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Incorporation of the trimethoxyphenyl group at position 7 of flavin can drastically change the photophysical properties of flavin. We show unique fast singlet 1 (π,π*) excited state deactivation pathway through nonadiabatic transition to the 1 (n,π*) excited- state, and subsequent deactivation to the ground electronic state (S 0 ), closing the photocycle. This mechanism explains the exceptionally weak fluorescence and the short excited-state lifetime for the flavin trimethoxyphenyl derivative and the lack of excited triplet T 1 state formation. Full recovery of flavin in its ground state takes place within a 15 ps time window after photoexcitation in a polar solvent such as acetonitrile. According to quantum chemical calculations, the C (2) -O distance elongates by 0.16 Å in the 1 (n,π*) state, with respect to the ground state. Intermediate-state structures are predicted by theoretical ab initio calculations and their dynamics are investigated using broadband vis-NIR time-resolved transient absorption and fluorescence up-conversion techniques., (© 2024. The Author(s).)

Two BODIPY-C 60 -peptide assemblies were synthesized by CuAAC reactions of BODIPY-C 60 dyads and a helical peptide functionalized with a terminal alkyne group and an azide group, respectively. The helical peptide within these assemblies was functionalized at its other end by a disulfide group, allowing formation of self-assembled monolayers (SAMs) on gold surfaces. Characterizations of these SAMs, as well as those of reference molecules (BODIPY-C 60 -alkyl, C 60 -peptide and BODIPY-peptide), were carried out by PM-IRRAS and cyclic voltammetry. BODIPY-C 60 -peptide SAMs are more densely packed than BODIPY-C 60 -alkyl and BODIPY-peptide based SAMs. These findings were attributed to the rigid peptide helical conformation along with peptide-peptide and C 60 -C 60 interactions within the monolayers. However, less dense monolayers were obtained with the target assemblies compared to the C 60 -peptide, as the BODIPY entity likely disrupts organization within the monolayers. Finally, electron transfer kinetics measurements by ultra-fast electrochemistry experiments demonstrated that the helical peptide is a better electron mediator in comparison to alkyl chains. This property was exploited along with those of the BODIPY-C 60 dyads in a photo-current generation experiment by converting the resulting excited and/or charge separated states from photo-illumination of the dyad into electrical energy., (© 2024 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)

In photochemistry the excited-state intramolecular proton transfer process (ESIPT) is often observed as a highly efficient singlet excited state depletion pathway, which in the presence of a strong intramolecular hydrogen bond may proceed on a subpicosecond time scale. The present work describes the suppression of unwanted transoid-trans isomer formation in photochromic 3H-naphthopyran derivatives by the introduction of a 5-hydroxy substituent. According to time-resolved spectroscopy experiments and excited-state ab initio calculations, transoid-cis → transoid-trans photoisomerization is reduced by a competitive ESIPT channel in nonpolar solvent (cyclohexane). Upon specific solute-solvent interactions (methanol, acetonitrile) the intramolecular hydrogen bond in the transoid-cis form is perturbed, favoring the internal conversion S 1  → S 0 process as photostabilizing channel., (© 2022. The Author(s).)

The orange carotenoid protein (OCP) is a photoactive protein involved in cyanobacterial photoprotection. Here, we report on the functional, spectral and structural characteristics of the peculiar Planktothrix PCC7805 OCP (Plankto-OCP). We show that this OCP variant is characterized by higher photoactivation and recovery rates, and a stronger energy-quenching activity, compared to other OCP studied thus far. We characterize the effect of the functionalizing carotenoid and of his-tagging on these reactions, and identify the time scales on which these modifications affect photoactivation. The presence of a his-tag at the C-terminus has a large influence on photoactivation, thermal recovery and PBS-fluorescence quenching, and likewise for the nature of the carotenoid that additionally affects the yield and characteristics of excited states and the ns-s dynamics of photoactivated OCP. By solving the structures of Plankto-OCP in the ECN- and CAN-functionalized states, each in two closely-related crystal forms, we further unveil the molecular breathing motions that animate Plankto-OCP at the monomer and dimer levels. We finally discuss the structural changes that could explain the peculiar properties of Plankto-OCP., (Copyright © 2022. Published by Elsevier B.V.)

Photophysical studies on a BODIPY-fullerene-distyryl BODIPY triad (BDP-C 60 -DSBDP) and its reference dyads (BODIPY-fullerene; BDP-C 60 and distyryl BODIPY-fullerene; DSBDP-C 60 ) are presented herein. In the triad, the association of the two chromophore units linked by a fullerene moiety leads to strong near UV-Visible light absorption from 300 to 700 nm. The triplet-excited state was observed upon visible excitation in all these assemblies, and shown to be localized on the C 60 or BODIPY moieties. Using quantitative nanosecond transient absorption, we provide a complete investigation on the lifetime and formation quantum yield of the triplet-excited state. In the BDP-C 60 dyad, the triplet excited state of C 60 (τ = 7 ± 1 μs) was obtained with a quantum yield of 40 ± 8%. For the DSBDP-C 60 dyad and BDP-C 60 -DSBDP triad, a longer-lived triplet excited state with a lifetime of around 250 ± 20 μs centered on the DSBDP moiety was formed, with respective quantum yields of 37 ± 8 and 20 ± 4%. Triplet-triplet annihilation up-conversion is characterized in the BDP-C 60 dyad and the bichromophoric triad in the presence of perylene and DSBDP-monomer as respective annihilators. The photo-induced formation of a long-lived 3 DSBDP* in the triad coupled with panchromatic light absorption offers potential applications as a heavy-atom-free organic triplet photosensitizer., (© 2022. The Author(s), under exclusive licence to European Photochemistry Association, European Society for Photobiology.)

