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Ionic liquids (ILs) have attracted increasing attention since last few decades due to their high molecular design abilities and wide applications in different fields. In this study, four novel fluorescent isoquinolino [2,1-a]quinoxalin-5-ium ILs were designed and synthesized via a two-step process including a simple dual Schiff's base formation and a subsequent [RhCp∗Cl2]2-catalyzed oxidative C–H activation/annulation reaction. The as-synthesized ILs were extensively characterized using FT-IR, 1H-NMR, 13C-NMR, 19F-NMR, HSQC-NMR, HMBC-NMR and HR-MS. Their photophysical properties were determined by steady-state fluorescence spectroscopy. The results demonstrate that all these ILs showed dual or triple emissions, large stokes shift (90 nm) and mechanochromic behaviors. Basing on solvatochromism and titration experiments, it is thought that the emission bands of the ILs are raised from their local excited states, charge transfer states or excited state proton transfer of cations, while the substitute effect of these quinoxaline derived ILs on their stokes shifts is negligible.

Upconversion nanosensitizers have been widely considered to have important applications in the treatment of major diseases such as tumors and the utilization of solar energy. Majority of the efforts so far have been focused on improving the efficiency of energy transfer (ET) between upconversion nanoparticles (UCNPs) and the anchored sensitizers with premise that high ET efficiency will lead to high acceptor efficacy. This premise is, however, proved by our current work to be invalid for commonly used load. Interaction between adjacent sensitizing molecules was found to be critical which undermines the amount of excited monomer sensitizers and thus fades the efficacy. Here NaYF4:Yb3+,Er3+ UCNPs and rose bengal (RB) photosensitizer molecules were used as the model energy donors and acceptors, respectively. Contrary to monotonous increase of the ET efficiency from UCNPs to RB species with increasing RB loading, acceptor efficacy characterized by the reactive oxygen species, as well as the RB fluorescence, exhibits bizarre dependence on the RB loading. The underlying mechanism was well studied by the steady-state and time-resolved spectroscopy of a series of samples. RB aggregates are believed to be responsible for the severe deviation between the ET efficiency and acceptor efficacy. The conclusion was validated by in vitro test where the photodynamic therapy with the most monomer RB in UCNPs-RB nanosensitizers kills 35.8% more cells than that with the highest RB loading. This understanding sheds light on construction of new ET based nanosystems for broad applications, such as medicine, solar energy utilization and optical storage.

Luminescent metal–organic frameworks (MOFs) are of interest for sensing, theranostics, dosimetry, and other applications. The use of lanthanoids in MOF metal nodes allows for intrinsic met-al-based luminescence. In this work, a facile route for modulat-ing the photoluminescent and radioluminescent properties of Tb(III)-based MOFs is reported. By using Tb(III)-cluster nodes as X-ray attenuators, and organic linkers with varying excited state energies as sensitizers, MOFs with metal-based, linker-based, and metal+linker-based photo- and radioluminescence are reported.

Preliminary explorations of the annihilation electrogenerated chemiluminescence (ECL) of mixed metal complexes have revealed opportunities to enhance emission intensities and control the relative intensities from multiple luminophores through the applied potentials. However, the mechanisms of these systems are only poorly understood. Herein, we present a comprehensive characterisation of the annihilation ECL of mixtures of tris(2,2'-bipyridine) ruthenium(II) hexafluorophosphate ([Ru(bpy)(3)](PF6)(2)) and fac-tris(2-phenylpyridine)iridium(III) ([Ir(ppy)(3)]). This includes a detailed investigation of the change in emission intensity from each luminophore as a function of both the applied electrochemical potentials and the relative concentrations of the two complexes, and a direct comparison with two mixed (Ru/Ir) ECL systems for which emission from only the ruthenium-complex was previously reported. Concomitant emission from both luminophores was observed in all three systems, but only when: (1) the applied potentials were sufficient to generate the intermediates required to form the electronically excited state of both complexes; and (2) the concentration of the iridium complex (relative to the ruthenium complex) was sufficient to overcome quenching processes. Both enhancement and quenching of the ECL of the ruthenium complex was observed, depending on the experimental conditions. The observations were rationalised through several complementary mechanisms, including resonance energy transfer and various energetically favourable electron-transfer pathways. Refereed/Peer-reviewed

We investigate the long-range, two-body interactions between rubidium and potassium atoms in highly excited ($n=70$) Rydberg states. After establishing properly symmetrized asymptotic basis states, we diagonalize an interaction Hamiltonian consisting of the standard Coulombic potential expansion and atomic fine structure to calculate electronic potential energy curves. We find that when both atoms are excited to either the $70s$ state or the $70p$ state, both the $\Omega=0+$ symmetry interactions and the $\Omega=0-$ symmetry interactions demonstrate a deep potential well capable of supporting many bound levels; the size of the corresponding dimer states are on the order of 2.25 $\mu$m. We estabish $n$-scaling relations for the equilibrium separation $R_e$ and the dissociation energy $D_e$ and find these relations to be consistent with similar calculations involving the homonuclear interactions between rubidium and cesium. We discuss the specific effects of $\ell$-mixing and the exact composition of the calculated potential well \textit{via} the expansion coefficients of the asymptotic basis states. Finally, we apply a Landau-Zener treatment to show that the dimer states are stable with respect to predissociation., Comment: 8 pages, 4 figures, 4 tables

Recent developments in quantum hardware and quantum algorithms have made it possible to utilize the capabilities of current noisy intermediate-scale quantum devices for addressing problems in quantum chemistry and condensed matter physics. Here we report a demonstration of solving the dynamical mean-field theory (DMFT) impurity problem for the Hubbard-Holstein model on the IBM 27-qubit Quantum Falcon Processor Kawasaki, including self-consistency of the DMFT equations. This opens up the possibility to investigate strongly correlated electron systems coupled to bosonic degrees of freedom and impurity problems with frequency-dependent interactions. The problem involves both fermionic and bosonic degrees of freedom to be encoded on the quantum device, which we solve using a recently proposed Krylov variational quantum algorithm to obtain the impurity Green's function. We find the resulting spectral function to be in good agreement with the exact result, exhibiting both correlation and plasmonic satellites and significantly surpassing the accuracy of standard Trotter-expansion approaches. Our results provide an essential building block to study electronic correlations and plasmonic excitations on future quantum computers with modern ab initio techniques.

