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Femtosecond time-resolved absorption and picosecond time-resolved emission measurements were carried out for highly concentrated aqueous solutions of K2 [Pt(CN)4 ] to investigate excited-state dynamics of the [Pt(CN)4 2- ] oligomers formed with metallophilic interactions. Time-resolved absorption spectra exhibit complicated dynamics that are represented with five time constants. Among them, the 90-ps and 400-ps dynamics were assigned to the S1 → T1 intersystem crossing of the trimer and tetramer coexisting in the solution by comparison with the fluorescence decays. Clear oscillations of transient absorption were observed in the first few picoseconds, and the frequency-detected-wavelength 2D analysis revealed that the 135-cm-1 and 65-cm-1 oscillations arise from the Pt-Pt stretch motions of the S1 trimer and S1 tetramer, respectively. The obtained time-resolved spectroscopic data provide a clear view of the excited-state dynamics of the [Pt(CN)4 2- ] oligomers in the femto-/picosecond time region.

Photoexcited molecular trajectories on potential energy surfaces (PESs) prior to thermalization are intimately connected to the photochemical reaction outcome. The excited-state trajectories of a diplatinum complex featuring photo-activated metal–metal σ-bond formation and associated Pt−Pt stretching motions were detected in real time using femtosecond wide-angle X-ray solution scattering. The observed motions correspond well with coherent vibrational wavepacket motions detected by femtosecond optical transient absorption. Two key coordinates for intersystem crossing have been identified, the Pt−Pt bond length and the orientation of the ligands coordinated with the platinum centers, along which the excited-state trajectories can be projected onto the calculated PESs of the excited states. This investigation has gleaned novel insight into electronic transitions occurring on the time scales of vibrational motions measured in real time, revealing ultrafast nonadiabatic or non-equilibrium processes along excited-state trajectories involving multiple excited-state PESs.

Photoactive metal complexes employing Earth‐abundant metal ions are a key to sustainable photophysical and photochemical applications. We exploit the effects of an inversion center and ligand non‐innocence to tune the luminescence and photochemistry of the excited state of the [CrN6] chromophore [Cr(tpe)2]3+ with close to octahedral symmetry (tpe=1,1,1‐tris(pyrid‐2‐yl)ethane). [Cr(tpe)2]3+ exhibits the longest luminescence lifetime (τ=4500 μs) reported up to date for a molecular polypyridyl chromium(III) complex together with a very high luminescence quantum yield of Φ=8.2 % at room temperature in fluid solution. Furthermore, the tpe ligands in [Cr(tpe)2]3+ are redox non‐innocent, leading to reversible reductive chemistry. The excited state redox potential and lifetime of [Cr(tpe)2]3+ surpass those of the classical photosensitizer [Ru(bpy)3]2+ (bpy=2,2′‐bipyridine) enabling energy transfer (to oxygen) and photoredox processes (with azulene and tri(n‐butyl)amine)., Super‐long luminescence lifetime (4500 μs) at room temperature, high quantum yield (8.2 %) and reversible redox chemistry in the complex [Cr(tpe)2]3+ containing an Earth‐abundant first row transition metal ion is enabled by ligand bite angle, inversion symmetry and ligand non‐innocence (tpe=1,1,1‐tris (pyrid‐2‐yl)ethane). [Cr(tpe)2]3+ is competent in light‐induced energy and electron transfer processes similar to classical noble metal ion complexes.

Understanding excited-state dynamics is critical for improving the photoluminescence (PL) efficiency of exciplexes. A series of exciplexes based on conventional hole-transporting materials as donor and newly developed phenylpyridinato boron derivatives as acceptor were investigated. High PL efficiencies were achieved in only some combinations, and a large difference in performance among combinations provided insight into nonradiative processes in exciplex systems. Furthermore, the triplet local excited states (3 LE) of each donor and acceptor were found play an important role in triplet exciplex harvesting. Significant contributions from triplets were clearly observed when the charge-transfer excited states (1 CT and 3 CT) and 3 LE were ideally aligned. We also demonstrated fine control of relative energy alignment via the concentration to improve the PL efficiency.