In all published photoactivation mechanisms of orange carotenoid protein (OCP), absorption of a single photon by the orange dark state starts a cascade of red-shifted OCP ground-state intermediates that subsequently decay within hundreds of milliseconds, resulting in the formation of the final red form OCP R , which is the biologically active form that plays a key role in cyanobacteria photoprotection. A major challenge in deducing the photoactivation mechanism is to create a uniform description explaining both single-pulse excitation experiments, involving single-photon absorption, and continuous light irradiation experiments, where the red-shifted OCP intermediate species may undergo re-excitation. We thus investigated photoactivation of Synechocystis OCP using stationary irradiation light with a biologically relevant photon flux density coupled with nanosecond laser pulse excitation. The kinetics of photoactivation upon continuous and nanosecond pulse irradiation light show that the OCP R formation quantum yield increases with photon flux density; thus, a simple single-photon model cannot describe the data recorded for OCP in vitro . The results strongly suggest a consecutive absorption of two photons involving a red intermediate with ≈100 millisecond lifetime. This intermediate is required in the photoactivation mechanism and formation of the red active form OCP R ., Competing Interests: The authors declare no competing interests., (© 2022 The Authors.)

Two graphene oxide nanoassemblies using 5-(4-(aminophenyl)-10,15,20-triphenylporphyrin (TPPNH 2 ) were fabricated by two synthetic methods: covalent (GO-CONHTPP) and noncovalent bonding. GO-CONHTPP was achieved through amide formation at the periphery of GO sheets and the hybrid material was fully characterized by FTIR, XPS, Raman spectroscopy, and SEM. Spectroscopic measurements together with theoretical calculations demonstrated that assembling TPPNH 2 on the GO surface in DMF-H 2 O (1:2, v/v) via non-covalent interactions causes changes in the absorption spectra of porphyrin, as well as efficient quenching of its emission. Interestingly, covalent binding to GO does not affect notably neither the porphyrin absorption nor its fluorescence. Theoretical calculations indicates that close proximity and π-π-stacking of the porphyrin molecule with the GO sheet is possible only for the non-covalent functionalization. Femtosecond pump-probe experiments revealed that only the non-covalent assembly of TPPNH 2 and GO enhances the efficiency of the photoinduced electron transfer from porphyrin to GO. In contrast to the non-covalent hybrid, the covalent GO-CONHTPP material can generate singlet oxygen with quantum yields efficiency (ΦΔ = 0.20) comparable to that of free TPPNH 2 (ΦΔ = 0.26), indicating the possible use of covalent hybrid materials in photodynamic/photothermal therapy. The spectroscopic studies combined with detailed quantum-chemical analysis provide invaluable information that can guide the fabrication of hybrid materials with desired properties for specific applications., (© 2022. The Author(s).)

The orange carotenoid protein (OCP) is a photoactive protein involved in cyanobacterial photoprotection by quenching of the excess of light-harvested energy. The photoactivation mechanism remains elusive, in part due to absence of data pertaining to the timescales over which protein structural changes take place. It also remains unclear whether or not oligomerization of the dark-adapted and light-adapted OCP could play a role in the regulation of its energy-quenching activity. Here, we probed photoinduced structural changes in OCP by a combination of static and time-resolved X-ray scattering and steady-state and transient optical spectroscopy in the visible range. Our results suggest that oligomerization partakes in regulation of the OCP photocycle, with different oligomers slowing down the overall thermal recovery of the dark-adapted state of OCP. They furthermore reveal that upon non-photoproductive excitation a numbed state forms, which remains in a non-photoexcitable structural state for at least ≈0.5 μs after absorption of a first photon., Competing Interests: Declaration of interests The authors declare no competing interests., (Copyright © 2022 Biophysical Society. Published by Elsevier Inc. All rights reserved.)

3,3-Diphenylbenzo[f]chromene (1) represents an important architectural platform for photochromic systems. Since the practical utility of such chromophores is largely dependent upon the kinetics of coloration and decoloration, elucidating the mechanistic details of these processes is of great value. Toward this end, we studied the photochromic reaction of (3-(2-methoxyphenyl)-3-phenyl-3H-benzo[f]chromene (2) by both time-resolved UV-vis and mid-IR spectroscopies. We found that irradiation of 2 at 365 nm generates long-lived colored transoid-cis isomers with lifetimes of 17.1 s and 17.5 min (at 21 °C) and even longer-lived transoid-trans isomers with a lifetime of 16 h. These experimental results were supplemented with ab initio ground-state and excited-state calculations, and the resulting theoretical interpretation may be useful for the design of new photochromic systems with optimized photofunctionality., (© 2022. The Author(s).)

A substantial number of Orange Carotenoid Protein (OCP) studies have aimed to describe the evolution of singlet excited states leading to the formation of a photoactivated form, OCP R . The most recent one suggests that 3 ps-lived excited states are formed after the sub-100 fs decay of the initial S 2 state. The S* state, which has the longest reported lifetime of a few to tens of picoseconds, is considered to be the precursor of the first red photoproduct P 1 . Here, we report the ultrafast photodynamics of the OCP from Synechocystis PCC 6803 carried out using visible-near infrared femtosecond time-resolved absorption spectroscopy as a function of the excitation pulse power and wavelength. We found that a carotenoid radical cation can form even at relatively low excitation power, obscuring the determination of photoactivation yields for P 1 . Moreover, the comparison of green (540 nm) and blue (470 nm) excitations revealed the existence of an hitherto uncharacterized excited state, denoted as S ∼ , living a few tens of picoseconds and formed only upon 470 nm excitation. Because neither the P 1 quantum yield nor the photoactivation speed over hundreds of seconds vary under green and blue continuous irradiation, this S ∼ species is unlikely to be involved in the photoactivation mechanism leading to OCP R . We also addressed the effect of His-tagging at the N- or C-termini on the excited-state photophysical properties. Differences in spectral signatures and lifetimes of the different excited states were observed at a variance with the usual assumption that His-tagging hardly influences protein dynamics and function. Altogether our results advocate for the careful consideration of the excitation power and His-tag position when comparing the photoactivation of different OCP variants and beg to revisit the notion that S* is the precursor of photoactivated OCP R ., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