Understanding excited states is vital to photochemistry and spectroscopy, yet the study of excited states from a theoretical viewpoint is often much more challenging than that of ground states due to the more complicated nature of excited states systems. This thesis is primarily focused on a series of topics regarding excited state electronic structure theory, aiming to improve the accuracy, efficiency and interpretability of computational methods. In particular, we generalize the recently developed ALMO-CIS approach, which is a formulation of configuration interaction singles (CIS) for molecular complexes or clusters based on absolutely-localized molecular orbitals (ALMOs), in two ways. The first is to reintroduce charge-transfer (CT) effects, and the resulting ALMO-CIS+CT method is shown to provide better accuracy in simulating spectra of large helium clusters. Secondly, a multi-reference version of ALMO-CIS is formulated, and shown to be a promising method for systems where pure charge-transfer excitations are important. We also develop and implement an energy decomposition analysis (EDA) method for studying intermolecular interactions in excited molecular systems. This EDA scheme brings insight to interesting excited-state phenomena such as solvatochromism, charge-transfer-to-solvent (CTTS) spectrum and the formation of excimers.

It is of great significance to understand the role of carrier in piezocatalysis of composites by studying the separation mode of carriers under dynamic polarization field. Herein, the separation and migration pathways of carriers under piezoelectric field are investigated by synthesizing heterojunctions with Bi2WO6 (BWO) nanosheets grown vertically on g-C3N4 (CN) coated ZnO nanorods and directly on ZnO. Compared with the photocatalysis, the piezocatalytic efficiency of Rhodamine B (RhB) by BWO/ZnO is significantly increased to 0.121 min−1, which indicated the polarization field promotes band tilt and Z-scheme formation. After introducing the CN interlayer, the piezocatalytic efficiency of BWO/CN/ZnO is further improved (0.217 min−1), which can be attributed to the unique core–shell structure with Z-scheme heterojunctions. This unique structure provides more active sites and excited carrier concentration, the intermediate layer CN also reduces the direct contact and recombination of electrons and holes controlled by polarization potential at the interface between BWO and ZnO. This work deeply analyzes the influence of carrier concentration, separation efficiency and transport process on piezocatalysis, which provides a reference for the design of efficient catalysts.

Carbon dots (CDs) are the unique class of luminescent nanomaterials consist of various chromophoric units heterogeneously distributed throughout the nanoparticle, resulting intriguing multistate emissive properties. Herein, we have critically investigated the specific locations of the blue and green-emitting centers inside dual emissive CDs by steady-state and time-resolved polarized emission study. It is further clarified by a temperature-dependent fluorescence study for both the emitting domains. Results suggest that the blue chromophoric units are located at the interior part of CDs, while green units are mostly at the exterior region. Furthermore, we have investigated the solvent-dependent inter-chromophoric interactions between the two emissive domains by the Time-Resolved Area Normalized Emission Spectroscopy (TRANES). Results suggest that at polar aprotic solvent acetone, time-dependent positive evolution of green-emitting states and negative evolution of blue emissive domains have been observed. This reversible emitting properties evolve due to the excited state energy migration from blue emissive domains to green emissive domains at polar aprotic medium, while in the case of polar protic solvent water, this phenomenon is missing. This switchable inter-chromophoric interaction are correlated further with the inter-particle interactions of CDs.

International audience; Three room-temperature metallomesogens based on Zn(II) cations pentacoordinated by different chelating N^N^N terpyridines and two monodentate gallate co-ligands were designed and synthesized. Depending on the terpyridine ligand's tip functionality, the complexes self-assemble into either a 3D hexagonal mesophase or into a columnar hexagonal mesophase. A systematic study between the structure (molecular architecture, arrangement of the molecules and columns, and chains in both types of mesophases) and photophysical properties (emission maxima and yields, lifetimes of the excited states in the mesophase), correlated with investigations of single molecules in solution, was conducted. Remarkably, one complex exhibited a record quantum yield of 95.0% in solution, while in the mesophase, despite quenching due to the radiative deactivation from the ILCT state, still retained a considerable emission yield of ϕ = 20.2%. The polarized emission of an oriented film, determined for the first time in columnar metallomesogens, shows a dichroic emission ratio (I||/I⊥) of 1.30. DFT and TDDFT computational studies confirmed the origin of the observed fluorescence anisotropy from the transition dipole moment oriented along the C2 symmetry axis of the molecule combined with a high level of order in the 3D mesophase.

In this study, a new series of zinc oxide (ZnO) with high specific surface area and narrow energy band gap are prepared using a facile microwave-induced method. The corresponding formation mechanism is also discussed for the first time. Due to the introduction of C, these ZnO can be excited by long wave temperature light without harmful short wave radiation, and play an efficient photocatalytic activity. This valuable property fundamentally improves the biological safety of its photocatalytic application. Herein, taking teeth whitening as an example, the photocatalytic performance of ZnO is evaluated. The “pure” yellow light-emitting diode (PYLED) with high biological safety is used as the excitation source. It is found that this method could effectively remove pigment on the tooth surface through physical adsorption. In addition, these ZnO could generate active oxygen to degrade the pigment on the tooth surface under the irradiation of yellow light. Some further optimization of these “warm light” responsive ZnO is also discussed in this systematical study, which could open up new opportunities in biomedical field., Graphical abstract Image 1, Highlights • A series of ZnO (PZCs, ZnO-BC) with high specific surface area and low band gap were synthesized by simple microwave-induced synthesis. • The introduction of C or BC can effectively reduce the band gap of ZnO. • Long wavelength warm light can effectively stimulate the photocatalytic activity of PZCs and ZnO-BC. • Under the yellow light, ZnO can effectively decompose the pigment on the tooth surface. • Warm light whitening, from the light source and material two levels to reduce the stimulation of teeth, and no obvious damage to enamel.

Near-infrared (NIR) fluorophores are emerging tools for biophotonics because of their reduced scattering, increased tissue penetration and low phototoxicity. However, the library of NIR fluorophores is still limited. Here, we report the NIR fluorescence of two benzene-fused oligo-BODIPYs in their hexameric (H) and octameric (O) forms. These dyes emit bright NIR fluorescence (H: maxima 943/1075 nm, O: maxima 976/1115 nm) that can be excited in the NIR (H = 921 nm, O = 956 nm) or non-resonantly over a broad range in the visible region. The emission bands of H show a bathochromic shift and peak sharpening with increasing dye concentration suggesting the presence of J-aggregates. Furthermore, the emission maxima of both H and O shift up to 20 nm in solvents of different polarity. These dyes can be used as NIR ink and imaged remotely on the macroscopic level with a stand-off distance of 20 cm. We furthermore demonstrate their versatility for biophotonics by coating microscale beads and performing microrheology via NIR video particle tracking (NIR-VPT) in biopolymer (F-actin) networks. No photodamaging of the actin filaments takes place, which is typically observed for visible fluorophores and highlights the advantages of these NIR dyes.