A set of flapping acene dimers fused with an 8π cyclooctatetraene (COT) ring showed distinct excited-state dynamics in solution. While the anthracene dimer showed a fast V-shaped-to-planar conformational change within 10 ps in the lowest excited singlet state, reminding us of extended Baird aromaticity, the tetracene dimer and the pentacene dimer underwent intramolecular singlet fission (SF) in different manners: A fast and reversible SF with a characteristic delayed fluorescence (FL), and a fast and quantitative SF, respectively. Conformational flexibility of the fused COT linkage plays an important role in these ultrafast dynamics, demonstrating the utility of the flapping molecular series as a versatile platform for designing photofunctional systems.

HIV-1 nucleocapsid (NCp7) is a two Cys2 HisCys zinc knuckle (N-Zn and C-Zn) protein that plays a key role in viral replication. NCp7 conformational dynamics is characterized by NMR relaxation dispersion and chemical exchange saturation transfer measurements. While the N-Zn knuckle is conformationally stable, the C-Zn knuckle interconverts on the millisecond timescale between the major state, in which the zinc is coordinated by three cysteines and a histidine, and two folded minor species (with populations around 1 %) in which one of the coordination bonds (Cys413-Sγ-Zn or His421-Nϵ2-Zn) is hydrolyzed. These findings explain why antiretroviral thioesters specifically disrupt the C-Zn knuckle by initial acylation of Cys413, and show that transient, sparsely-populated ("dark"), excited states of proteins can present effective targets for rational drug design.

Mechanochromic mechanophores are reporter molecules that indicate mechanical events through changes of their photophysical properties. Supramolecular mechanophores in which the activation is based on the rearrangement of luminophores and/or quenchers without any covalent bond scission, remain less well investigated. Here, we report a cyclophane-based supramolecular mechanophore that contains a 1,6-bis(phenylethynyl)pyrene luminophore and a pyromellitic diimide quencher. In solution, the blue monomer emission of the luminophore is largely quenched and a faint reddish-orange emission originating from a charge-transfer (CT) complex is observed. A polyurethane elastomer containing the mechanophore displays orange emission in the absence of force, which is dominated by the CT-emission. Mechanical deformation causes a decrease of the CT-emission and an increase of blue monomer emission, due to the spatial separation between the luminophore and quencher. The ratio of the two emission intensities correlates with the applied stress.

Utilizing light is a smart way to fuel chemical transformations as it allows the energy to be selectively focused on certain molecules. Many reactions involving electronically excited species proceed via open‐shell intermediates, which offer novel and unique routes to expand the hitherto used synthetic toolbox in organic chemistry. The direct conversion of non‐prefunctionalized, less activated compounds is a highly desirable goal to pave the way towards more sustainable and atom‐economic chemical processes. Photoexcited closed‐shell anions have been shown to reach extreme potentials in single electron transfer reactions and reveal unusual excited‐state reactivity. It is, therefore, surprising that their use as a reagent or photocatalyst is limited to a few examples. In this Review, we briefly discuss the characteristics of anionic photochemistry, highlight pioneering work, and show recent progress which has been made by utilizing photoexcited anionic species in organic synthesis., Photoactivated anions act as powerful single‐electron reductants and can be used as either a catalyst or a reactant. In the presence of a base, their absorption is shifted bathochromically compared to the neutral molecules through deprotonation, with visible light often being sufficient for their excitation.

Knowledge of the factors controlling excited state dynamics in excitonically coupled dimers and higher aggregates is critical for understanding natural and artificial solar energy conversion. In this work, we report ultrafast solvent polarity dependent excited state dynamics of the structurally well‐defined subphthalocyanine dimer, μ‐OSubPc2. Stationary electronic spectra demonstrate strong exciton coupling in μ‐OSubPc2. Femtosecond transient absorption measurements reveal ultrafast excimer formation from the initially excited exciton, mediated by intramolecular structural evolution. In polar solvents the excimer state decays directly through symmetry breaking charge transfer to form a charge separated state. Charge separation occurs under control of solvent orientational relaxation., Solvent polarity tunes the interplay of excimer formation and symmetry breaking charge separation (SB–CS) in the photoexcited subphthalocyanine dimer.

