Molecular Entities: Central Role of Electron-Vibrational Coupling.

According to Kasha's rule, the emission of a photon in a molecular system always comes from the lowest excited state. A corollary of this rule (i.e., the Kasha-Vavilov rule) states that the emission spectra are independent of the excitation wavelength. Although these rules apply for most of the molecular systems, violations of these rules are often reported. The prototypical case of a Kasha's rule violation is the fluorescence observed from S2 in azulene. Thanks to the advances in both theoretical and experimental research, other types of anomalous fluorescence (e.g., excitation energy transfer (EET)-based dual emissions, thermally activated fluorescence, etc.) are more recurrently reported in the literature. Sometimes, these anomalous processes involve higher-lying excited states but are mechanistically different from the azulene-like anomalous fluorescence. However, the underlying mechanisms leading to these anomalous emissions can be numerous and are not yet well understood.In order to shed some light on the above phenomena, this Account provides a comprehensive review of this topic. We herein report quantum chemical investigations in target molecular systems breaking Kasha's rule. The latter molecules were chosen because they were unambiguously reported to display anti-Kasha fluorescence. Our studies highlight three different types of anti-Kasha scenarios. Specifically, (i) the strong electronic, weak vibrational nonadiabatic coupling (NAC) regime (here named the type I case, i.e., azulene-like); (ii) the strong electronic, strong vibrational NAC regime (type II case, i.e., thermally activated S2 fluorescence); and the (iii) very weak electronic NAC regime (type III case, i.e., EET dyads). In addition, by combining state-of-the-art quantum chemical calculations with excited-state decay rate theories and appropriate excited-state kinetic models, we provide semiquantitative estimations of photoluminescence quantum yields for the most rigid molecular entities. Finally, we propose the use of simple theoretical descriptors relying on calculations of the excited-state density difference and the electron-vibrational coupling to classify anomalous emissions according to their coupling scenario.Besides the fundamental interest of the above investigations, the herein developed computational protocols and descriptors will be useful for the tailored design of dyes with tunable and unconventional fluorescence properties and their exploitation in a wide range of areas (i.e., from organic light-emitting diodes (OLEDs) to bioimaging, small-molecule fluorescent probes, and photocatalysis). Finally, our theoretical framework enables the attainment of a holistic understanding of the interconversion processes between excited states, where the electron-vibrational coupling is shown to play a central role in determining the efficacy.

Excitation-Wavelength-Dependent and Auxiliary-Ligand-Tuned Intersystem-Crossing Efficiency in Cyclometalated Platinum(II) Complexes: Spectroscopic and Theoretical Studies.

Understanding the factors affecting the intersystem-crossing (ISC) rate constant (kISC) of transition-metal complexes is crucial to material design with tailored photophysical properties. Most of the works on ISC to date focused on the influence by the chromophoric ligand and the understanding of the ISC efficiency were mainly drawn from the steady-state fluorescence to phosphorescence intensity ratio and ground-state calculations, with only a few high-level calculations on kISC that take excited-state structural change and solvent reorganization into account for quantitative comparisons with the experimental data. In this work, a series of [Pt(thpy)X)]+ complexes were prepared [Hthpy = 2-(2'-thienyl)pyridine, where X = auxiliary ligands] and characterized by both steady-state and time-resolved luminescence spectroscopies. A panel of auxiliary ligands with varying σ-donating/π-accepting character have been used. For comparison, analogues of [Pt(ppy)(P^P)]+ (Hppy = 2-phenylpyridine and P^P = diphosphino ligand) were also examined. The [Pt(thpy)(P^P)]+ complexes exhibit dual fluorescence-phosphorescence emission, with their ISC rate constants varied with the electronic characteristics of the auxiliary ligand: the more electron-donating ligand induces faster ISC from the S1 excited state to the triplet manifold. Density functional theory (DFT)/time-dependent DFT calculations of kISC(S1→T2) at the optimized excited-state geometries give excellent quantitative agreement with the femtosecond time-resolved fluorescence measurements; it was revealed that the more electron-donating auxiliary ligand increases metal contributions to both occupied and virtual orbitals and decreases the energy gap of the coupling excited states, leading to a decrease in the activation energy and an increase in spin-orbit coupling. Furthermore, the ISC rate constants of [Pt(thpy)(P^P)]+ complexes are found to depend on the excitation wavelengths. The deviation from Kasha-Vavilov's rule upon photoexcitation at λexc < 350 nm is due to the ultrafast S2 → T2 and S2 → T3 ISCs, as demonstrated by the calculated τISC < 100 fs, giving hints as to why S2 → S1 internal conversion (τIC ∼ ps) is not competitive with this hyper-ISC.