A new donor-acceptor dyad composed of a BODIPY (4,4'-difluoro-4-bora-3a,4a-diaza- s -indacene) donor and a fullerene C 60 acceptor has been synthesized and characterized. This derivative has been prepared using a clickable fullerene building block that bears an alkyne moiety and a maleimide unit. The post-functionalization of the maleimide group by a BODIPY thiol leads to a BODIPY-C 60 dyad, leaving the alkyne moiety for further functional arrangement. On the basis of the combination of semi-empirical and density functional theory (DFT) calculations, spectroelectrochemical experiments, and steady-state and time-resolved spectroscopies, the photophysical properties of this new BODIPY-C 60 dyad were thoroughly studied. By using semi-empirical calculations, the equilibrium of three conformations of the BODIPY-C 60 dyad has been deduced, and their molecular orbital structures have been analyzed using DFT calculations. Two short fluorescence lifetimes were attributed to two extended conformers displaying variable donor-acceptor distances (17.5 and 20.0 Å). Additionally, the driving force for photoinduced electron transfer from the singlet excited state of BODIPY to the C 60 moiety was calculated using redox potentials determined with electrochemical studies. Spectroelectrochemical measurements were also carried out to investigate the absorption profiles of radicals in the BODIPY-C 60 dyad in order to assign the transient species in pump-probe experiments. Under selective photoexcitation of the BODIPY moiety, occurrences of both energy and electron transfers were demonstrated for the dyad by femtosecond and nanosecond transient absorption spectroscopies. Photoinduced electron transfer occurs in the folded conformer, while energy transfer is observed in extended conformers.

In the photochromic reactions of 3 H -naphthopyrans, two colored isomers TC (transoid- cis ) and TT (transoid- trans ) are formed. In terms of optimized photo-switchable materials, synthetic efforts are nowadays evolving toward developing 3 H -naphthopyran derivatives that would not be able to photoproduce the long-living transoid- trans , TT, photoproduct. The substitution with a methoxy group at position 10 results in significant reduction of the TT isomer formation yield. The TC photophysics responsible for TT suppression were revealed here using a combination of multi-scale time resolved absorption UV-vis spectroscopy and ab initio calculations. The substitution changes the TC excited-state potential energy landscape, the bicycle-pedal isomerization path is favored over the rotation around a single double bond. The bicycle-pedal path is aborted in halfway to TT formation due to S 1 →S 0 internal conversion populating back the TC species in the ground electronic state. This is validated by a shorter TC S 1 state lifetime for methoxy derivative in comparison to that of the parent-unsubstituted compound (0.47 ± 0.05 ps vs. 0.87 ± 0.09 ps) in cyclohexane.

Two noncovalent nanohybrids between cationic porphyrin (free-base TMPyP and zinc(II) ZnTMPyP) bearing cationic ( N -methylpyridyl) groups and graphene oxide (GO) were constructed with the aim of generating a photocatalyst active for rhodamine B (RhB) degradation. The obtained materials were thoroughly characterized by steady-state and time-resolved absorption and emission methods, which indicated that metalation of the porphyrin with Zn(II) increases the affinity of the porphyrin toward the GO surface. Photocurrent experiment together with femtosecond transient absorption spectroscopy clearly showed the existence of electron transfer from the photoexcited porphyrin to GO. Both hybrid materials demonstrated higher photocatalytic activity toward RhB degradation as compared to GO; however, ZnTMPyP-GO exhibited more efficient performance (19% of RhB decomposition after 2 h of irradiation). Our data indicate that the presence of Zn(II) in the core of the porphyrin can promote charge separation in the ZnTMPyP-GO composites. The higher degradation rate seen with ZnTMPyP-GO as compared to the TMPyP-GO assemblies highlights the beneficial role of Zn(II)-metalation of the porphyrin ring., Competing Interests: The authors declare no competing financial interest.

The present study explores the influence of graphene oxide (GO) on deactivation pathways of the excited states of zinc 5,10,15,20-tetrakis(4-(hydroxyphenyl))porphyrin (ZnTPPH). The interaction of light with free ZnTPPH molecules and with ZnTPPH molecules adsorbed on graphene oxide sheets was probed via UV-vis spectroscopy, fluorescence spectroscopy, femtosecond pump-probe technique and nanosecond flash photolysis. Formation of the ground-state ZnTPPH-GO complex in solution was monitored by the red-shift of the porphyrin Soret absorption band. It was found that Stern-Volmer fluorescence quenching can be described in terms of two different quenching regimes depending on the GO concentration. In addition, our comprehensive analysis of the steady-state and time-resolved emission experiments led to the conclusion that the observed quenching was entirely attributable to a static mechanism. Laser flash photolysis showed that the triplet lifetime of the ZnTPPH increased in the presence of GO from 174 μs to 292 μs, which is related to the decrease in the rate constant of a radiationless decay mechanism involving rotation of the peripheral hydroxyphenyl rings of the porphyrin. Femtosecond transient absorption spectroscopy demonstrated the presence of a fast photoinduced electron transfer from the singlet excited state of ZnTPPH to the GO sheets, as indicated by the formation of a porphyrin radical cation. Quantum chemical calculations were used to gain deeper insights into the nature of the electronically excited states in the free ZnTPPH as well as in the ZnTPPH-GO complex.

Structural details on the species involved in the photochromic reaction of 3H-naphthopyrans in solution have been formerly determined using NMR spectroscopy. Herein we show that at room temperature time-resolved FT-IR spectroscopy is a simple and efficient tool for structural characterization of colored species generated upon continuous UV light irradiation of the model compound 3H-naphthopyran: 3,3-diphenyl-3H-naphtho[2,1-b]pyran. In solution and in the polymer matrix phase, a colored species transoid-cis is formed after a single-photon excitation process, while transoid-trans is a secondary long-lived photoproduct generated after two-step excitation involving two photons. Understanding the reaction mechanism leading to long-lived colored species can help with the design of new 3H-naphthopyran derivatives structurally optimized for making a photochromic reaction free from transoid-trans products, which is often important for applications. Ab initio calculations show that photoinduced ring-opening followed by isomerization occurs on a multidimensional potential-energy surface. The barriers separating the considered isomeric forms, both in the ground and in the excited state, help to interpret the step-by-step dynamics of the photoprocesses. The system is composed of a variety of ground state equilibrium forms. Each of them is characterized by fast excited-state deactivation pathways which may drive the system through different conical intersection regions.