The carbon suboxide anion C3O2 − is generated in solid neon matrix. It is characterized by infrared absorption spectroscopy as well as quantum chemical calculations to have a planar C s structure where two CO groups with significantly different bond lengths and angles are attached in a zigzag fashion to the central carbon atom. Bonding analysis indicates that it is best described by the bonding interactions between a neutral CO in a triplet excited state and a doublet excited state of CCO−., The carbon suboxide anion C3O2 − is generated in a solid neon matrix, and is characterized to have an unsymmetrical structure by the bonding interactions between a neutral CO in a triplet excited state and a doublet excited state of CCO−.

Push-pull systems comprising of triphenylamine-tetracyanobutadiene (TPA-TCBD), a high-energy charge-transfer species, are linked to a near-IR sensitizer, azaBODIPY, for promoting excited-state CS. These systems revealed panchromatic absorption owing to intramolecular CT and near-IR absorbing azaBODIPY. Using electrochemical and computational studies, energy levels were established to visualize excited state events. Fs-TA studies were performed to monitor excited state CT events. From target analysis, the effect of solvent polarity, number of linked CT entities, and excitation wavelength dependence in governing the lifetime of CS states was established. Electron exchange between two TPA-TCBD entities in 3 seem to prolong lifetime of the CS state. We have been successful in demonstrating efficient CS upon both high-energy CT and low-energy near-IR excitations, signifying importance of these push-pull systems for optoelectronic applications operating in the wide optical window.

The [2+2] photocycloaddition is the most valuable and intensively investigated photochemical process. Here we demonstrate that irradiation of N‐acryloyl heterocycles with blue LED light (440 nm) in the presence of an IrIII complex leads to efficient and high yielding fused γ‐lactam formation across a range of substituted heterocycles. Quantum calculations show that the reaction proceeds via cyclization in the triplet excited state to yield a 1,4‐diradical; intersystem crossing leads preferentially to the closed shell singlet zwitterion. This is geometrically restricted from undergoing recombination to yield a cyclobutane by the planarity of the amide substituent. A prototropic shift leads to the observed bicyclic products in what can be viewed as an interrupted [2+2] cycloaddition., Irradiation of N‐acryloyl heterocycles with blue LED light and an IrIII complex leads to fused γ‐lactam formation. The reaction proceeds via cyclization in the triplet excited state to yield a 1,4‐diradical; intersystem crossing leads to a singlet zwitterion that is geometrically restricted from yielding a cyclobutane. Proton transfer leads to the products in an interrupted [2+2] cycloaddition.

There has been controversy surrounding the roles of the metal core (metal-metal interaction) and the shell (metal-ligand interaction) in photoluminescence of ligand-protected metal nanoclusters. We have discovered aggregation-induced room-temperature phosphorescence of a platinum-thiolate complex and its silver ion inclusion complex (a silver-doped platinum sub-nanocluster). The inclusion of silver ion boosted the photoluminescent quantum yield by 18 times. Photophysical measurements indicate that the rate of nonradiative decay was slower for the silver-doped platinum sub-nanocluster. DFT calculations showed that the LUMO, which had the main contribution from Ag s-orbital and Pt d-orbitals, played a critical role in suppressing the structural distortion at the excited state. This work will hopefully stimulate more research on designing strategies based on molecular orbitals of atomicity-precise luminescent multimetallic nanoclusters.

Controlling the spectral tunability and isomerization activity is currently one of the hot topics in the design of photoreversible molecular switches for application in optoelectronic devices. The present work demonstrates how to manipulate the absorption of the retinal protonated Schiff base (rPSB) chromophore over the entire visible range by targeted functionalization of the retinal backbone. Moreover, a correlation between the vertical excitation energy and the profile of the potential energy surface of the bright excited state responsible for the photoreactivity of rPSB is established. This correlation was exploited to rank the functionalized rPSBs into different classes with characteristic photoisomerization activity. Eventually, the synergic effects of functionalization and of external electric fields in the range of a few MV cm−1 were applied to achieve reversable and regioselective control of the photoisomerization propensity of selected rPBS derivatives.