The nitric oxide vibrationally excited levels in the daytime are studied, at altitudes between 80 and 200 km. For that, we use a coupled 1D Boltzmann kinetic-fluid model to find density profiles of the major ions: O 2 + ; N 2 + ; NO + ; N + ; O + , nitrogen atoms: N ( 4 S ) ; N ( 2 D ) and vibrationally excited levels: NO ( v ⩽ 7 ) . A variety of processes are included in the model calculations that are neutrals chemistry, ions chemistry, photoabsorption, energetic electrons acting on the neutral atmosphere, molecular diffusion, and turbulent diffusion transport. The vibrational excitation of the nitric oxide is under strong solar control, reaching its maximum value near noon, when the solar zenith angle has the smallest value and then decreases away from noon. Data measurements of NO 5.3 μ m volume emission rate (VER) provided by SABER (Sounding of the Atmosphere using Broadband Emission Radiometry) satellite instrument corroborate our numerical results.

The synthesis, structural characterization and photophysical properties of a series of platinum(II) complexes of benzannulated pincer-type diarylamido ligands are described. The ligands all contain tricyclic phenanthridine (3,4-benzoquinoline) rings as donor arms, which were elaborated into N∧N−∧O-coordinating β-enaminoketonato chelates via partial condensation with acetylacetone. The proligands are easily deprotonated, and metallation can be achieved under mild conditions using simple Pt(II) salts and Ag2O as a base. The resulting Pt(II) complexes exhibit strong metal-to-ligand charge-transfer absorptions in the region of ∼450–575 nm and are phosphorescent in solution at room temperature, emitting bright orange light (λmax ∼ 600 nm) with quantum yields of up to 16% and excited-state lifetimes on the order of ∼20 μs, representing significant improvements to these photophysical properties compared with many previously reported N∧N∧O or N∧N∧N-ligated systems. Computational modelling reveals that the lowest-lying triplet state is populated efficiently thanks to strong coupling between singlet and triplet excited state manifolds, as in cyclometallated compounds of Pt(II). Substituents (CH3, tBu, or CF3) in the 2-position of the phenanthridinyl unit are found to have little influence on the optical properties, but the emission is severely quenched when a methyl substituent is introduced ortho to the coordinating nitrogen. Molecular distortions in the excited state are shown to be primarily responsible for the quenching in this complex.

In this work, a series of acenaphthene derivatives (AC-derivatives) were designed and synthesized by incorporating imidazole as an electron deficient moiety and triphenylamine (TPA) as an electron rich moiety with different functional groups at the N1 position of imidazole. All the dyes were structurally characterized by spectroscopic methods (1H NMR, 13C NMR, IR, and Mass) and some of the dyes were characterized by single crystal X-ray diffraction. The detailed thermal, photophysical and electrochemical properties were systematically investigated. All the dyes showed good thermal stability with high thermal decomposition (Td) temperatures ranging from 400 to 430 °C. All the dyes had similar absorption behaviour, with peak wavelengths at 240 nm and 350 nm assigned to the π → π* transitions of the aromatic segments. All the dyes exhibited a broad bluish-white to yellowish-orange emission with the emission maximum in the range of 520–600 nm. Electrochemical analysis was performed to discover the HOMO and LUMO energy levels of the dyes, which were verified using DFT calculations. Theoretical investigations, such as optimization, singlet–triplet and HOMO and LUMO energy levels calculations, were calculated using DFT and TD-DFT analysis. The excited singlet–triplet energy gaps of the dyes were estimated and correlated to the structural and energetic characteristics of the known host materials. In addition, examinations were carried out to find the optical, electronic, charge transport and stability properties of dyes for use as emissive and charge transport materials in organic light emitting devices (OLEDs). All the dyes are good emissive materials with their hole transporting nature more favourable than the electron transporting nature. The theoretical investigations clearly indicate that AC-mCF3 has more potential as an emitter for OLED applications.

The delta self-consistent field (ΔSCF) method was applied to the simulation of low-lying singlet and triplet excited states of multiple-resonance (MR)-type thermally activated delayed fluorescence (TADF) molecules, which form a promising group for organic light-emitting diode (OLED) emitters. A comparison with the experimental values of 13 emitters from the literature showed that ΔSCF gave fairly accurate S1 and T1 excitation energies (mean absolute errors (MAEs) of 0.092 and 0.055 eV, respectively) as well as quite accurate ΔEST (S1-T1 gap, MAE of 0.041 eV), which could not be calculated with sufficient accuracy by the conventional time-dependent density functional theory (TDDFT). ΔSCF also demonstrated its utility for the analysis of photophysical properties through a simulation of the reverse intersystem crossing (RISC) process of an MR-type emitter.

An asymmetric two-way proton transfer molecule 3-(benzo[d]-thiazol-2-yl)-2-hydroxy-5-methoxybenzaldehyde (BTHMB) with the function of white-light emission was synthesized in a recent experiment (Bhattacharyya, A.; Mandal, S. K.; Guchhait, N. J. Phys. Chem. A 2019, 123, 10246). The particularity of this molecule is that there are two possible forms, one of which contained a six-membered H-bonded network toward a N atom (BTHMB-NH) present in the molecule as a proton acceptor and the other was toward an O atom (BTHMB-OH). Unfortunately, the experimental work lacked the theoretical explanation about the determination of the BTHMB-NH form and its excited-state intramolecular proton transfer (ESIPT) process under different solvents. Therefore, this study has explored these two points by means of the time-dependent density functional theory (TDDFT) method. The calculated relative energy and potential energy profile (PEP) of the transformation between BTHMB-NH and BTHMB-OH forms illustrated that BTHMB-NH was more stable, and the transfer from BTHMB-NH to BTHMB-OH was almost impossible at both S0 and S1 states under all solvents due to high potential energy barriers (PEBs) (11.67-21.59 kcal/mol). These calculated results provided the theoretical explanation and verification for the conclusion that the BTHMB molecule exists in the BTHMB-NH form in the experiment. Subsequently, the constructed PEPs of the ESIPT process for BTHMB-NH have proved that it was prone to the ESIPT process due to low PEBs (0.11-0.28 kcal/mol) at the S1 state. In particular, as the solvent polarity increased, the intensity of the intramolecular hydrogen bond (IHB) (O3-H4···N5) increased and the ESIPT process was more likely to occur. In addition, the twisted intramolecular charge-transfer (TICT) process was studied to explore the possible fluorescence quenching pathway of BTHMB-NH. Based on the PEPs of BTHMB-NH-T as a function of the N5-C6-C7-C8 dihedral angle at the S0 and S1 states, it is seen that the S0 state TICT process was inhibited due to the large PEBs (16.45-23.93 kcal/mol). Although the S1 state PEBs have been greatly reduced, they were still maintained at about 3.60 kcal/mol (3.60-3.84 kcal/mol), and hence, this process was still relatively difficult to occur. Due to the fact that BTHMB can be regarded as a standard in future designs involving red light and solvent-specific white-light emitters, a certain amount of investigative work on the ESIPT process was done in detail, and it paved the way for future research on the directionality of ESIPT in double ESIPT probes.