Ultrafast photoisomerization reactions generally start at a higher excited state with excess of internal vibrational energy and occur via conical intersections. This leads to ultrafast dynamics which are difficult to investigate with a single transient absorption spectroscopy technique, be it in the ultraviolet-visible (UV-vis) or infrared (IR) domain. On one hand, the information available in the UV-vis domain is limited as only slight spectral changes are observed for different isomers. On the other hand, the interpretation of vibrational spectra is strongly hindered by intramolecular relaxation and vibrational cooling. These limitations can be circumvented by fusing UV-vis and IR transient absorption spectroscopy data in a multiset multivariate curve resolution analysis. We apply this approach to describe the spectrodynamics of the ultrafast cis-trans photoisomerization around the C-N double bond observed for aromatic Schiff bases. Twisted intermediate states could be elucidated, and isomerization was shown to occur through a continuous complete rotation. More broadly, data fusion can be used to rationalize a vast range of ultrafast photoisomerization processes of interest in photochemistry.

Instantaneous coloration with large absorbance and quick color fading in the dark are desired properties for thermally reversible photochromic compounds. In the case of naphthopyran derivatives, which have been employed to commercial ophthalmic lenses, the quick color fading has been recently achieved by suppression of the generation of the transoid-trans (TT) form by steric hindrance of bulky substituents. However, there are still open questions whether the steric hindrance decreases the photochromic reaction efficiency, which is a crucial problem for industrial applications. Herein, we apply a wide range of electronic and vibrational time-resolved spectroscopies and reveal that the photochromic reaction yields of the naphthopyrans with bulky substituents are almost comparable (∼0.7) to that of nonsubstituted naphthopyran. The suppression of the formation of the TT form and the effect of solvent polarity on the photodynamics are systematically investigated. These findings are important for fundamental photochemistry and developing naphthopyran-based optimal photofunctional materials.

Betanin is the best known natural dye belonging to the betacyanin family. In this work, efficient singlet oxygen quenching by betanin in deuterated water with the rate constant 1.20 ± 0.15 × 10(8) M(-1) s(-1) is reported, deduced from the (1)O2 phosphorescence decays measured as a function of betanin concentration. The quenching occurs by a chemical mechanism, as confirmed by the analysis of the transient absorption kinetics at the probe λ ∼ 535 nm, by comparison of the initial triplet signal amplitude of perinaphthenone acting as the (1)O2 photosensitizer with the final bleaching signal of betanin. The main betanin oxidation product is 2-decarboxy-2,3-dehydrobetanin, with its formation observed as the transient absorption signal at λ ∼ 445 nm. LC-MS/MS analysis of the photolyzed solutions supports the product identification as 2-decarboxy-2,3-dehydrobetanin, based on the molecular ion [M](+) observed at m/z 505. Isobetanin also undergoes a similar photooxidation reaction.

The photophysical properties of betanin in aqueous and alcoholic solutions were determined at room temperature using ultrafast UV-vis-NIR transient absorption spectroscopy (λexc = 535 nm). Its S1 → Sn (n > 1) absorption bands appear with maxima at about λ ∼ 450 and 1220 nm. The short betanin S1 state lifetime (6.4 ps in water) is mainly determined by the efficient S1 → S0 radiationless relaxation, probably requiring a strong change in geometry, since the S1 lifetime grows to 27 ps in the more viscous ethylene glycol. The fluorescence quantum yield is very low (Φf ∼ 0.0007 in water), therefore this deactivation path is of minor importance. Other processes, such as S1 → T1 intersystem crossing or photoproduct formation, are virtually absent, since full S0 ← S1 ground state recovery is observed within tens of picoseconds after photoexcitation. The observed fast light-to-heat conversion in the absence of triplet excited state formation supports the idea that betanin is a photoprotector in vivo.

The photochemistry of 4,5-carbomethoxy-1,2,3-thiadiazole in solution was studied at room temperature with use of UV-vis and IR transient absorption spectroscopies (λ(ex) = 266 nm). Ultrafast time-resolved techniques demonstrate that there is a very fast rise (<0.4 ps) of bis(carbomethoxy)thiirene in acetonitrile, and that it is the only intermediate formed. The lifetime of the thiirene is limited by dimerization to eventually form tetra(carbomethoxy)thiophene.

Photochemistry of 4-phenyl-1,2,3-thiadiazole (PT) and 4,5-diphenyl-1,2,3-thiadiazole (DPT) in solution was studied at room temperature using UV-vis and IR transient absorption spectroscopies (λ(ex) = 266 nm). Ultrafast techniques show a very fast rise (<0.3 ps) of thiirene and thioketene species, formed from 1,2,3-thiadiazoles in the singlet excited state. The remarkable unimolecular stability of thiirenes in solution is observed. On a millisecond time scale thiirenes with phenyl substituents undergo an intermolecular reaction (dimerization of thiirene-thioketene complexes) leading to 1,3-dithiole derivatives.

The photochemistry of diazocyclohexadienone (1), o-phenylene thioxocarbonate (2), and 2-chlorophenol (3) in solution was studied using time-resolved UV-vis and IR transient absorption spectroscopies. In these three cases, the same product cyclopentadienyl ketene (5) is formed, and two different mechanistic pathways leading to this product are discussed: (a) rearrangement in the excited state (RIES) and (b) a stepwise route involving the intermediacy of vibrationally excited or relaxed carbene. Femtosecond UV-vis detection allows observation of an absorption band assigned to singlet 2-oxocyclohexa-3,5-dienylidene (4), and this absorption feature decays with an ∼30 ps time constant in hexane and acetonitrile. The excess vibrational energy present in nascent carbenes results in the ultrafast Wolff rearrangement of the hot species. IR detection shows that photoexcited o-phenylene thioxocarbonate (2) and 2-chlorophenol (3) efficiently form the carbene species while diazocyclohexadienone (1) photochemistry proceeds mainly by a concerted process.

Photochemistry of 4-methyl-5-carboethoxy-1,2,3-thiadiazole (MCT) in solution was studied at room temperature using UV-vis and IR transient absorption spectroscopies (λ(ex) = 266 nm). Three deactivation pathways are discussed: thiirene formation, thioketene generation, and the internal conversion by repopulating MCT in the ground state. Ultrafast techniques show a very fast rise (<0.4 ps) of thiirene species in acetonitrile, possibly as a result of a rearrangement in the singlet excited state of MCT in concert with molecular nitrogen extrusion. The remarkable stability of thiirene in solution on a millisecond time scale is limited by the process of dimerization (thiirene-thiirene, thiirene-thioketene). NMR analysis permitted identification of stable photoproducts as 1,3-dithietane, 1,3-dithiole, and thiophene derivatives.

