Excited-state Reaction Research Articles

Photochemical [2+4]-Dimerization Reaction from the Excited State.

Aryl-maleimides undergo a novel [2+4]-photodimerization instead of the expected [2+2]-photodimerization under both direct irradiation with visible light and under sensitized energy transfer conditions. This new excited state reactivity in aryl-maleimides is deciphered through photochemical, photophysical, and spectroscopic studies. The stereochemistry of the photodimer depends on the type of non-bonding interactions prevalent during photodimerization which is in turn dictated by the substituents on the maleimide ring. More importantly, the stereochemistry of the photodimer formed is complementary to the product observed under thermal conditions.

Insights into the influence of hydrogen bonding interactions and proton-transfer behaviours in excited state of DNHBO fluorophore: solvent effects

Inspired by designing distinguished optical materials, novel organic molecules with ESIPT characteristics have become the hot topic in current research. Dual-m-N,N-dimethylaniline substituted HBO derivative (DNHBO), as a kind of new dual solid-state and solution-state emission (DSSE) emitter, is focused on its excited state dynamics theoretically in this work. Considering four aprotic solvents with different polarities, the solvent-polarity-regulated photo-induced hydrogen bonding interactions and associated ESIPT behaviours are confirmed. Briefly speaking, via comparing and metering the magnitudes of excited-state reaction barriers in different solvents, we claim that nonpolar solvents drive the ESIPT reaction for DNHBO fluorophore.

Ab initio molecular dynamics study of intersystem crossing dynamics for MH2 (M = Si, Ge, Sn, Pb) on spin-pure and spin-mixed potential energy surfaces.

Recently, surface-hopping ab initio molecular dynamics (SH-AIMD) simulations have come to be used to discuss the mechanisms and dynamics of excited-state chemical reactions, including internal conversion and intersystem crossing. In dynamics simulations involving intersystem crossing, there are two potential energy surfaces (PESs) governing the motion of nuclei: PES in a spin-pure state and PES in a spin-mixed state. The former gives wrong results for molecular systems with large spin-orbit coupling (SOC), while the latter requires a potential gradient that includes a change in SOC at each point, making the computational cost very high. In this study, we systematically investigate the extent to which the magnitude of SOC affects the results of the spin-pure state-based dynamics simulations for the hydride MH2 (M = Si, Ge, Sn, Pb) by performing SH-AIMD simulations based on spin-pure and spin-mixed states. It is clearly shown that spin-mixed state PESs are indispensable for the dynamics simulation of intersystem crossing in systems containing elements Sn and Pb from the fifth period onward. Furthermore, in addition to the widely used Tully's fewest switches (TFS) algorithm, the Zhu-Nakamura (ZN) global switching algorithm, which is computationally less expensive, is applied to SH for comparison. The results from TFS- and ZN-SH-AIMD methods are in qualitative agreement, suggesting that the less expensive ZN-SH-AIMD can be successfully utilized to investigate the dynamics of photochemical reactions based on quantum chemical calculations.

The solvent-regulated excited state reaction mechanism of 2-(2'-hydroxyphenyl)benzothiazole aggregates.

The excited state relaxation dynamics of 2-(2'-hydroxyphenyl)benzothiazole (HBT) in the gas phase and the solvents have been explored experimentally and theoretically. However, the fundamental mechanism of its emission in aggregates is still unexplored. In this article, we have presented a detail investigation of solvent-regulated excited state (ES) reactions for HBT aggregates with the aid of several experimental and theoretical research. The careful investigation of solvatochromic and electrochemical behavior elucidates that the emission around 460nm of HBT in DMSO and DMSO-water fraction correspond to the excited state internal charge transfer (ESICT). The quantum chemical analysis further supports this observation. The concentration-dependent 1H NMR and emission studies of HBT in DMSO revealed the formation of aggregates at higher concentrations that facilitate the charge transfer. The emission pattern of HBT in the AcN-water fraction demonstrates that the sequential internal charge transfer-proton transfer (ESICT-ESIPT) occurs in HBT aggregates. The pH studies show that HBT aggregates are potential ratiometric sensors for near-physiological pH ranges. Moreover, a ground-state zwitterionic conformation of HBT is observed in the basic medium formed by ground-state internal proton transfer (GSIPT). Overall, this study provides a better understanding of solvent-regulated ES reaction mechanism in the case of HBT aggregates and other substituted HBT compound aggregates published previously.

Asymmetric Synthesis of Cyclopamine, a Hedgehog (Hh) Signaling Pathway Inhibitor.