Excited-state intramolecular proton transfer (ESIPT) dyes typically show strong solid-state emission, but faint fluorescence intensity is observed in the solution state owing to detrimental molecular motions. This article investigates the influence of direct (hetero)arylation on the optical properties of 2-(2'-hydroxyphenyl)benzoxazole ESIPT emitters. The synthesis of two series of ESIPT emitters bearing substituted neutral or charged aryl, thiophene, or pyridine rings is reported herein along with full photophysical studies in solution and solid states, demonstrating the dual solution-/solid-state emission behavior. Depending on the nature of substitution, several excited-state dynamics are observed: quantitative or partially frustrated ESIPT process or deprotonation of the excited species. Protonation studies revealed that pyridine substitution triggered a strong increase of quantum yield in the solution state for the protonated species owing to favorable quinoidal stabilization. These attractive features led to the development of a second series of dyes with alkyl or aryl pyridinium moieties showing strong tunable solution/solid fluorescence intensity. For each series, ab initio calculations helped rationalize and ascertain their behavior in the excited state and the nature of the emission observed by the experimental results.

Excited state intramolecular proton transfer (ESIPT) has drawn much attention for its important applications in a variety of areas. Here, the steady-state and time-resolved absorption spectroscopic experiments as well as DFT/TD-DFT calculations are employed to study the photophysical properties and photochemical reaction mechanisms of 2-(2'-hydroxyphenyl) benzoxazole (HBO) and selected derivatives (compounds 1-3). Because of their larger π-conjugation framework, compounds 1-3 display red-shifted absorbance but blue-shifted fluorescence compared with HBO. A fast ESIPT process is observed directly for HBO while compound 3 has an enol/keto equilibrium type of ESIPT that exhibits dual emission. Interestingly, only the emission of the enol form is observed for compounds 1 and 2 which suggests that the ESIPT process is strongly inhibited. These results indicate the decoration with electron-withdrawing groups such as thiadiazol and pyrazine on the hydroxyphenyl ring (compounds 1 and 2) apparently suppresses the proton-transfer processes in their excited states. Whereas the ESIPT process is rarely increased for compound 3 that modified with the phenanthrol ring, because the effective conjugation is reduced for compound 3 compared with HBO. The work here provides fundamental insights that may be useful for designing novel ESIPT molecules in the future.

Quantum dots (QDs) are three-dimensional (3D) quantum confinement materials with confined size on the nanoscale. They are semiconductors, possessing a tunable energy gap in the range of visible light energy. In QDs, the 3D quantum confinements of excitons result in tunable fluorescence emission relying upon the QDs size and shape when excited by monochromatic light. Besides, the attempts to improve their outstanding optoelectronic properties, i.e. superior to those of bulk, thin-film semiconductor and organic dyes, many efforts have been conducted, in recent times, regarding sustainable QDs synthesis aiming at biocompatibility and cost reduction. Among the green synthesis routes of QDs there are two distinguished; namely inorganic QDs and carbon-based QDs. The first route is made of low-bandgap metal chalcogenide either extracted from a living being, e.g. earthworm, or capped with an organic ligand. While, the second route is made of carbon-core and passivating the surface with different functional groups, namely carboxyl, hydroxyl, in addition to amine. These functional groups are derived from coke or organic carbon reservoir, i.e. fruits and their juice, animal, vegetable, spice and waste paper. Numerous fundamental applications of QDs, such as biomedicine, sensing, catalysis, and solar cells, exploit the characteristic fluorescence emission of QDs, quantum yields and their modulation upon interaction with the external environment. In this review, two prototype QDs examples are used to highlight the route to sustainable QDs synthesis and solar cells implementation and some perspectives.

A series of functional platinum(II) complexes (Pt1-Pt3), which present high activity in four-photon absorption, in vivo imaging, and precise cancer therapy, as previously reported by the experimental work of Zhang et al. (Inorg. Chem.2021, 60, 2362-2371), are computationally investigated in the article. We find that after the complex goes through four-photon absorption to the S1 state, it undergoes intersystem crossing to the T2 state and eventually reaches the T1 state through internal conversion. On the T1 state, both radiative and nonradiative decay to S0 exit. The radiative decay forms the basis for the phosphorescence imaging in tissues as reported in the original paper. In addition, the nonradiative decay can simultaneously generate cytotoxic singlet oxygen by the excited energy transfer process, also known as triplet oxygen's quenching of triplet states. We conclude that the phosphorescence property as well as the photosensitizer character jointly bring high activity of in vivo imaging and photodynamic therapy to these complexes.

Substituted tetralones such as 3,3,6,8-tetramethyl-1-tetralone undergo photoenolization to produce a photoenol excited state with a lifetime around ~ 3 μs, which involves the carbonyl triplet state of the ketone (τ ~ 1.9 ns), as a precursor; the excited photoenol also has biradical character and is useful for the fast synthesis of gold nanostructures. In the case of excited photoenols like this one, if metal ion trapping fails, they return to the original ketone precursor and remain available for future events that can lead to the target nanoparticles. This study includes the characterization of the photochemistry of the substituted tetralone, and the dual behavior of reaction intermediates, as biradicals and excited states, in energy and electron transfer processes.