The synthesis of a highly twisted chrysene derivative incorporating two electron deficient o‐carboranyl groups is reported. The molecule exhibits a complex, excitation‐dependent photoluminescence, including aggregation‐induced emission (AIE) with good quantum efficiency and an exceptionally long singlet excited state lifetime. Through a combination of detailed optical studies and theoretical calculations, the excited state species are identified, including an unusual excimer induced by the presence of o‐carborane. This is the first time that o‐carborane has been shown to induce excimer formation ab initio, as well as the first observation of excimer emission by a chrysene‐based small molecule in solution. Bis‐o‐carboranyl chrysene is thus an initial member of a new family of o‐carboranyl phenacenes exhibiting a novel architecture for highly‐efficient multi‐luminescent fluorophores.

Three rigid and structurally simple heterocyclic stilbene derivatives, (E)-3H,3'H-[1,1'-biisobenzofuranylidene]-3,3'-dione, (E)-3-(3-oxobenzo[c] thiophen-1(3H)-ylidene)isobenzofuran-1(3H)-one, and (E)-3H,3'H-[1,1'-bibenzo[c] thiophenylidene]-3,3'-dione, are found to fluoresce in their neat solid phases, from upper (S2 ) and lowest (S1 ) singlet excited states, even at room temperature in air. Photophysical studies, single-crystal structures, and theoretical calculations indicate that large energy gaps between S2 and S1 states (T2 and T1 states) as well as an abundance of intra and intermolecular hydrogen bonds suppress internal conversions of the upper excited states in the solids and make possible the fluorescence from S2 excited states (phosphorescence from T2 excited states). These results, including unprecedented fluorescence quantum yields (2.3-9.6 %) from the S2 states in the neat solids, establish a unique molecular skeleton for achieving multi-colored emissions from upper excited states by "suppressing" Kasha's rule.

The OH+ cation is a well-known diatomic for which the triplet (3 Σ- ) ground state is 50.5 kcal mol-1 more stable than its corresponding singlet (1 Δ) excited state. However, the singlet forms a strong donor-acceptor bond to argon with a bond energy of 66.4 kcal mol-1 at the CCSDT(Q)/CBS level, making the singlet ArOH+ cation 3.9 kcal mol-1 more stable than the lowest energy triplet complex. Both singlet and triplet isomers of this molecular ion were prepared in a cold molecular beam using different ion sources. Infrared photodissociation spectroscopy in combination with messenger atom tagging shows that the two spin isomers exhibit completely different spectral signatures. The ground state of ArOH+ is the predicted singlet with a covalent Ar-O bond.

The synthesis and characterization is reported of (C9 NH20 )2 SnBr4 , a novel organic metal halide hybrid with a zero-dimensional (0D) structure, in which individual seesaw-shaped tin (II) bromide anions (SnBr42- ) are co-crystallized with 1-butyl-1-methylpyrrolidinium cations (C9 NH20+ ). Upon photoexcitation, the bulk crystals exhibit a highly efficient broadband deep-red emission peaked at 695 nm, with a large Stokes shift of 332 nm and a high quantum efficiency of around 46 %. The unique photophysical properties of this hybrid material are attributed to two major factors: 1) the 0D structure allowing the bulk crystals to exhibit the intrinsic properties of individual SnBr42- species, and 2) the seesaw structure enabling a pronounced excited state structural deformation as confirmed by density functional theory (DFT) calculations.

The endohedral fullerene Y3N@C80 exhibits luminescence with reasonable quantum yield and extraordinary long lifetime. By variable‐temperature steady‐state and time‐resolved luminescence spectroscopy, it is demonstrated that above 60 K the Y3N@C80 exhibits thermally activated delayed fluorescence with maximum emission at 120 K and a negligible prompt fluorescence. Below 60 K, a phosphorescence with a lifetime of 192±1 ms is observed. Spin distribution and dynamics in the triplet excited state is investigated with X‐ and W‐band EPR and ENDOR spectroscopies and DFT computations. Finally, electroluminescence of the Y3N@C80/PFO film is demonstrated opening the possibility for red‐emitting fullerene‐based organic light‐emitting diodes (OLEDs).