Cyclopamine is a teratogenic steroidal alkaloid, which inhibits the Hedgehog (Hh) signaling pathway by targeting the Smoothened (Smo) receptor. Suppression of Hh signaling with synthetic small molecules has been pursued as a therapeutic approach for the treatment of cancer. We report herein the asymmetric synthesis of cyclopamine based on a two-stage relay strategy. Stage-I: total synthesis of veratramine through a convergent approach, wherein a crucial photoinduced excited-state Nazarov reaction was applied to construct the basic [6-6-5-6] skeleton of C-nor-D-homo-steroid. Stage-II: conversion of veratramine to cyclopamine was achieved through a sequence of chemo-selective redox manipulations.

Critical role of empty in-gap states in the photocatalytic water splitting on carbon nitride nanosheets

Introducing nitrogen vacancies and non-metal dopants is one popular strategy to improve the photocatalytic H2O splitting efficiency of carbon nitride nanosheets. Especially, Nat. Energy2021, 6, 388–397 reported a fascinating solar-to-hydrogen efficiency of 1.16% for the carbon nitride nanosheets containing nitrogen vacancies and boron dopants. However, effects of these defects on the reaction mechanism remain unknown. Through first-principles calculations we reveal that H2O splitting on perfect melon can only be realized in the excited state under the assistance of charge-transfer excitons, moreover this excited-state reaction is easily destroyed by aqueous solution; the key role of nitrogen vacancies and boron dopants should be that they introduce empty in-gap states which can either make the reaction realized in the ground state or avoid the negative effect of aqueous solution. However, the inter-triazine nitrogen vacancy can be poisoned and the reduction capability can be damaged by boron dopants. These two phenomena do not occur at two-coordinated nitrogen vacancies, but H2O splitting at this defect requires charge-transfer excitons. Above shortcomings may limit further improvement of melon on photocatalytic H2O splitting by doping nitrogen vacancies and boron. Introducing appropriate empty states might be the way to design good photocatalysts for splitting H2O.

Excited‐state tautomerization of cytidine in water solution when exposed to UVC light

AbstractThe irradiation of water solution of cytidine with UVC light showed that the compound participates in a tautomerism following the kinetics of a first‐order reaction. The PIDA mechanism showed that the proton detachments in the tautomers of cytidine occur through the repulsive 1πσ* excited states and lead to conical intersections S0/S1, whose structures were optimized. More probable is the IRC mechanism, which proceeds along 1nπ* excited state reaction paths. This mechanism includes a water molecule as a catalyst, which assists the phototransformation of amino‐oxo tautomer of cytidine into imino‐hydroxy one.

Cavity-Modified Chemiluminescent Reaction of Dioxetane.

Chemiluminescence is a thermally activated chemical process that emits a photon of light by forming a fraction of products in the electronic excited state. A well-known example of this spectacular phenomenon is the emission of light in the firefly beetle, where the formation of a four-membered cyclic peroxide compound and subsequent dissociation produce a light-emitting product. The smallest cyclic peroxide, dioxetane, also exhibits chemiluminescence but with a low quantum yield as compared to that of firefly dioxetane. Employing the strong light-matter coupling has recently been found to be an alternative strategy to modify the chemical reactivity. In the presence of an optical cavity, the molecular degrees of freedom greatly mix with the cavity mode to form hybrid cavity-matter states called polaritons. These newly generated hybrid light-matter states manipulate the potential energy surfaces and significantly change the reaction dynamics. Here, we theoretically investigate the effects of a strong light-matter interaction on the chemiluminescent reaction of dioxetane using the extended Jaynes-Cummings model. The cavity couplings corresponding to the electronic and vibrational degrees of freedom have been included in the interaction Hamiltonian. We explore how the cavity alters the ground- and excited-state path energy barriers and reaction rates. Our results demonstrate that the formation of excited-state products in the dioxetane decomposition process can be either accelerated or suppressed, depending on the molecular orientation with respect to the cavity polarization.

Light in SmI2‐mediated chemistry: Synthetic applications and mechanistic studies

AbstractSmI2 is a versatile reagent in single electron transfer‐mediated reductive transformations. Photoexcitation of SmI2 generates a reactive excited state capable of transferring an electron to substrates that are recalcitrant towards accepting electrons. Synthetic results unequivocally indicate light as a green and sustainable promoter of SmI2‐mediated chemistry, with the potential to replace the suspected carcinogen hexamethylphosphoramide (HMPA). Rate constants of photoinduced electron transfer from SmI2 are in the range of 107–109 M−1 s−1, which are an order of magnitude higher in comparison with the ground state process. Recent advancement in EuII‐ and CeIII‐based photo‐redox catalysis rejuvenated the area of photo‐catalyzed reactions of low‐valent lanthanides. This review article aims to illustrate the role of photoexcitation on SmI2‐mediated reductive transformations.