The photochemistry of 2-naphthoyl azide was studied in various solvents by femtosecond time-resolved transient absorption spectroscopy with IR and UV-vis detection. The experimental findings were interpreted with the aid of computational studies. Using polar and nonpolar solvents, the formation and decay of the first singlet excited state (S(1)) was observed by both time-resolved techniques. Three processes are involved in the decay of the S(1) excited state of 2-naphthoyl azide: intersystem crossing, singlet nitrene formation, and isocyanate formation. The lifetime of the S(1) state decreases significantly as the solvent polarity increases. In all solvents studied, isocyanate formation correlates with the decay of the azide S(1) state. Nitrene formation correlates with the decay of the relaxed S(1) state only upon 350 nm excitation (S(0) → S(1) excitation). When S(n) (n ≥ 2) states are populated upon excitation (λ(ex) = 270 nm), most nitrene formation takes place within a few picoseconds through the hot S(1) and higher singlet excited states (S(n)) of 2-naphthoyl azide. The data correlate with the results of electron density difference calculations that predict nitrene formation from the higher-energy singlet excited states, in addition to the S(1) state. For all of these experiments, no recovery of the ground state was observed up to 3 ns after photolysis, which indicates that both internal conversion and fluorescence have very low efficiencies.

The photochemistry of two simple acyclic diazo carbonyl compounds, azibenzil and diazoacetone, were studied using the tools of ultrafast time-resolved spectroscopy. In the former case, UV-vis detection allows observation of an absorption band of singlet benzoylphenylcarbene, decaying with a 740 ± 150 ps time-constant in acetonitrile. IR detection shows that the ketene product of Wolff rearrangement (∼2100 cm(-1)) is formed by two parallel pathways: a stepwise mechanism with carbene intermediacy with a slow rise time-constant of 660 ± 100 ps, and directly in the diazo excited state as confirmed by the immediate formation of an IR band of a nascent hot ketene species. Photolysis (270 nm) of diazoacetone in chloroform leads mainly to the ketene species through a concerted process, consistent with the predominance of the syn conformation in the diazoacetone electronic ground state and a zero quantum yield of the internal conversion process.

The photochemistry of diphenylphosphoryl azide was studied by femtosecond transient absorption spectroscopy, by chemical analysis of light-induced reaction products, and by RI-CC2/TZVP and TD-B3LYP/TZVP computational methods. Theoretical methods predicted two possible mechanisms for singlet diphenylphosphorylnitrene formation from the photoexcited phosphoryl azide. (i) Energy transfer from the (π,π*) singlet excited state, localized on a phenyl ring, to the azide moiety, thereby leading to the formation of the singlet excited azide, which subsequently loses molecular nitrogen to form the singlet diphenylphosphorylnitrene. (ii) Direct irradiation of the azide moiety to form an excited singlet state of the azide, which in turn loses molecular nitrogen to form the singlet diphenylphosphorylnitrene. Two transient species were observed upon ultrafast photolysis (260 nm) of diphenylphosphoryl azide. The first transient absorption, centered at 430 nm (lifetime (τ) ∼ 28 ps), was assigned to a (π,π*) singlet S(1) excited state localized on a phenyl ring, and the second transient observed at 525 nm (τ ∼ 480 ps) was assigned to singlet diphenylphosphorylnitrene. Experimental and computational results obtained from the study of diphenyl phosphoramidate, along with the results obtained with diphenylphosphoryl azide, supported the mechanism of energy transfer from the singlet excited phenyl ring to the azide moiety, followed by nitrogen extrusion to form the singlet phosphorylnitrene. Ultrafast time-resolved studies performed on diphenylphosphoryl azide with the singlet nitrene quencher, tris(trimethylsilyl)silane, confirmed the spectroscopic assignment of singlet diphenylphosphorylnitrene to the 525 nm absorption band.

The mechanism of 1,2-H migration process in photoexcited alkyl diazo esters was studied by femtosecond IR transient absorption spectroscopy and theoretical calculations. Two possible processes are discussed: rearrangement in the diazo excited state (RIES) and the intermediacy of singlet carbene species. In chloroform solvent ulrafast IR data show a subpicosecond rise of alkene species indicating the occurrence of the RIES process. Failure in carbene species detection is explained by their absence or very low quantum yield of formation.

Ultrafast laser flash photolysis (lambda(ex) = 375 nm) of para-methoxy-3-phenyl-3-methyl diazirine (p-CH(3)OC(6)H(4)CN(2)CH(3)) produced a transient absorption band in the 400-700 nm region. The carrier of the transient absorption is assigned to the S(1) electronic excited state of this compound based on quantum chemical calculations. The strongest vibrational mode of this S(1) excited state, predicted by RI-CC2/TZVP calculations, was directly observed in the mid-infrared region and had the same lifetime as the transient absorption band detected in the visible region, confirming that the same species is responsible for both transient spectra. The S(1) state undergoes solvation within 20 ps after its formation in polar solvents. Decay of the S(1) state leads to the formation of the isomeric diazo compound and singlet carbene. With 270 nm excitation, both singlet carbene and diazo compound are formed in a much more rapid process from the initially populated diazirine S(2) state (<4 ps), in competition with internal conversion to the S(1) state. The ultrafast spectroscopy and quantum calculations presented in this study provide a rather complete and consistent understanding of the structures and the decay kinetics of the excited states of an aryldiazirine and provide some conclusive answers to the pending general mechanistic questions concerning the photoisomerization of diazirine into diazo compound and the denitrogenation into carbenes.

Ultrafast laser flash photolysis (lambda(ex) = 270 nm) of phenyldiazirine produces transient infrared absorptions at 2040 and 1582 cm(-1). The first band is assigned to phenyldiazomethane, and the second is assigned to singlet phenylcarbene. This assignment is consistent with DFT calculations. Diazo band integration reveals that photoisomerization from diazirine to diazo occurs within a few picoseconds of the laser pulse. The majority of carbene produced is also formed instantaneously.