Bright long-wavelength-excitable (green and beyond) semiconducting polymer dots (LWE-Pdots) are highly desirable for in vivo fluorescent imaging, as well as applications of multiple- wavelength-excitation based in vitro bioassays. Conventional LWE-Pdots have been obtained previously by incorporating a small amount of near-infrared (NIR) emitter into the backbone of a polymer host to develop a binary donor-acceptor (D-A) system. They usually suffer from severe concentration quenching and a trade-off between fluorescence quantum yield (Φ(f)) and absorption cross-section (σ), limiting the improvement in brightness. In this communication, we describe a ternary component (D(1)/D(2)-A) strategy to achieve ultrabright, green laser (532 nm)-excitable Pdots with narrow-band NIR emission by introducing a BODIPY-based assistant polymer donor as D(1). The novel use of BODIPY as predominant absorber in a Pdot allows strong, narrow-band absorption at 532 nm. The D(1)/D(2)-A Pdots possess simultaneously improved Φ(f) and σ compared to corresponding binary D(2)-A Pdots. Their Φ(f) is as high as 40.2%, one of the most efficient NIR Pdots reported. The ternary D(1)/D(2)-A Pdots show ultrahigh single-particle brightness, ~83 times brighter than Qdot 705 when excited by a 532 nm laser. Intravenously injected Pdots accumulate in implanted tumors in mice through the enhanced permeability and retention effect. Higher contrast in vivo tumor imaging was achieved using the ultrabright ternary Pdots versus the binary D-A Pdots. What’s more, this D(1)/D(2)-A design strategy supplies us a promising way to pursue ultrabright Pdots with even longer absorption and emission.

The synthesis and characterization of a covalent all-fullerene C60-Lu3N@Ih-C80 electron donor-acceptor conjugate has been realized by sequential 1,3-dipolar cycloaddition reactions of azomethine ylides on Lu3N@Ih-C80 and C60. To the best of our knowledge, this is the first time that two fullerenes behaving as both electron donor (Lu3N@Ih-C80) and acceptor (C60) are forming an electroactive dumbbell. DFT calculations reveal up to 16 diastereomeric pairs, that is, 8 syn and 8 with anti orientation, being the anti-RSSS isomer the most stable. Spectroelectrochemical absorption and femtosecond transient absorption experiments support the notion that a C60 --Lu3N@Ih-C80 + charge-separated state is formed. Spin conversion of the singlet C60 --Lu3N@Ih-C80 + charge-separated state into the triplet C60 --Lu3N@Ih-C80 + charge-separated state is facilitated by the heavy atom affect stemming from the Lu3N-cluster and, in turn, slows down the charge recombination by one order of magnitude Financial support from the European Research Council (ERC320441-Chirallcarbon and the MINECO of Spain (Projects CTQ2017-83531-R, CTQ2017-85341-P, and CTQ2017-84327- P, network CTQ2016-81911-REDT, and Juan de la Cierva formación contracts FJCI-2016-29448 to A.J.S. and FJCI-2017- 32757 to O.A.S.) is acknowledged. This work was also funded by the Deutsche Forschungsgemeinschaft (DFG) via SFB 953 “Synthetic Carbon Allotropes”, the Catalan DIUE (2017SGR39, XRQTC, and ICREA Academia 2014 Award to M.S.), and the FEDER fund (UNGI10-4E-801)

Lanthanide luminescence, while ideal for in vivo applications owing to sharp emission bands within the optical window, requires high-intensity, short-wavelength excitation of small organic "antenna" chromophores in the vicinity of the lanthanide complex to access excited f-orbital states through intersystem crossing. Herein, we explored Cherenkov radiation of the radioisotopes 18 F and 89 Zr as an in situ source of antenna excitation. The effective inter- and intramolecular excitation of the terbium(III) complexes of a macrocylic polyaminocarboxylate ligand (hydration number (q)=0, quantum yield (φ)=47 %) as well as its analogue functionalized to append an intramolecular Cherenkov excitation source (q=0.07, φ=63 %) was achieved. Using conventional small-animal fluorescence imaging equipment, we have determined a detection limit of 2.5 nmol of Tb(III) complex in presence of 10 μCi of 18 F or 89 Zr. Our system is the first demonstration of the optical imaging of discrete luminescent lanthanide complexes without external short-wave excitation.