Deciphering mechanism of excited state reactivity by spectroscopic methods

The Feature highlights Electron Paramagnetic Resonance (EPR) spectroscopy as an indispensable tool to understand the excited state reactivity of organic molecules.

Direct Evidence for Excited Ligand Field State-based Oxidative Photoredox Chemistry of a Cobalt(III) Polypyridyl Photosensitizer.

Increasing interest in sustainable chemistry coupled with the quest to explore new reactivity has spurred research on first-row transition metal complexes for potential applications in a variety of settings. One of the more active areas of research is photoredox catalysis, where the synthetically tunable nature of their electronic structures provides a rich palette of options for tailoring their reactivity to a desired chemical transformation. Understanding the mechanism of excited-state reactivity is critical for the informed development of next-generation catalysts, which in turn requires information concerning the propensity of their electronic excited states to engage in the desired electron or energy transfer processes. Herein we provide direct evidence of the highly oxidizing nature of the lowest-energy ligand-field (LF) excited state of a first-row d6-low-spin Co(III) photosensitizer [Co(4,4'-Br2bpy)3]3+ (where 4,4'-Br2bpy is 4,4'-dibromo-2,2'-bipyridine). The redox potential associated with the LF excited state of the Co(III) complex was bracketed by performing bimolecular quenching studies by using a series of simple organic electron donors. Time-resolved absorption spectroscopy confirmed a dynamic quenching process attributed to reductive quenching of the lowest-energy ligand-field excited state of the Co(III) chromophore. Analysis of the Stern-Volmer plots for each chromophore-quencher pair revealed a limiting value of Ered* ∼ 1.25 V vs Fc/Fc+ for the metal-centered excited state, which is significantly stronger than that of more commonly employed transition metal-based photoredox agents such as [Ru(bpy)3]2+ (Ered* = 0.32 V vs Fc/Fc+) and [Ir(ppy)2(bpy)]+ (Ered* = 0.27 V vs Fc/Fc+). These results suggest that this class of chromophores could find utility in applications requiring the activation of oxidatively resistant organic substrates for photoredox catalysis.

Experimental and theoretical study of the cytosine tautomerism through excited states.

The irradiation of water solution of cytosine with UV light (λmax = 254nm) shows oxo-hydroxy tautomerism with a rate constant of 6.297 × 10-3min-1. The order of the reaction implies a tautomeric conversion. After removing the UV light source, we observed a dark reaction with a rate constant of 1.473 × 10-3min-1 which leads to a restoration of the initial tautomer as before the irradiation. The mechanism of oxo-hydroxy tautomerism of cytosine in water solution was studied in the excited state. It was found that the transformations occur along the 1πσ* excited-state reaction paths which link the Franck-Condon geometries of the tautomers and the conical intersections S0/S1 connected with the H-detachment processes of the corresponding bonds. Furthermore, we established that the conical intersections S0/S1 are also mutually accessible along the 1πσ* excited-state reaction paths. The ground-state equilibrium geometries were optimized at the B3LYP/aug-cc-pVDZ level of theory in water environment according to PCM as well as at the CC2/aug-cc-pVDZ level in the gas phase. The TD B3LYP and CC2 methods were applied for the study of the excited states. The tautomerization mechanisms were studied with the use of the linear interpolation in internal coordinates approach using the optimized geometries of tautomers minima and conical intersections S0/S1 at the CASSCF(6,6)/6-31G* level. All calculations were performed with the GAUSSIAN 16 commercial software.

20Ne(α,p)23Na studied to constrain type Ia nucleosynthesis

The 20Ne(α,p)23Na reaction rate is important in determining the final abundances of various nuclei produced in type Ia supernovae. Previously, the ground state cross section was calculated from time reversal reaction experiments using detailed balance. The reaction rates extracted from these studies do not consider contributions from the population of excited states, and therefore, are only estimates. A resonance scan, populating both the ground and first excited states, was performed for the 20Ne(α,p)23Na reaction, measuring between 2.9 and 5 MeV center of mass energies at the Nuclear Science Lab at the University of Notre Dame. Data analysis is underway and preliminary results show substantial contribution from the excited state reaction.

Control of Photoswitching Kinetics with Strong Light-Matter Coupling in a Cavity.