Cover Feature: Fluorescence Properties of Flavin Semiquinone Radicals in Nitronate Monooxygenase (ChemBioChem 13/2019)

The neutral flavin semiquinone radical stabilized in the active site of nitronate monooxygenase shows novel fluorescence behavior. It displays a broad UV–visible absorption spectrum in the near-UV and visible light range and emits red fluorescence when excited with yellow and red light. Such fluorescence is not observed when using excitation light of a shorter wavelength. How the excitation-wavelength-dependent fluorescence behavior violates the Kasha–Vavilov rule is discussed in depth in the communication by G. Gadda et al. on page 1646 in Issue 13, 2019 (DOI: 10.1002/cbic.201900016).

Fluorescence Properties of Flavin Semiquinone Radicals in Nitronate Monooxygenase.

Fluorescent cofactors like flavins can be exploited to probe their local environment with spatial and temporal resolution. Although the fluorescence properties of the oxidized and two-electron-reduced states of flavins have been studied extensively, this is not the case for the one-electron-reduced state. Both the neutral and anionic semiquinones have proven particularly challenging to examine, as they are unstable in solution and are transient, short-lived species in many catalytic cycles. Here, we report that the nitronate monooxygenase (NMO) from Pseudomonas aeruginosa PAO1 is capable of stabilizing both semiquinone forms anaerobically for hours, thus enabling us to study their spectroscopy in a constant protein environment. We found that in the active site of NMO, the anionic semiquinone exhibits no fluorescence, whereas the neutral semiquinone radical shows a relatively strong fluorescence, with a behavior that violates the Kasha-Vavilov rule. These fluorescence properties are discussed in the context of time-dependent density functional theory calculations, which reveal low-lying dark states in both systems.

Ground-State Heterogeneity along with Fluorescent Byproducts Causes Excitation-Dependent Fluorescence and Time-Dependent Spectral Migration in Citric Acid-Derived Carbon Dots.

The integrity of fluorescent carbon dot (FCD) emission deserves its highest appreciation when sample purification is performed with extreme care. Several controversial phenomena of FCD fluorescence including excitation-dependent emission, spectral migration with time, and thereby violation of the Kasha-Vavilov rule, which sparked intense debate during recent reports, disappeared when we rigorously purified the as-synthesized FCD sample. Purification was performed by first visual silica column chromatography (observing the emissions under UV illumination) and subsequently prolonged membrane dialysis. Most of the surprising phenomena of FCD fluorescence reported earlier apparently arose from ground-state spectral heterogeneity of FCD sample containing a large amount of fluorescent impurities (mostly polymeric or oligomeric in nature). Observation of our ensemble spectroscopic measurements, albeit nicely matched with recent reports based on single-particle experiments, differed largely from that of other ensemble measurements. Our results reconciled a number of long-standing controversies on FCD emission mostly by emphasizing the urgency of sample purification with more scientific rigor.

Ultrafast Elementary Photochemical Processes of Organic Molecules in Liquid Solution.

Ultrafast photochemical reactions in liquids occur on similar or shorter time scales compared to the equilibration of the optically populated excited state. This equilibration involves the relaxation of intramolecular and/or solvent modes. As a consequence, the reaction dynamics are no longer exponential, cannot be quantified by rate constants, and may depend on the excitation wavelength contrary to slower photochemical processes occurring from equilibrated excited states. Such ultrafast photoinduced reactions do no longer obey the Kasha-Vavilov rule. Nonequilibrium effects are also observed in diffusion-controlled intermolecular processes directly after photoexcitation, and their proper description gives access to the intrinsic reaction dynamics that are normally hidden by diffusion. Here we discuss these topics in relation to ultrafast organic photochemical reactions in homogeneous liquids. Discussed reactions include intra- and intermolecular electron- and proton-transfer processes, as well as photochromic reactions occurring with and without bond breaking or bond formation, namely ring-opening reactions and cis-trans isomerizations, respectively.

Time-Resolved Emission Reveals Ensemble of Emissive States as the Origin of Multicolor Fluorescence in Carbon Dots.