The electronic structure of the simplest Criegee intermediate, H2COO, is practically that of a closed shell. On the biradical scale (β), where 0 corresponds to the pure closed shell and 1 to a pure biradical, its β value is only 0.10, suggesting that its ground electronic state is best described as a H2C=O(δ+)-O(δ-) zwitterion. However, this picture of a nearly inert closed shell contradicts its rich reactivity in the atmosphere. It is shown that the mixing of its ground state with the first triplet excited state, which is a pure biradical state of the type H2C˙-O-O˙, is responsible for the formation of strongly bound products during reactions inducing atmospheric particle growth.

Frontier molecular orbitals can be visualized and selectively set to achieve blue phosphorescent metal complexes. For this purpose, the HOMOs and LUMOs of tridentate Pt(II) complexes were measured using scanning tunneling microscopy and spectroscopy. The introduction of electron-accepting or -donating moieties enables independent tuning of the frontier orbital energies, and the measured HOMO-LUMO gaps are reproduced by DFT calculations. The energy gaps correlate with the measured and the calculated energies of the emissive triplet states and the experimental luminescence wavelengths. This synergetic interplay between synthesis, microscopy, and spectroscopy enabled the design and realization of a deep-blue triplet emitter. Finding and tuning the electronic "set screws" at molecular level constitutes a useful experimental method towards an in-depth understanding and rational design of optoelectronic materials with tailored excited state energies and defined frontier-orbital properties.

The self-assembly of salt nanocrystals from chemical reactions inside liquid helium is reported for the first time. Reaction is initiated by an electron impacting a helium nanodroplet containing sodium atoms and SF6 molecules, leading to preferential production of energetically favorable structures based on the unit cell of crystalline NaF. These favorable structures are observed as magic number ions (anomalously intense peaks) in mass spectra and are seen in both cationic and anionic channels in mass spectra, for example, (NaF)n Na(+) and (NaF)n F(-) . In the case of anions the self-assembly is not directly initiated by electrons: the dominant process involves resonant electron-induced production of metastable electronically excited He(-) anions, which then initiate anionic chemistry by electron transfer.

The electronic structure of the iron(II) spin crossover complex [Fe(H2bpz)2(phen)] deposited as an ultrathin film on Au(111) is determined by means of UV-photoelectron spectroscopy (UPS) in the high-spin and in the low-spin state. This also allows monitoring the thermal as well as photoinduced spin transition in this system. Moreover, the complex is excited to the metastable high-spin state by irradiation with vacuum-UV light. Relaxation rates after photoexcitation are determined as a function of temperature. They exhibit a transition from thermally activated to tunneling behavior and are two orders of magnitude higher than in the bulk material.

The fluorescence lifetime of the radical cation of N,N,N',N'-tetramethyl-p-phenylenediamine (Wurster's blue) decreases from 260 ps at 82 K to 200 fs at room temperature. Calculations indicate a small barrier between the excited-state minimum (D1 min) and a conical intersection (CI) of the excited and ground state potentials. The intersection is reached within 200 fs upon torsion of one of the C—N bonds.

Zeises anion is the quintessential organometallic compound first synthesized byWilliam Zeise in the 1820s. In their Communication on page 6356 ff., S. S. Xantheaset al. present a combined gas-phase photoelectron spectroscopic and computationalstudy of Zeises anion, which provides rich and detailed chemical-bonding andinteraction information on the anion and its bromine and iodine analogues (Zeisesportrait taken from the Wikipedia entry on William C. Zeise).Gas-Phase ElectrochemistryIn their Communication on page 6350 ff., D. J. Caruna et al. show that it is possibleto control redox reactions at the solid/gas interface by using voltammetrictechniques. A flame plasma is used as the electrolyte.HeteronanostructuresS.-H. Yu et al. report in their Communication on page 6365 ff. how the form of screw-, dumbbell-, and sandwich-like hexagonal-prismatic Cu–S–Zn nanostructures can becontrolled by the molar ratio of the copper and zinc precursors.Single-Molecule MagnetsIn their Communication on page 6361 ff., H. Oshio and co-workers describe acyanide-bridged [Fe

Wrong handedness? No problem! K.-H. Ernst et al. describe in their Communication on page 4065 ff. how the chirality of single adsorbates can be switched into the opposite enantiomeric state. By using inelastically tunneling electrons from the tip of a scanning tunneling microscope in an ultra-high vacuum, certain molecular vibrations are excited that, in turn, cause different actions such as hopping, rotation, and chirality conversion at the surface.