Most photochemistry occurs in the regime of weak light-matter coupling, in which a molecule absorbs a photon and then performs photochemistry from its excited state. In the strong coupling regime, enhanced light-matter interactions between an optical field and multiple molecules lead to collective hybrid light-matter states called polaritons. This strong coupling leads to fundamental changes in the nature of the excited states including multi-molecule delocalized excitations, modified potential energy surfaces, and dramatically altered energy levels relative to non-coupled molecules. The effect of strong light-matter coupling on covalent photochemistry has not been well explored. Photoswitches undergo reversible intramolecular photoreactions that can be readily monitored spectroscopically. In this work, we study the effect of strong light-matter coupling on the kinetics of photoswitching within optical cavities. Reproducing prior experiments, photoswitching of spiropyran/merocyanine photoswitches is decelerated in a cavity. Fulgide photoswitches, however, show the opposite effect, with strong coupling accelerating photoswitching. While modified merocyanine switching can be explained by changes in radiative decay rates or the amount of light in the cavity, modified fulgide switching kinetics suggest direct changes to excited-state reaction kinetics.

Seasonal variations in the production of singlet oxygen and organic triplet excited states in aqueous PM2.5 in Hong Kong SAR, South China

Abstract. Photooxidants drive many atmospheric chemical processes. The photoexcitation of light-absorbing organic compounds (i.e., brown carbon, BrC) in atmospheric waters can lead to the generation of reactive organic triplet excited states (3C∗), which can undergo further reactions to produce other photooxidants such as singlet oxygen (1O2∗). To determine the importance of these aqueous photooxidants in secondary organic aerosol (SOA) formation and transformation, we must know their steady-state concentrations and quantum yields. However, there have been limited measurements of aqueous 3C∗ and 1O2∗ in atmospheric samples outside of North America and Europe. In this work, we report the first measurements of the steady-state concentrations and quantum yields of 3C∗ and 1O2∗ produced in aerosols in South China. We quantified the production of 3C∗ and 1O2∗ in illuminated aqueous extracts of PM2.5 collected in different seasons at two urban sites and one coastal semi-rural site during a year-round study conducted in Hong Kong SAR, South China. The mass absorption coefficients at 300 nm for BrC in the aqueous PM2.5 extracts ranged from 0.49 to 2.01 m2 g-C−1 for the three sites. Both 1O2∗ and 3C∗ were produced year-round. The steady-state concentrations of 1O2∗ ([1O2∗]ss) in the illuminated aqueous extracts ranged from 1.56×10-14 to 1.35×10-12 M, with a study average of (4.02±3.52)×10-13 M. At nearly 2 orders of magnitude lower than [1O2∗]ss, the steady-state concentrations of 3C∗ ([3C∗]ss) ranged from 2.93×10-16 to 8.08×10-14 M, with a study average of (1.09±1.39)×10-14 M. The quantum yields of 1O2∗ and 3C∗ also spanned wide ranges across samples, with a range of 1.19 % to 13.74 % and an average of (5.19±2.63) % for 1O2∗ and a range of 0.05 % to 3.24 % and an average of (0.56±0.66) % for 3C∗. The [1O2∗]ss and [3C∗]ss correlated with the concentration and absorbance of BrC, thus implying that the amount of BrC drives the steady-state concentrations of these photooxidants. The locations (urban vs. semi-rural) did not have a significant effect on [3C∗]ss and [1O2∗]ss, which indicated that BrC from local sources did not have a significant influence on the year-round 3C∗ and 1O2∗ production. 3C∗ and 1O2∗ production were found to be the highest in winter and the lowest in summer for all three sites. The observed seasonal trends of 1O2∗ and 3C∗ production could be attributed to the seasonal variations in the long-range air mass transport. Our analysis highlighted the key role that regional sources play in influencing the composition and concentrations of water-soluble BrC in winter PM2.5 in Hong Kong SAR, which contributed to their highest 3C∗ and 1O2∗ production. The current results will be useful for modeling seasonal aqueous organic aerosol photochemistry in the South China region.

Exploring Differences in Lanthanide Excited State Reactivity Using a Simple Example: The Photophysics of La and Ce Thenoyltrifluoroacetone Complexes.

A series of four lanthanide thenoyltrifluoroacetone (TTA) complexes consisting of two f0 (La3+ and Ce4+) and two f1 (Ce3+) complexes was examined using steady-state and time-resolved spectroscopic techniques. The wide range of spectroscopic techniques presented herein have enabled us to discern the nature of the excited states (charge transfer, CT vs ligand localized, LL) as well as construct a Jablonski diagram for detailing the excited state reactivity within the series of molecules. The wavelength and excitation power dependence for these series of complexes are the first direct verification for the presence of simultaneous competing, noninteracting CT and LL excited states. Additionally, a computational framework is described that can be used to support spectroscopic assignments as a guide for future studies. Finally, the relationship between the obtained photophysics and possible photochemical separation mechanisms is described.