Electron transfer dissociation (ETD) is an analytically useful tool for primary structure interrogation of intact proteins, but its utility is limited by higher-order reactions with the products. To inhibit these higher-order reactions, first-generation fragment ions are kinetically excited by applying an experimentally tailored parallel ion parking waveform during ETD (ETD-PIP). In combination with subsequent ion/ion proton transfer reactions, precursor-to-product conversion was maximized as evidenced by the consumption of more than 90% of the 21 kDa Protein G precursor to form ETD product ions. The employment of ETD-PIP increased sequence coverage to 90% from 80% with standard ETD. Additionally, the inhibition of sequential electron transfers was reflected in the high number of complementary ion pairs from ETD-PIP (90%) compared to standard ETD (39%).

Exciton coupling between the transition dipole moments of ordered dyes in supramolecular assemblies, so-called J/H-aggregates, leads to shifted electronic transitions. This can lower the excited state energy, allowing for emission well into the near-infrared regime. However, as we show here, it is not only the excited state energy modifications that J-aggregates can provide. A bay-alkylated quaterrylene was synthesized, which was found to form J-aggregates in 1,1,2,2-tetrachloroethane. A combination of superradiance and a decreased nonradiative relaxation rate made the J-aggregate four times more emissive than the monomeric counterpart. A reduced nonradiative relaxation rate is a nonintuitive consequence following the 180 nm (3300 cm–1) red-shift of the J-aggregate in comparison to the monomeric absorption. However, the energy gap law, which is commonly invoked to rationalize increased nonradiative relaxation rates with increasing emission wavelength, also contains a reorganization energy term. The reorganization energy is highly suppressed in J-aggregates due to exciton delocalization, and the framework of the energy gap law could therefore reproduce our experimental observations. J-Aggregates can thus circumvent the common belief that lowering the excited state energies results in large nonradiative relaxation rates and are thus a pathway toward highly emissive organic dyes in the NIR regime.

Proton transfer reactions are ubiquitous in chemistry, especially in aqueous solutions. We investigate photoinduced proton transfer between the photoacid 8-hydroxypyrene-1,3,6-trisulfonate (HPTS) and water using fast fluorescence spectroscopy and ab initio molecular dynamics simulations. Photoexcitation causes rapid proton release from the HPTS hydroxyl. Previous experiments on HPTS/water described the progress from photoexcitation to proton diffusion using kinetic equations with two time constants. The shortest time constant has been interpreted as protonated and photoexcited HPTS evolving into an "associated" state, where the proton is "shared" between the HPTS hydroxyl and an originally hydrogen bonded water. The longer time constant has been interpreted as indicating evolution to a "solvent separated" state where the shared proton undergoes long distance diffusion. In this work, we refine the previous experimental results using very pure HPTS. We then use excited state ab initio molecular dynamics to elucidate the detailed molecular mechanism of aqueous excited state proton transfer in HPTS. We find that the initial excitation results in rapid rearrangement of water, forming a strong hydrogen bonded network (a "water wire") around HPTS. HPTS then deprotonates in ≤3 ps, resulting in a proton that migrates back and forth along the wire before localizing on a single water molecule. We find a near linear relationship between the emission wavelength and proton-HPTS distance over the simulated time scale, suggesting that the emission wavelength can be used as a ruler for the proton distance. Our simulations reveal that the "associated" state corresponds to a water wire with a mobile proton and that the diffusion of the proton away from this water wire (to a generalized "solvent-separated" state) corresponds to the longest experimental time constant.

Is it possible to form an image using light produced by stimulated emission? Here we study light scatter off an assembly of excited chromophores. Due to the Optical Theorem, stimulated emission is necessarily accompanied by excited state Rayleigh scattering. Both processes can be used to form images, though they have different dependencies on scattering direction, wavelength and chromophore configuration. Our results suggest several new approaches to optical imaging using fluorophore excited states., 11 pages, 4 figures

Evidence of strong photoelectron-valence electron (PEVE) interactions has been observed in the anion photoelectron (PE) spectra of several lanthanide suboxide clusters, which are exceptionally complex from an electronic structure standpoint and are strongly correlated systems. The PE spectrum of Gd2O-, which should have relatively simple electronic structure because of its half-filled 4f subshell, exhibits numerous electronic transitions. The electron affinity determined from the spectrum is 0.26 eV. The intensities of transitions to excited states increase relative to the lower-energy states with lower photon energy, which is consistent with shakeup transitions driven by time-dependent electron-neutral interactions. A group of intense spectral features that lie between electron binding energies of 0.7 and 2.3 eV are assigned to transitions involving detachment of an electron from outer-valence σu and σg orbitals that have large Gd 6s contributions. The spectra show parallel transition manifolds in general, which is consistent with detachment from these orbitals. However, several distinct perpendicular transitions are observed adjacent to several of the vertical transitions. A possible explanation invoking interaction between the ejected electron and the high-spin neutral is proposed. Specifically, the angular momentum of electrons ejected from σu or σg orbitals, which is l = 1, can switch to l = 0, 2 with an associated change in the Ms of the remnant neutral, which is spin-orbit coupling between a free electron and the spin of a neutral.

Femtosecond time-resolved absorption measurements were carried out for the dark and signaling states of a BLUF (Blue Light Using FAD) protein, PixD, from the cyanobacterium Synechocystis. When the dark state was excited, FAD semiquinone radical (FADH•) was produced from the S1 state, and FADH• led to the signaling state. On the other hand, photoexcitation of the signaling state generated FADH• and FAD anion radical (FAD•-), and they decayed back to the original signaling state. In both cases, FADH• was formed and decayed with a proton-coupled electron transfer (PCET) via the hydrogen-bond network that involves FAD, Gln50, and Tyr8, and hence the kinetics of FADH• directly reflects the hydrogen-bond structure in the FAD-binding sites. It was found that the formation rate of FADH• was significantly different between the dark and signaling states, whereas the decay rate was the same. This indicates that the hydrogen-bond network of FAD-Gln50-Tyr8 in the dark and signaling states is initially different but it becomes indistinguishable after FADH• is formed, implying that the FAD-Gln50-Tyr8 hydrogen-bond network is rearranged during the PCET to generate FADH•. The present results best agree with the model in which the Gln tautomerizes without rotation in the signaling-state formation.