The unique light-driven enzyme protochlorophyllide oxidoreductase (POR) is an important model system for understanding how light energy can be harnessed to power enzyme reactions. The ultrafast photochemical processes, essential for capturing the excitation energy to drive the subsequent hydride- and proton-transfer chemistry, have so far proven difficult to detect. We have used a combination of time-resolved visible and IR spectroscopy, providing complete temporal resolution over the picosecond–microsecond time range, to propose a new mechanism for the photochemistry. Excited-state interactions between active site residues and a carboxyl group on the Pchlide molecule result in a polarized and highly reactive double bond. This so-called “reactive” intramolecular charge-transfer state creates an electron-deficient site across the double bond to trigger the subsequent nucleophilic attack of NADPH, by the negatively charged hydride from nicotinamide adenine dinucleotide phosphate. This work provides the crucial, missing link between excited-state processes and chemistry in POR. Moreover, it provides important insight into how light energy can be harnessed to drive enzyme catalysis with implications for the design of light-activated chemical and biological catalysts.

Light‐induced spin‐state switching is one of the most attractive properties of spin‐crossover materials. In bulk, low‐spin (LS) to high‐spin (HS) conversion via the light‐induced excited spin‐state trapping (LIESST) effect may be achieved with a visible light, while the HS‐to‐LS one (reverse‐LIESST) requires an excitation in the near‐infrared range. Now, it is shown that those phenomena are strongly modified at the interface with a metal. Indeed, an anomalous spin conversion is presented from HS state to LS state under blue light illumination for FeII spin‐crossover molecules that are in direct contact with metallic (111) single‐crystal surfaces (copper, silver, and gold). To interpret this anomalous spin‐state switching, a new mechanism is proposed for the spin conversion based on the light absorption by the substrate that can generate low energy valence photoelectrons promoting molecular vibrational excitations and subsequent spin‐state switching at the molecule–metal interface.

Covalency is found to even out charge separation after photo amp; 8208;oxidation of the metal center in the metal amp; 8208;to amp; 8208;ligand charge amp; 8208;transfer state of an iron photosensitizer. The amp; 963; amp; 8208;donation ability of the ligands compensates for the loss of iron 3d electronic charge, thereby upholding the initial metal charge density and preserving the local noble amp; 8208;gas configuration. These findings are enabled through element amp; 8208;specific and orbital amp; 8208;selective time amp; 8208;resolved X amp; 8208;ray absorption spectroscopy at the iron L amp; 8208;edge. Thus, valence orbital populations around the central metal are directly accessible. In conjunction with density functional theory we conclude that the picture of a localized charge amp; 8208;separation is inadequate. However, the unpaired spin density provides a suitable representation of the electron hole pair associated with the electron amp; 8208;transfer process

Photo-mediated 6π cyclization is a valuable method for the formation of fused heterocyclic systems. Here we demonstrate that irradiation of cyclic 2-aryloxyketones with blue LED light in the presence of an IrIII complex leads to efficient and high yielding arylation across a panoply of substrates by energy transfer. 2-Arylthioketones and 2-arylaminoketones also cyclize effectively under these conditions. Quantum calculation demonstrates that the reaction proceeds via conrotatory ring closure in the triplet excited state. Subsequent suprafacial 1,4-hydrogen shift and epimerization leads to the observed cis-fused products.