Photoinduced Aryl Transfer from Imidazolyl-Quinoline π-Conjugated Systems.

Aryl transfer between heteroatoms was photochemically available through radical initiation followed by a bimolecular reaction. However, such an excited-state reaction has rarely been reported through a photoinduced intramolecular pathway in the π-conjugated systems. Herein, we found, for the first time, a clean photoinduced intramolecular aryl shift for imidazolyl-quinoline derivatives 2NQ (imidazophenanthrene) and 4NQX (imidazophenanthroline), of which the photoproducts are thermally reversible. Upon light irradiation of the studied compounds in solution, an appreciable blue fluorescence along with a gradual change in color appearance was observed, the photoluminescence and photoconversion quantum yields of which were shown to be competitive in the same excited state. We were able to harness the photoconversion quantum yields of the NQ compounds with facile electronic modifications. These, in combination with time-resolved studies on the NQ compounds, gave an oxygen-insensitive aryl transfer rate within 1-100 ns. The anomalously slow intramolecular reaction rates were further proven to be associated with the ∼5.0 kcal/mol transition free energy. The photoproducts NQ_rs were isolated, identified by X-ray analyses, and also shown to demonstrate anti-Vavilov reverse reactions back to the NQ compounds in the higher-lying excited state. The discovery of photoinduced intramolecular aryl transfer paves a new pathway in the synthetic field, which may also be extended and far-reaching to solar-chemical storage under an appropriate design strategy.

A General Light-Driven Organocatalytic Platform for the Activation of Inert Substrates.

Due to their strong covalent bonds and low reduction potentials, activating inert substrates is challenging. Recent advances in photoredox catalysis offered a number of solutions, each of which useful for activating specific inert bonds. Developing a general catalytic platform that can consistently target a broad range of inert substrates would be synthetically useful. Herein, we report a readily available indole thiolate organocatalyst that, upon excitation with 405 nm light, acquires a strongly reducing power. This excited-state reactivity served to activate, by single-electron reduction, strong C-F, C-Cl, and C-O bonds in both aromatic and aliphatic substrates. This catalytic platform was versatile enough to promote the reduction of generally recalcitrant electron-rich substrates (Ered <-3.0 V vs SCE), including arenes that afforded 1,4-cyclohexadienes. The protocol was also useful for the borylation and phosphorylation of inert substrates with a high functional group tolerance. Mechanistic studies identified an excited-state thiolate anion as responsible of the highly reducing reactivity.

Insights into photo-induced excited state behaviors for 2-[4-(Di-tert-butyl-amino)-phenyl]-5-(5-fluoro-benzooxazol-2-yl)-benzofuran-6-ol: Solvent effects

Inspired by distinguished white emitters characteristics and potential fluorescence probe performance, we mainly focus on exploring photo-induced behaviors of 2-[4-(Di-tert-butyl-amino)-phenyl]-5-(5-fluoro-benzooxazol-2-yl)-benzofuran-6-ol (DPFB) fluorophore. By comparing changes of chemical structure parameters and variations of infrared (IR) spectrum, we confirm hydrogen bond should be strengthened after photoexcitation. Combined with charge recombination caused by photoexcitation in different solvents, we propose nonpolar solvents are favorable to excited-state dynamic behavior. By searching transition state (TS) form along with excited state reaction path as well as constructing energy profiles, we clearly reveal the solvent polarity dependent excited state intramolecular proton transfer (ESIPT) mechanism for DPFB fluorophore.

Blinking of CdSe/Cd.33Zn.67S semiconductor nanoplatelets

Unstable photoluminescence quantum yield is important because it indicates changes in the transition rates between excited states. We synthesized 4.5 monolayer CdSe core, Cd.33Zn.67S gradient shell semiconductor nanoplatelets. The platelets exhibit a variety of blinking behaviors. Change points in the brightness of the platelets were investigated with frequentist and Bayesian techniques. We measured blinking power law constants ranging from 1.4 to 2.3. The brightness levels of blinking quantum particles are important because they are an accessible, if ambiguous, way to study surface photochemistry. Using histograms and a clustering algorithm, we determined that the number of brightness levels in the nanoplatelets is in the range of two to nine, with the lower end of that range appearing most likely and common. We conclude that the thickness and ensemble spectra are insufficient information to understand the evolving coupling between the excited states of platelets. Models of the interplay of excited state localization and reaction kinetics that span 10−10m to 10−8m and 10−10s to 102s are needed.