The origin of photoluminescence in carbon dots has baffled scientists since its discovery. We show that the photoluminescence spectra of carbon dots are inhomogeneously broadened due to the slower relaxation of the solvent molecules around it. This gives rise to excitation-dependent fluorescence that violates the Kasha-Vavilov rule. The time-resolved experiment shows significant energy redistribution, relaxation among the emitting states, and spectral migration of fluorescence spectra in the nanosecond time scale. The excitation-dependent multicolor emission in time-integrated spectra is typically governed by the relative population of these emitting states.

Ultrafast Intersystem-Crossing Dynamics and Breakdown of the Kasha-Vavilov's Rule of Naphthalenediimides.

The fluorescence quantum yield of a red naphthalenediimide dye (rNDI) with amino and Br core substituents has been found to decrease by a factor of almost 2 by going from S1 ← S0 to S2 ← S0 excitation. Time-resolved spectroscopic measurements reveal that this deviation from the Kasha-Vavilov's rule is due to an ultrafast, < 200 fs, intersystem-crossing (ISC) from the S2 state to the triplet manifold, due to the ππ* → nπ* character of the transition and to the presence of the heavy Br atom. In non-core substituted naphthalenediimide (pNDI), ISC is slower, ∼2 ps, and was found to be reversible on a time scale shorter than that of vibrational cooling. The fluorescence and triplet quantum yields of rNDI, thus, can be substantially changed by a simple variation of the excitation wavelength.

Excitation Wavelength Dependence of the Dynamics of Bimolecular Photoinduced Electron Transfer Reactions.

The dynamics of photoinduced electron transfer between polar acceptors and donors has been investigated in apolar solvents using femtosecond-resolved fluorescence spectroscopy. It was found to be ultrafast and to continuously accelerate by varying the excitation wavelength from the maximum to the red edge of the absorption band of the acceptor, the overall difference being as large as a factor 4-5. This violation of the Kasha-Vavilov rule is explained by a correlation between the composition of the acceptor environment and its transition energy, that is, the more donors around an acceptor, the longer its absorption wavelength, and the faster the quenching. Because of preferential solvation, this dependence is already observed at low quencher concentrations. This effect, which requires quenching to be faster than the fluctuations of the environment composition, should be quite general for photoinduced charge transfer processes in low-polarity, viscous, or rigid media, such as those used in organic optoelectronic devices.

Emission wavelength variation with changes in excitation in a Re(i)–bisthiazole ligand complex that breaks the Kasha–Vavilov rule

We report highly unusual photophysical properties of a fac-Re(CO)3–bisthiazole complex, which is shown to break the Kasha–Vavilov rule. Herein, we show that such a complex has unusual emission wavelength variation due to the presence of photo-induced isomerisation from the stable, ground-state N,N-bound thiazole complex to S,N- and S,S-donation in the photo-induced excited state. A triple excitation, triple emission profile along with extensive DFT calculations support this theory to showcase an unusual circumstance of suulfur donation to the fac-Re(CO)3 core upon luminescence. fac-Rhenium tricarbonyl complexes are extensively studied due to their fluorescent properties, high stability, and ready incorporation into conjugates with broad applicability in imaging and targeting. The spectroscopic features of the complex under study have broad fundamental interest while also offering potential for design of novel agents for use in biological imaging studies.

Quantum Dot/Plasmonic Nanoparticle Metachromophores with Quantum Yields That Vary with Excitation Wavelength

Coupled plasmonic/chromophore systems are of interest in applications ranging from fluorescent biosensors to solar photovoltaics and photoelectrochemical cells because near-field coupling to metal nanostructures can dramatically alter the optical performance of nearby materials. We show that CdSe quantum dots (QDs) near single silver nanoprisms can exhibit photoluminescence lifetimes and quantum yields that depend on the excitation wavelength, in apparent violation of the Kasha-Vavilov rule. We attribute the variation in QD lifetime with excitation wavelength to the wavelength-dependent coupling of higher-order plasmon modes to different spatial subpopulations of nearby QDs. At the QD emission wavelength, these subpopulations are coupled to far-field radiation with varying efficiency by the nanoprism dipolar resonance. These results offer an easily accessible new route to design metachromophores with tailored optical properties.

On the applicability of the Kasha—Vavilov rule to C60

Abstract Via full correction for the instrumental response function, the fluorescence excitation spectrum of C 60 in methylcyclohexane between 240 and 580 nm is shown to match the absorption spectrum. This proves that, in contrast to earlier reports, also after UV excitation into higher S n states, deactivation proceeds virtually completely via the S 1 state, in accordance with the Kasha—Vavilov rule.