Substituted fluorene structures have demonstrated unusual photochemical properties. Previous reports on the substituted fluorene Schiff base FR0-SB demonstrated super photobase behavior with a ΔpK(b) of ~14 upon photoexcitation. In an effort to understand the basis for this unusual behavior, we have examined the electronic structure and relaxation dynamics of the structural precursor of FR0-SB, the aldehyde FR0, in protic and aprotic solvents using time-resolved fluorescence spectroscopy and quantum chemical calculations. The calculations show three excited singlet states in relatively close energetic proximity. The spectroscopic data are consistent with relaxation dynamics from these electronic states that depend on the presence and concentration of solvent hydroxyl functionality. These results underscore the central role of solvent hydrogen bonding to the FR0 aldehyde oxygen in mediating the relaxation dynamics within this molecule.

The kinetics of the nonradiative photoinduced processes (charge-separation and charge-recombination) experimented in solution by a supramolecular complex formed by an electron-donating bowl-shaped truxene-tetrathiafulvalene (truxTTF) derivative and an electron-accepting fullerene fragment (hemifullerene, C30H12) has been theoretically investigated. The truxTTF·C30H12 heterodimer shows a complex decay mechanism after photoexcitation with the participation of several low-lying excited states of different nature (local and charge-transfer excitations) all close in energy. In this scenario, the absolute rate constants for all of the plausible charge-separation (CS) and charge-recombination (CR) channels have been successfully estimated using the Marcus-Levich-Jortner (MLJ) rate expression, electronic structure calculations, and a multistate diabatization method. The outcomes suggest that for a reasonable estimate of the CS and CR rate constants, it is necessary to include the following: (i) optimally tuned long-range (LC) corrected density functionals, to predict a correct energy ordering of the low-lying excited states; (ii) multistate effects, to account for the electronic couplings; and (iii) environmental solvent effects, to provide a proper stabilization of the charge-transfer excited states and accurate external reorganization energies. The predicted rate constants have been incorporated in a simple but insightful kinetic model that allows estimating global CS and CR rate constants in line with the most generalized three-state model used for the CS and CR processes. The values computed for the global CS and CR rates of the donor-acceptor truxTTF·C30H12 supramolecular complex are found to be in good agreement with the experimental values.

Summary Host-guest complexation is an important supramolecular route to materials. Clear design rules have been developed for complexation in solution. This has proved more challenging for solid-state host-guest co-crystals because they often exhibit polymorphism, leading many researchers to focus instead on bonded frameworks, such as metal-organic frameworks. Here, we report an anthracene-based organic cage (1) that forms isoskeletal host-guest co-crystals with five similarly sized solid organic guests. The co-crystals were designed using inexpensive computational methods to identify appropriate guests that have packing coefficients (PCs) ranging from 44% to 50%, coupled with consideration of the guest shape. By complexing highly emissive BODIPY guests into the host structure, we enhanced its two-photon excited photoluminescent properties by a factor of six. Our crystal design approach was also transferrable to hard-to-design ternary organic crystals that were accessed by inserting specific guests into different sized voids in the host.

A two-step route to strongly absorbing and efficiently orange to deep red fluorescent, doubly B/N-doped, ladder-type pyrrolo[3,2-b]pyrroles has been developed. We synthesize and study a series of derivatives of these four-coordinate boron-containing, nominally quadrupolar materials, which mostly exhibit one-photon absorption in the 500–600 nm range with the peak molar extinction coefficients reaching 150 000, and emission in the 520–670 nm range with the fluorescence quantum yields reaching 0.90. Within the family of these ultrastable dyes even small structural changes lead to significant variations of the photophysical properties, in some cases attributed to reversal of energy ordering of alternate-parity excited electronic states. Effective preservation of ground-state inversion symmetry was evidenced by very weak two-photon absorption (2PA) at excitation wavelengths corresponding to the lowest-energy, strongly one-photon allowed purely electronic transition. π-Expanded derivatives and those possessing electron-donating groups showed the most red-shifted absorption- and emission spectra, while displaying remarkably high peak 2PA cross-section (σ2PA) values reaching ∼2400 GM at around 760 nm, corresponding to a two-photon allowed higher-energy excited state. At the same time, derivatives lacking π-expansion were found to have a relatively weak 2PA peak centered at ca. 800–900 nm with the maximum σ2PA ∼50–250 GM. Our findings are augmented by theoretical calculations performed using TD-DFT method, which reproduce the main experimental trends, including the 2PA, in a nearly quantitative manner. Electrochemical studies revealed that the HOMO of the new dyes is located at ca. −5.35 eV making them relatively electron rich in spite of the presence of two B−–N+ dative bonds. These dyes undergo a fully reversible first oxidation, located on the diphenylpyrrolo[3,2-b]pyrrole core, directly to the di(radical cation) stage., Ladder-type heterocycles encompassing two B−–N+ dative bonds possess intense green to red emission, large 2PA cross-sections and superb photostability.

In the search for new multifunctional materials, particularly for application in solid-state lighting, a set of terbium salicylato (Sal) complexes of general composition [Cat][Tb(Sal)4] with the commonly ionic liquid-forming (IL) cations [Cat] = (2-hydroxyethyl)trimethylammonium (choline) (Chol+), diallyldimethylammonium (DADMA+), 1-ethyl-3-methylimidazolium (C2C1Im+), 1-butyl-3-methylimidazolium (C4C1Im+), 1-ethyl-3-vinylimidazolium (C2Vim+), and tetrabutylphosphonium (P4444+) were synthesized. All Tb compounds exhibit strong green photoluminescence of high color purity by energy transfer from the ligand in comparison with what the analogous La compounds show, and quantum yields can reach up to 63% upon ligand excitation. When excited with an HF generator, the compounds show strong green electroluminescence with the same features of mission. The findings promise a high potential of application as emitter materials in solid-state lighting. As an additional feature, the Tb compounds show a strong response to applied external fields, rendering them multifunctional materials., Terbium-containing organic-inorganic hybrid materials such as ionic complexes allow for unique property combinations that can open up new applications

Epigenetic DNA modifications play a fundamental role in modulating gene expression and regulating cellular and developmental biological processes, thereby forming a second layer of information in DNA. The epigenetic 2′-deoxycytidine modification 5-methyl-2′-deoxycytidine, together with its enzymatic oxidation products (5-hydroxymethyl-2′-deoxycytidine, 5-formyl-2′-deoxycytidine, and 5-carboxyl-2′-deox- ycytidine), are closely related to deactivation and reactivation of DNA transcription. Here, we combine sub-30-fs transient absorption spectroscopy with high-level correlated multiconfigurational CASPT2/MM computational methods, explicitly including the solvent, to obtain a unified picture of the photophysics of deoxycytidine-derived epigenetic DNA nucleosides. We assign all the observed time constants and identify the excited state relaxation pathways, including the competition of intersystem crossing and internal conversion for 5-formyl-2′-deoxycytidine and ballistic decay to the ground state for 5-carboxy-2′-deoxycytidine. Our work contributes to shed light on the role of epigenetic derivatives in DNA photodamage as well as on their possible therapeutic use.

