Time-resolved Optical Absorption Research Articles

Photochemical Formation and Electronic Structure of an Alkane σ-Complex from Time-Resolved Optical and X-ray Absorption Spectroscopy.

C-H bond activation reactions with transition metals typically proceed via the formation of alkane σ-complexes, where an alkane C-H σ-bond binds to the metal. Due to the weak nature of metal-alkane bonds, σ-complexes are challenging to characterize experimentally. Here, we establish the complete pathways of photochemical formation of the model σ-complex Cr(CO)5-alkane from Cr(CO)6 in octane solution and characterize the nature of its metal-ligand bonding interactions. Using femtosecond optical absorption spectroscopy, we find photoinduced CO dissociation from Cr(CO)6 to occur within the 100 fs time resolution of the experiment. Rapid geminate recombination by a fraction of molecules is found to occur with a time constant of 150 fs. The formation of bare Cr(CO)5 in its singlet ground state is followed by complexation of an octane molecule from solution with a time constant of 8.2 ps. Picosecond X-ray absorption spectroscopy at the Cr L-edge and O K-edge provides unique information on the electronic structure of the Cr(CO)5-alkane σ-complex from both the metal and ligand perspectives. Based on clear experimental observables, we find substantial destabilization of the lowest unoccupied molecular orbital upon coordination of the C-H bond to the undercoordinated Cr center in the Cr(CO)5-alkane σ-complex, and we define this as a general, orbital-based descriptor of the metal-alkane bond. Our study demonstrates the value of combining optical and X-ray spectroscopic methods as complementary tools to study the stability and reactivity of alkane σ-complexes in their role as the decisive intermediates in C-H bond activation reactions.

Influence of the RF voltage amplitude on the space- and time-resolved properties of RF–LF dielectric barrier discharges in α–γ mode

This work reports the results of an experimental and modeling study on dual-frequency Ar–NH3 dielectric barrier discharges (DBDs) exhibiting the α–γ transition. A combination of space- and time-resolved optical absorption and emission spectroscopy is used to record spatio-temporal mappings of the Ar metastable number density, Ar 750.4 nm line emission intensity, and electron–Ar bremsstrahlung continuum emission intensity. With the increase of the radio frequency (RF) voltage amplitude in a 50 kHz–5 MHz DBD, maximum populations of Ar excited species (1s and 2p states, linked to the population of high-energy electrons) observed in the γ mode decrease and appear earlier in the low-frequency cycle. On the other hand, the density of the bulk electrons, monitored from the continuum emission intensity, increases, with a more prominent rise in the RF-α mode than in the γ regime. Such behaviors are consistent with the predictions of 1D fluid model and results from a decrease of the gas voltage required for self-maintenance of the cathode sheath in the γ breakdown.

Time-resolved optical absorption measurements of calcium fluoride crystals

This paper examines time-resolved optical absorption measurements in a CaF2 crystal. It is shown that defects with a concentration of about 1017 cm−3 are introduced into the sample within about 10−8 s. The decay curves of defects created by a nanosecond electron pulse in CaF2 were measured in the temperature range from 300 to 700 K. It is found that decay curves are decomposed into three bimolecular decay stages. The totality of the obtained experimental data can be consistently explained within the framework of the assumption of thermal disorder of the fluorite anionic sublattice. The result of electron-hole recombination is the formation of fairly “simple” defect structures in the CaF2 crystal.

Mapping the Ultrafast Mechanistic Pathways of Co Photocatalysts in Pure Water through Time-resolved X-ray Spectroscopy.

Nanosecond time-resolved X-ray (tr-XAS) and optical transient absorption spectroscopy (OTA) are applied to study 3 multimolecular photocatalytic systems with [Ru(bpy)3]2+photoabsorber, ascorbic acid electron donor and Co catalysts with methylene (1), hydroxomethylene (2) and methyl (3) amine substituents in pure water. OTA and tr-XAS of 1 and 2 show that the favored catalytic pathway involves reductive quenching of the excited photosensitizer and electron transfer to the catalyst to form a CoII square pyramidal intermediate with a bonded aqua molecule followed by a CoI square planar derivative that decays within ~8 µs. By contrast, a CoI square pyramidal intermediate with a longer decay lifetime of ~35µs is formed from an analogous CoII geometry for 3 in H2O. These results highlight the protonation of CoI to form the elusive hydride species to be the rate limiting step and show that the catalytic rate can be enhanced through hydrogen containing pendant amines that act as H-H bond formation proton relays.