The photochemistry of Diazo Meldrum's acid (DM) was investigated by fs time-resolved UV-vis and IR spectroscopic methods. UV (266 nm) excitation of DM pumps the molecule to the S 5 and S 7 excited states. After fast internal conversion (IC), the S 2 state is formed, which will undergo Wolff rearrangement to form vibrationally excited ketene, which relaxes in 9 ps. The S 2 state will also relax to the S 1 state, which isomerizes to diazirine, fragments to form carbene, and relaxes further to the ground state of DM. The singlet carbene absorbs at 305 nm, is formed within 300 fs of the laser pulse, and has a lifetime of 2.3 ps in acetonitrile. The lifetime of DM in the S 2 and S 1 states is less than 300 fs. The quantum efficiency of DM decomposition is approximately 50% in chloroform with 266 nm excitation.

Oligothiophenes incorporating MM quadruple bonds have been prepared from the reactions between Mo(2)(TiPB)(4) (TiPB = 2,4,6-triisopropyl benzoate) and 3',4'-dihexyl-2,2'-:5',2''-terthiophene-5,5''-dicarboxylic acid. The oligomers of empirical formula Mo(2)(TiPB)(2)(O(2)C(Th)-C(4)(n-hexyl)(2)S-(Th)CO(2)) are soluble in THF and form thin films with spin-coating (Th = thiophene). The reactions between Mo(2)(TiPB)(4) and 2-thienylcarboxylic acid (Th-H), 2,2'-bithiophene-5-carboxylic acid (BTh-H), and (2,2':5',2''-terthiophene)-5-carboxylic acid (TTh-H) yield compounds of formula trans-Mo(2)(TiPB)(2)L(2), where L = Th, BTh, and TTh (the corresponding thienylcarboxylate), and these compounds are considered as models for the aforementioned oligomers. In all cases, the thienyl groups are substituted or coupled at the 2,5 positions. Based on the x-ray analysis, the molecular structure of trans-Mo(2)(TiPB)(2)(BTh)(2) reveals an extended Lpi-M(2)delta-Lpi conjugation. Calculations of the electronic structures on model compounds, in which the TiPB are substituted by formate ligands, reveal that the HOMO is mainly attributed to the M(2)delta orbital, which is stabilized by back-bonding to one of the thienylcarboxylate pi* combinations, and the LUMO is an in-phase combination of the thienylcarboxylate pi* orbitals. The compounds and the oligomers are intensely colored due to M(2)delta-thienyl carboxylate pi* charge transfer transitions that fall in the visible region of the spectrum. For the molybdenum complexes and their oligomers, the photophysical properties have been studied by steady-state absorption spectroscopy and emission spectroscopy, together with time-resolved emission and transient absorption for the determination of relaxation dynamics. Remarkably, THF solutions the molybdenum complexes show room-temperature dual emission, fluorescence and phosphorescence, originating mainly from (1)MLCT and (3)MM(deltadelta*) states, respectively. With increasing number of thienyl rings from 1 to 3, the observed lifetimes of the (1)MLCT state increase from 4 to 12 ps, while the phosphorescence lifetimes are approximately 80 micros. The oligomers show similar photophysical properties as the corresponding monomers in THF but have notably longer-lived triplet states, approximately 200 micros in thin films. These results, when compared with metallated oligothiophenes of the later transition elements, reveal that M(2)delta-thienyl pi conjugation leads to a very small energy gap between the (1)MLCT and (3)MLCT states of <0.6 eV.

The photochemistry of a p-biphenylyl diazo ester (BpCN2CO2CH3) and diazo ketone (BpCN2COCH3) were studied by ultrafast time-resolved UV-vis and IR spectroscopies. The excited states of these diazo compounds were detected and found to decay with lifetimes of less than 300 fs. The diazo ester produces singlet carbene with greater quantum efficiency than the ketone analogue due to competing Wolff rearrangement (WR) in the excited state of the diazo ketone. Carbene BpCCO2CH3 has a singlet-triplet gap that is close to zero in cyclohexane, but the triplet is the ground state. The two spin states are in rapid equilibrium in this solvent relative to reaction with cyclohexane. There is (for a carbene) a slow rate of singlet to triplet intersystem crossing (isc) in this solvent because the orthogonal singlet must rotate to a higher energy orientation prior to isc. In acetonitrile and in dichloromethane BpCCO2CH3 has a singlet ground state. Ketocarbene BpCCOCH3 has a singlet ground state in cyclohexane, in dichloromethane, and in acetonitrile and decays by WR to form a ketene detected by ultrafast IR spectroscopy in these solvents. Ketocarbenes have more stable singlet states, relative to carbene esters, because of the superior conjugation of the filled hybrid orbital of the carbene with the pi system of the carbonyl group, the same factor that makes methyl ketones more acidic than the analogous esters. The rate of WR of BpCCOCH3 is faster in cyclohexane than in dichloromethane and acetonitrile because of intimate solute-solvent interactions between the empty p orbital of the carbene and nonbonding electron pairs of heteroatoms of the solvent. These interactions stabilize the carbene and retard the rate of WR.

Femtosecond broadband transient absorption experiments of 1-nitropyrene, a nitro-polycyclic aromatic hydrocarbon of environmental concern are presented in cyclohexane and hexane solutions. The transient absorption spectra show the presence of three species that are assigned to the Franck-Condon excited lowest singlet (S1) state, the structurally relaxed S1 state, and the lowest excited triplet state. The spectral changes at early times are interpreted in terms of conformational dynamics; primarily due to an ultrafast rotation of the nitro group in the S1 state. This excited state relaxation is followed by intersystem crossing with a time constant of 7 ps. CIS/6-31G(d,p) calculations predict planarization of the nitro-aromatic torsional angle as the major nuclear relaxation coordinate, from 32.8 degrees at the HF/6-31G(d,p) level of theory in the ground state (27.46 degrees at B3LYP/6-31++G(d,p)) to 0.07 degrees in the S1 state. Vertical excitation energies at the TDDFT/6-31++G(d,p) and TDDFT/IEFPCM/6-31++G(d,p) levels of theory predict a small energy gap (<0.12 eV) between the S1(pipi*) state and the third excited triplet state T3(npi*) in the gas phase and in cyclohexane, respectively. The small energy gap suggests a large spin-orbit coupling between the S1(pipi*) and T3(npi*) states, which explains the ultrafast intersystem crossing of 1-nitropyrene in nonpolar solvents.