This paper presents a new approach for material removal on silicon at atomic and close-to-atomic scale assisted by photons. The corresponding mechanisms are also investigated. The proposed approach consists of two sequential steps: surface modification and photon irradiation. The back bonds of silicon atoms are first weakened by the chemisorption of chlorine and then broken by photon energy, leading to the desorption of chlorinated silicon. The mechanisms of photon-induced desorption of chlorinated silicon, i.e., SiCl2 and SiCl, are explained by two models: the Menzel–Gomer–Redhead (MGR) and Antoniewicz models. The desorption probability associated with the two models is numerically calculated by solving the Liouville–von Neumann equations for open quantum systems. The calculation accuracy is verified by comparison with the results in literatures in the case of the NO/Pt (111) system. The calculation method is then applied to the cases of SiCl2/Si and SiCl/Si systems. The results show that the value of desorption probability first increases dramatically and then saturates to a stable value within hundreds of femtoseconds after excitation. The desorption probability shows a super-linear dependence on the lifetime of excited states.

A series of platinum(II) bimetallic complexes were studied to investigate the effects of ligands on both the geometric and electronic structure. Modulating the Pt-Pt distance through the bridging ligand architecture was found to dictate the nature of the lowest energy electronic transitions, localized in one-half of the molecule or delocalized across the entire molecule. By reducing the separation between the platinum atoms, the lowest energy electronic transitions will be dominated by the metal-metal-to-ligand charge transfer transition. Conversely, by increasing the distance between the platinum atoms, the lowest electronic transition will be largely localized metal-to-ligand charge transfer or ligand centered in nature. Additionally, the cyclometalating ligands were observed to have a noticeable stabilizing effect on the triplet excited states as the conjugation increased, arising from geometric reorientation and increased electron delocalization of the ligands. Such stabilization of the triplet state energy has been shown to alter the excited state potential energy landscape as well as the excited state trajectory.

Processes that proceed in femtoseconds are usually referred to as being ultrafast, and they are investigated in experiments that involve laser pulses with femtosecond duration in so-called pump probe schemes, where a light pulse triggers a molecular process and a second light pulse interrogates the temporal evolution of the molecular population. The focus of this review is on the reactivity patterns that arise when energy is not equally distributed on all the available degrees of freedom as a consequence of the very short time scale in play and on how the localization of internal energy in a specific mode can be thought of as directing a process toward (or away from) a certain outcome. The nonstatistical aspects are illustrated with examples from photophysics and photochemistry for a range of organic molecules. The processes are initiated by a variety of nuclear motions that are all governed by the energy gradients in the Franck-Condon region. Essentially, the molecules will start to adapt to the new electronic environment on the excited state to eventually reach the equilibrium structure. It is this structural change that is enabling an ultrafast electronic transition in cases where the nuclear motion leads to a transition point with significant coupling between to electronic states and to ultrafast reaction if there is a coupling to a reactive mode at the transition point between the involved states. With the knowledge of the relation between electronic excitation and equilibrium structure, it is possible to predict how the nuclei move after excitation and often whether an ultrafast (and inherently nonstatistical) electronic transition or even a bond breakage will take place. In addition to the understanding of how nonstatistical photoinduced processes proceed from a given excited state, it has been found that randomization of the energy does not even always take place when the molecule takes part in processes that are normally considered statistical, such as for example nonradiative transitions between excited states. This means that energy can be localized in a specific degree of freedom on a state other than the one that is initially prepared. This is a finding that could kickoff the ultimate dream in applied photochemistry; namely light excitation that leads to the rupture of a specific bond.

Research on small-molecule dissociation on plasmonic silver nanoparticles is on the rise. Herein, we investigate the effect of various parameters of light, i.e., field strength, polarization direction, and energy of oscillation, on the dynamics of oxygen upon photoexcitation of the O2@Ag8 composite using real-time time-dependent density functional theory calculations with Ehrenfest dynamics. From our excited-state dynamics calculations, we found that increasing the strength of the external electric field brings a significant contribution to the O-O dissociation. In addition, the polarization direction of the incident light becomes important, especially at weaker field strengths. The light that is polarized along the direction of charge transfer from the metal to adsorbate and the light that is polarized along the long axis of molecular oxygen were found to enhance the bond breaking of O2 significantly. We also found that at the weakest electric field strength, the oxygen molecule stays adsorbed to the silver cluster when the incident light resonates with low-energy excited states and desorbs away from the metal cluster with high-energy excitations. With strong electric fields, oxygen either desorbs or dissociates.

Nitroaromatic compounds are inherently nonfluorescent, and the subpicosecond lifetimes of the singlet excited states of many small nitrated polycyclic aromatic hydrocarbons, such as nitronaphthalenes, render them unfeasible for photosensitizers and photo-oxidants, despite their immensely beneficial reduction potentials. This article reports up to a 7000-fold increase in the singlet-excited-state lifetime of 1-nitronaphthalene upon attaching an amine or an N-amide to the ring lacking the nitro group. Varying the charge-transfer (CT) character of the excited states and the medium polarity balances the decay rates along the radiative and the two nonradiative pathways and can make these nitronaphthalene derivatives fluoresce. The strong electron-donating amine suppresses intersystem crossing (ISC) but accommodates CT pathways of nonradiate deactivation. Conversely, the N-amide does not induce a pronounced CT character but slows down ISC enough to achieve relatively long lifetimes of the singlet excited state. These paradigms are key for the pursuit of electron-deficient (n-type) organic conjugates with promising optical characteristics.