We introduce a new approach to transient spectroscopy, fluorescence‐detected pump–probe (F‐PP) spectroscopy, that overcomes several limitations of traditional PP. F‐PP suppresses excited‐state absorption, provides background‐free detection, removes artifacts resulting from pump–pulse scattering, from non‐resonant solvent response, or from coherent pulse overlap, and allows unique extraction of excited‐state dynamics under certain conditions. Despite incoherent detection, time resolution of F‐PP is given by the duration of the laser pulses, independent of the fluorescence lifetime. We describe the working principle of F‐PP and provide its theoretical description. Then we illustrate specific features of F‐PP by direct comparison with PP, theoretically and experimentally. For this purpose, we investigate, with both techniques, a molecular squaraine heterodimer, core–shell CdSe/ZnS quantum dots, and fluorescent protein mCherry. F‐PP is broadly applicable to chemical systems in various environments and in different spectral regimes., Ultrafast pump–probe spectroscopy detected by fluorescence is introduced. Combining sensitive fluorescence detection with ultrafast pulse‐limited time resolution, this approach provides a complementary technique to standard transient absorption.

Funding: Horizon 2020 Framework Programme (Grant Number(s): 897098; Grant recipient(s): Tao Wang, Eli Zysman-Colman); Horizon 2020 Framework Programme (Grant Number(s): 101025143; Grant recipient(s): Eli Zysman-Colman, Joydip De); Engineering and Physical Sciences Research Council (Grant Number(s): EP/P010482/1; Grant recipient(s): Eli Zysman-Colman); Royal Society (Grant Number(s): SRF\R1\201089; Grant recipient(s): Abhishek Kumar Gupta, Eli Zysman-Colman); China Scholarship Council (GrantNumber(s): 201906250199; Grant recipient(s): Sen Wu) Room-temperature phosphorescence (RTP) originating from higher-lying triplet excitons remains a rather rarely documented occurrence for purely organic molecular systems. Here, we report two naphthalene-based RTP luminophores whose phosphorescence emission is enabled by radiative decay of high-lying triplet excitons. In contrast, upon cooling the dominant phosphorescence originates from the lowest-lying triplet excited state, which is manifested by a red-shifted emission. Photophysical and theoretical studies reveal that the unusual RTP results from thermally activated excitonic coupling between different conformations of the compounds. Aggregation-regulated excitonic coupling is observed when increasing the doping concentration of the emitters in poly(methylmethacrylate) (PMMA). Further, the RTP quantum efficiency improves more than 80-fold in 1,3-bis(N-carbazolyl)benzene (mCP) compared to that in PMMA. This design principle offers important insight into triplet excited state dynamics and has been exploited in afterglow-indicating temperature sensing. Publisher PDF

Understanding photodriven multielectron reaction pathways requires the identification and spectroscopic characterization of intermediates and their excited‐state dynamics, which is very challenging due to their short lifetimes. To the best of our knowledge, this manuscript reports for the first time on in situ spectroelectrochemistry as an alternative approach to study the excited‐state properties of reactive intermediates of photocatalytic cycles. UV/Vis, resonance‐Raman, and transient‐absorption spectroscopy have been employed to characterize the catalytically competent intermediate [(tbbpy)2RuII(tpphz)RhICp*] of [(tbbpy)2Ru(tpphz)Rh(Cp*)Cl]Cl(PF6)2 (Ru(tpphz)RhCp*), a photocatalyst for the hydrogenation of nicotinamide (NAD‐analogue) and proton reduction, generated by electrochemical and chemical reduction. Electronic transitions shifting electron density from the activated catalytic center to the bridging tpphz ligand significantly reduce the catalytic activity upon visible‐light irradiation.

Understanding the impact of the excited state wavefunction confinement is crucial for the engineering of the photophysical properties and applications of organic chromophores. In the present contribution, the localization of the triplet state wavefunctions of some symmetric ethyne/butadiyne bridged BODIPY dimers and asymmetric BODIPY derivatives presenting extended π-conjugation frameworks is studied with time-resolved electron paramagnetic resonance spectroscopy and time-dependent density functional theory computations. Based on the Zero Field Splitting D parameters, we conclude that the triplet state wavefunctions are highly localized on one BODIPY unit in the symmetric dimers, which is consistent with the ab initio modelling that finds delocalized triplet state destabilized by 12-14 kcal mol