The photochemistry of two isomeric aryl diazo ketones was investigated by fs time-resolved UV-vis and IR spectroscopies. Both diazo ketone excited states decompose in less than 300 fs by multiple pathways. One pathway involves concerted Wolff rearrangement and nitrogen extrusion, most likely in the syn rotomer. In the anti rotomer of one isomer, oxygen migration proceeds in concert with nitrogen extrusion to form rearranged keto carbene. This rotomer excited state also decomposes to form unrearranged carbene, which isomerizes in 5 ps.

The rate of protonation of singlet 2-fluorenylnitrene was studied in eight protic solvents. The protonation rates vary between 10(11) and 10(9) s(-1) and are well-correlated with Swain's acity parameters. This demonstrates that Swain acity parameters and nitrene protonation rates can be used to evaluate bulk solvent acidity.

Exposure of 2-naphthyl azide in acetonitrile at ambient temperature to femtosecond pulses of 266 nm light produces a transient absorption with maxima at 350 and 420 nm. The carrier of the 350 nm band decays more rapidly than that of the 420 nm band which has a lifetime of 1.8 ps. Analogous experiments with 1-chloro-2-naphthyl azide in methanol allow the assignment of the 350 nm band to a singlet excited state of 2-naphthyl azide and the carrier of the 420 nm band to singlet 2-naphthylnitrene. This reactive intermediate has the shortest lifetime of any singlet nitrene observed to date and is a true reactive intermediate. Computational studies at the RI-CC2 level of theory support these conclusions and suggest that initial excitation populates the S2 state of 2-naphthyl azide. The S2 state, best characterized as a pi --> (pi*, aryl) transition, has a geometry similar to S0. S2 of 2-naphthyl azide can then populate the S1 state, a pi --> (in-plane, pi*, azide) excitation, and in the S1 state, electron density is depleted along the proximal N-N bond. S1 is dissociative along that N-N coordinate to form the singlet nitrene, and with a barrier of only approximately 5 kcal/mol for N2 extrusion.

p-biphenylyl, o-biphenylyl, and 1-naphthyl azides were deposited in argon at low temperature in the presence and absence of HCl. In the absence of HCl, the known electronic and vibrational spectra of the corresponding triplet nitrenes, azirines, and didehydroazepines were observed, whereas in the presence of HCl, photolysis of these azides produces new electronic spectra assigned to the corresponding nitrenium cations. For p-biphenylyl azide the resulting spectrum of the nitrenium ion is very similar to the previously observed solution-phase spectrum of this species. The vibrational spectrum of this cation was recorded for the first time. Spectroscopic evidence for the previously unknown o-biphenylylnitrenium cation and 1-naphthylnitrenium cation are provided. The spectra of p- and o-biphenylylnitrenium cations and 1-naphthylnitrenium cation are well reproduced by CASSCF and CASPT2 calculations. The same nitrenium cations were detected in solution by femtosecond time-resolved laser flash photolysis of the appropriate azides in 88% formic acid. The transient spectra of the nitrenium cations recorded in solution are in good agreement with the spectra obtained in HCl matrices. The rates of formation of these cations equal the rates of decay of the singlet nitrenes in 88% formic acid and are as follows: p-biphenylyl (taugrowth = 11.5 ps), o-biphenylyl (taugrowth = 7.7 ps), and 1-naphthylnitrenium cations (taugrowth = 8.4 ps). The decay lifetimes of p- and o-biphenylylnitrenium cations are 50 and 27 ns, respectively. The decay lifetimes of 1-naphthylnitrenium cation is 860 ps in 88% formic acid.

Ultrafast photolysis of p-biphenylyldiazoethane (BDE) produces an excited state of the diazo compound in acetonitrile, cyclohexane, and methanol with lambdamax = 490 nm and lifetimes of less than 300 fs. The decay of the diazo excited state correlates with the growth of singlet carbene absorption at 360 nm. The optical yields of diazo excited states produced by photolysis of p-biphenylyldiazomethane (BDM) and BDE are the same; however, the optical yield of singlet p-biphenylylmethylcarbene (1BpCMe) is 30-40% less than that of p-biphenylylcarbene (1BpCH) in all three solvents. The results are explained by rearrangement in the excited state (RIES) of BDE to form p-vinylbiphenyl (VB) in parallel with extrusion of nitrogen to form 1BpCMe in reduced yield. This interpretation is consistent with product studies (ethanol-OD in cyclohexane) which indicate that there is an approximately 25% yield of VB that is formed by a mechanism that bypasses the relaxed singlet carbene. The decay of 1BpCMe is biexponential, and that of 1BpCH is monoexponential. This is attributed either to efficient relaxation of vibrationally excited 1BpCMe by 1,2 migration of hydrogen to form VB (minor) or to the increased number of low-frequency vibrational modes provided by the methyl group (major). A methyl group retards the rate of intersystem crossing (ISC), relative to a hydrogen atom, and ISC is more rapid in nonpolar solvents. Reaction of 1BpCMe with methanol is much faster than spin equilibration. Both the lifetime of 1BpCMe and 1BpCH are the same in cyclohexane and in cyclohexane-d12. This demonstrates that spin equilibration is faster than reaction of either carbene with the solvent. The lifetimes of 1BpCMe and 1BpCMe-d3 are the same in cyclohexane. This indicates that 1,2 hydrogen migration of 1BpCMe to form VB is slower than spin equilibration in cyclohexane. In acetonitrile, however, the lifetime of 1BpCMe-d3 is 1.5 times longer than that of 1BpCMe in the same solvent. Thus, in acetonitrile, where ISC is slow, the rate of 1,2 hydrogen shift of 1BpCMe is competitive with ISC. In cyclohexene, the lifetime of 1BpCH is shortened relative to that in cyclohexane. The lifetime of 1BpCMe is the same in cyclohexene and cyclohexane. The data indicate that spin relaxation is slow relative to reaction of 1BpCH with neat alkene but that spin relaxation is fast for 1BpCMe relative to reaction with neat cyclohexene.