Energy transfer plays a special role in photocatalysis by utilizing the potential energy of the excited state through indirect excitation, in which a photosensitizer determines the thermodynamic feasibility of the reaction. Bioinspired by the energy-transfer ability of natural product cercosporin, here we developed a green and highly efficient organic photosensitizer HiBRCP (hexaisobutyryl reduced cercosporin) through structural modification of cercosporin. After structural manipulation, its triplet energy was greatly improved, and then, it could markedly promote the efficient geometrical isomerization of alkenes from the E-isomer to the Z-isomer. Moreover, it was also effective for energy-transfer-mediated organometallic catalysis, which allowed realization of the cross-coupling of aryl bromides and carboxylic acids through efficient energy transfer from HiBRCP to nickel complexes. Thus, the study on the relationship between structural manipulation and their photophysical properties provided guidance for further modification of cercosporin, which could be applied to more meaningful and challenging energy-transfer reactions.

Nonadiabatic (NA) molecular dynamics (MD) goes beyond the adiabatic Born-Oppenheimer approximation to account for transitions between electronic states. Such processes are common in molecules and materials used in solar energy, optoelectronics, sensing, and many other fields. NA-MD simulations are much more expensive compared to adiabatic MD due to the need to compute excited state properties and NA couplings (NACs). Similarly, application of machine learning (ML) to NA-MD is more challenging compared with adiabatic MD. We develop an NA-MD simulation strategy in which an adiabatic MD trajectory, which can be generated with a ML force field, is used to sample excitation energies and NACs for a small fraction of geometries, while the properties for the remaining geometries are interpolated with kernel ridge regression (KRR). This ML strategy allows for one to perform NA-MD under the classical path approximation, increasing the computational efficiency by over an order of magnitude. Compared to neural networks, KRR requires little parameter tuning, saving efforts on model building. The developed strategy is demonstrated with two metal halide perovskites that exhibit complicated MD and are actively studied for various applications.

The photochemical release of nitric oxide (NO) from a NO precursor is advantageous in terms of spatial, temporal, and dosage control of NO delivery to target sites. To realize full control of the quantitative NO administration from photoactivated NO precursors, it is necessary to have detailed dynamical information on the photodissociation of NO from NO precursors. We synthesized two new water-soluble Roussin's red esters (RREs), [Fe2(μ-N-acetylcysteine)2(NO)4] and [Fe2(μ-N-acetylpenicillamine)2(NO)4], which have five times longer lifetime than the well-known [Fe2(μ-cysteine)2(NO)4]. The photodissociation dynamics of NO from these RREs in water were investigated over a broad time range from 0.3 ps to 10 μs after excitation at 310 and 400 nm using femtosecond time-resolved infrared (IR) spectroscopy. When these RREs are excited, they either release one NO, producing a radical species deficient in one NO (R), [Fe2(μ-RS)2(NO)3], or relax into the ground state without photodeligation via an electronically excited intermediate state (M). R appears immediately after photoexcitation, suggesting that one NO is photodissociated faster than 0.3 ps. A certain fraction of R undergoes geminate recombination (GR) with NO with a time constant of 7-9 ps, while the remaining R competitively binds to the solvent. Solvent-bound R eventually bimolecularly recombines with NO with a rate constant of (1.3-1.6) × 108 M-1 s-1. For a given RRE molecule, the fractional yield of M (0.62-0.76) depends on the excitation wavelength (λex); however, the relaxation time of M (6 ± 1 ns) is independent of λex. Although the primary quantum yield of NO photodissociation (Φ1) was found to be 0.24-0.38, the final yield of NO suitable for other reactions (Φ2) was reduced to 0.14-0.29 due to the picosecond GR of the dissociated NO with R. Detailed photoexcitation dynamics of RRE can be utilized in the quantitative control of NO administration at a specific site and time, promoting pin-point usage of NO in chemistry and biology. We demonstrate that femtosecond IR spectroscopy combined with quantum chemical calculations is a powerful method for obtaining detailed dynamic information on photoactivated NO precursors such as Φ1 and Φ2, the GR yield, and secondary reactions of the nascent photoproducts, which are essential information for the design of efficient photoactivated NO precursors and their quantitative utilization.

A series of Gd3+ complexes (Gd1-Gd3) with the general formula GdL3(EtOH)2, where L is a β-diketone ligand with polycyclic aromatic hydrocarbon substituents of increasing size (1-3), was studied by combining time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy and DFT calculations to rationalize the anomalous spectroscopic behavior of the bulkiest complex (Gd3) through the series. Its faint phosphorescence band is observed only at 80 K and it is strongly red-shifted (∼200 nm) from the intense fluorescence band. Moreover, the TR-EPR spectral analysis found that triplet levels of 3/Gd3 are effectively populated and have smaller |D| values than those of the other compounds. The combined use of zero-field splitting and spin density delocalization calculations, together with spin population analysis, allows us to explain both the large red shift and the low intensity of the phosphorescence band observed for Gd3. The large red shift is determined by the higher delocalization degree of the wavefunction, which implies a larger energy gap between the excited S1 and T1 states. The low intensity of the phosphorescence is due to the presence of C-H groups which favor non-radiative decay. These groups are present in all complexes; nevertheless, they have a relevant spin density only in Gd3. The spin population analysis on NaL models, in which Na+ is coordinated to a deprotonated ligand, mimicking the coordinative environment of the complex, confirms the outcomes on the free ligands.

The synthesis, structure, magnetic, and photophysical properties of two dinuclear, luminescent, mixed-ligand [CrIII2 L(O2 CR)]3+ complexes (R=CH3 (1), Ph (2)) of a 24-membered binucleating hexa-aza-dithiophenolate macrocycle (L)2- are presented. X-ray crystallographic analysis reveals an edge-sharing bioctahedral N3 Cr(μ-SR)2 (μ1,3 -O2 CR)CrN3 core structure with μ1,3 -bridging carboxylate groups. A ferromagnetic superexchange interaction between the electron spins of the Cr3+ ions leads to a high-spin (S=3) ground state. The coupling constants (J=+24.2(1) cm-1 (1), +34.8(4) cm-1 (2), H=-2JS1 S2 ) are significantly larger than in related bis-μ-alkoxido-μ-carboxylato structures. DFT calculations performed on both complexes reproduce both the sign and strength of the exchange interactions found experimentally. Frozen methanol-dichloromethane 1 : 1 solutions of 1 and 2 luminesce at 750 nm when excited into the 4 LMCT state on the 4 A2 → 2 T1 (ν2 ) bands (λexc =405 nm). The absolute quantum yields (ΦL ) for 1 and 2 were found to be strongly temperature dependent. At 77 K in frozen MeOH/CH2 Cl2 glasses, ΦL =0.44±0.02 (for 1), ΦL =0.45±0.02 (for 2).