Ultrafast photolysis (lambdaex = 270, 350, or 360 nm) of bromophenyl, chlorophenyl, fluorophenyl, and fluoro-para-trifluoromethylphenyl diazirines produces transient species which absorb broadly in the UV and visible regions. Transient decay can be fit to either mono- or biexponential functions (tau1 approximately 0.3-10 ps, tau2 approximately 10-350 ps; dependent on solvent and halogen). Fluoro- and chlorophenylcarbene are formed within the time resolution of the spectrometer (300 fs, 270 nm excitation). Bromophenyl diazirine decay (270 nm excitation) correlates with the growth of bromophenylcarbene. Solvent and substituent effects on the slower decays of the transient absorptions are consistent with assigning the carriers of transient absorption in the visible region to ring-opened zwitterionic species.

The photochemistry of para- and ortho-biphenylyl azides and 1-naphthyl azide was studied by ultrafast spectroscopy. In every case, the singlet azide second excited states were observed by transient absorption spectroscopy and were found to have lifetimes of hundreds of femtoseconds. The decay of the S(2) states of the azides was accompanied by the growth of transient absorption of the corresponding singlet nitrenes. The intermediate S(1) state of the azides could not be observed due to its low instantaneous concentration resulting from fast fragmentation and nitrene formation. Quantum chemical calculations predict that the S(2) state of the azide is bound and that there is a much lower barrier toward arylnitrene formation from the S(1) state of the azide. Vibrational cooling of para-biphenylnitrene (11 ps) was experimentally observed. The lifetime of singlet ortho-biphenylnitrene was 16 ps in acetonitrile and was not affected by perdeuteration of the aryl ring. The lifetime of singlet 1-naphthylnitrene is 12 ps in acetonitrile at ambient temperature.

p-Biphenylyldiazomethane was excited by femtosecond pulses of UV light in acetonitrile, in cyclohexane, and in methanol. Ultrafast photolysis produces a singlet excited state of p-biphenylyldiazomethane with lambdamax = 490 nm, and lifetimes of less than 300 fs in acetonitrile, in cyclohexane, and in methanol. The decay of the excited state is accompanied by the growth of transient absorption with lambdamax = 360 nm. The carrier of this transient absorption is attributed to singlet p-biphenylylcarbene, a result that is consistent with the predictions of TD-DFT calculations. The singlet carbene lifetimes are 200 and 77 ps in acetonitrile and cyclohexane, respectively, and are controlled by intersystem crossing to the lower energy triplet state. The transient absorption does not decay to baseline in acetonitrile, because of the formation of nitrile ylide. The equilibrium mixture of singlet and triplet p-biphenylylcarbene reacts with acetonitrile to form a nitrile ylide (lambdamax = 370 nm), and with cyclohexane by C-H insertion 1-20 ns after the laser pulse. The singlet carbene lifetime is only 7.9 ps in methanol, owing to a rapid reaction with the solvent. Reaction with the solvent gives rise, in part, to a p-biphenylylbenzyl cation (lambdamax = 450 nm, tau = 6.3 ps) in methanol.

[reaction: see text] Ultrafast time-resolved studies of the photochemistry of 2-azidonitrobenzene demonstrate that the lifetimes of excited singlet 2-azidonitrobenzene and 2-nitrophenylnitrene are 500 fs and 8.3 ps, respectively, in solution at ambient temperature. The singlet nitrene is a discrete intermediate but is too short lived to undergo bimolecular reactions.

The reactive intermediate produced upon photolysis of 8-azidoadenosine was studied by chemical trapping studies, laser flash photolysis with UV-vis and IR detection, and modern computational chemistry. It is concluded that photolysis of 8-azidoadenosine in aqueous solution releases the corresponding singlet nitrene which rapidly tautomerizes to form a closed adenosine diazaquinodimethane in less than 400 fs. A perbenzoylated derivative of 8-azidoadenosine cannot undergo this tautomerization, and instead, it fragments upon photolysis to form an opened adenosine diazaquinodimethane. The singlet nitrene is too short-lived to be observed and, thus, to relax to the lowest triplet state or to become covalently attached to targeted biological macromolecules. The pivotal closed adenosine diazaquinodimethane, the product of nitrene tautomerization, has a lifetime of ca. 1 min or longer in water and in HEPES buffer at ambient temperature. However, this intermediate reacts rapidly with good nucleophiles such as amines, thiols, and phenolates, and significantly more slowly with weak nucleophiles such as alcohols and water. On the basis of these studies, it is clear that the closed adenosine diazaquinodimethane, and not the singlet or triplet nitrene, is the pivotal reactive intermediate involved in photolabeling and cross-linking studies using the 8-azidoadenosine family of photoaffinity labeling reagents.

Laser flash photolysis (LFP, 400 nm excitation) of the anti-cancer drug tirapazamine (TPZ) in acetonitrile produces the singlet excited-state S1 with lambda(max) = 544 nm. The lifetime of this state is 130 ps, in good agreement with the reported fluorescence lifetime. The excited state is reduced to the corresponding radical anion by KSCN or KI. The spectrum of the radical anion is in good agreement with previously reported pulse radiolysis studies and time-dependent density functional theory (TD-DFT) calculations. LFP of desoxytirapazamine (dTPZ) also produces the first excited singlet state, S1. The fluorescence quantum yield and lifetime (5.4 ns) of the dTPZ singlet excited state are both much greater than the corresponding values of TPZ. This is explained by DFT calculations that predict that cyclization of TPZ to form an oxaziridine is thermodynamically facile but that cyclization of dTPZ to form an oxadiaziridine is not. Thus, the S1 state of TPZ has a short lifetime and low fluorescence quantum yield due to ready cyclization whereas the cyclization of the S1 state of dTPZ is unimportant and does not limit either the fluorescence quantum yield or the fluorescence lifetime. This conclusion is confirmed by studies of dTPZ', an isomer of dTPZ containing the C=N-O moiety which has a low quantum yield and short fluorescence lifetime similar to that of TPZ.