Characterization of Triplet State of Cyanine Dyes with Two Chromophores Effect of Molecule Structure

Quantum yields (φT) and energies (ET) of the first triplet state T1 for four molecules of cyanine dyes with two chromophores (BCDs), promising photoactive compounds for various applications, for example, as photosensitizers in photodynamic therapy (PDT) and fluorescence diagnostics (FD), were studied in 1-propanol solutions by steady-state and time-resolved optical absorption techniques. BCDs differ by the structure of the central heterocycle, connecting the chromophores. The heterocycle structure is responsible for electron tunneling between chromophores, for which efficiency can be characterized by splitting of the BCD triplet energy levels. It was shown that the increase in the tunneling efficiency reduces ET values and increases φT values. This aspect is very promising for the synthesis of new effective photosensitizers based on cyanine dyes with two interacting chromophores for various applications, including photodynamic therapy.

Engineering Band Gap and Photoconduction in Semiconducting Metal Organic Frameworks: Metal Node Effect.

We report a systematic study on the correlation of the metal nodes in M-THQ conducting MOFs (M = Fe, Ni, Cu, and Zn; THQ = tetra-hydroxybenzoquinone) with their structure, photophysical property, and photoconductivity. We found that the structural preference in these MOFs is controlled by metal node identity where Cu prefers a square planar coordination which leads to a 2D Kagome-type structure. Fe, Ni, and Zn prefer an octahedral sphere which leads to a 3D structure. Fe-THQ has the smallest band gap and highest photoconduction as well as a long-lived ligand-to-metal charge transfer state due to the mixed valence state revealed by time-resolved optical and X-ray absorption and terahertz spectroscopy. These results demonstrate the importance of the metal node in tuning the photophysical and photocatalytic properties of MOFs.

Biscarbocyanine dye for fluorescence imaging: Binding with albumin and DNA, cell accumulation, intracellular distribution and molecular modeling

The photophysical characteristics of a new bis-carbocyanine dye (BCD) with 4-methylpyridine fragment in the polymethine chain as well as its interaction with human serum albumin (HSA) and DNA were studied by means of steady-state and time-resolved optical absorption and fluorescence spectroscopies. We also obtained the rate of penetration and localization of BCD in the human colon adenocarcinoma cells (HTC116) and the data on its dark and photoinduced cytotoxicity toward these cells. The molecular dynamics method was employed to detect the localization of the BCD molecule within the HSA and DNA structures and to assess the BCD conformational behavior in different environments. The BCD binding constants to HSA and DNA were (8.2 ± 2.3) × 104 M−1 and (2.6 ± 1.3) × 105 M−1, respectively. The BCD fluorescence quantum yield increases 10-fold after binding to HSA. The molecular docking and molecular dynamics analysis showed that BCD bound to HSA is located in a wide moderately polar pocket between the IIA and IIIA albumin subdomains. BCD demonstrated rapid infiltration into the HCT116 cell interior and exceptionally low phototoxicity toward these cells which is explained by the absence of the BCD triplet state upon direct photoexcitation. This makes BCD a promising fluorescence agent for in vivo imaging in angiography. In the field of medical diagnostics, there is a request for the creation of fluorescent labels with fluorescence in the 650–700 nm range for existing equipment that does not require IR lasers and cameras.

Photobleaching and Recovery Kinetics of a Palette of Carbon Nanodots Probed by In Situ Optical Spectroscopy.

Carbon dots (CDs) are a family of fluorescent nanoparticles displaying a wide range of interesting properties, which make them attractive for potential applications in different fields like bioimaging, photocatalysis, and many others. However, despite many years of dedicated studies, wide variations exist in the literature concerning the reported photostability of CDs, and even the photoluminescence mechanism is still unclear. Furthermore, an increasing number of recent studies have highlighted the photobleaching (PB) of CDs under intense UV or visible light beams. PB phenomena need to be fully addressed to optimize practical uses of CDs and can also provide information on the fundamental mechanism underlying their fluorescence. Moreover, the lack of systematic studies comparing several types of CDs displaying different fluorescence properties represents another gap in the literature. In this study, we explored the optical properties of a full palette of CDs displaying a range from blue to red emissions, synthesized using different routes and varying precursors. We investigated the photostability of different CDs by observing in situ their time-resolved fluorescence degradation or optical absorption changes under equivalent experimental conditions and laser irradiation. The results about different PB kinetics clearly indicate that even CDs showing comparable emission properties may exhibit radically different resistances to PB, suggesting systematic connections between the resistance to PB, the characteristic spectral range of emission, and CD quantum yields. To exploit the PB dynamics as a powerful tool to investigate CD photophysics, we also carried out dedicated experiments in a partial illumination geometry, allowing us to analyze the recovery of the fluorescence due to diffusion. Based on the experimental results, we conclude that the nature of the CD fluorescence cannot be solely ascribable to small optically active molecules free diffusing in solution, contributing to shed light on one of the most debated issues in the photophysics of CDs.

Toward Improved Charge Separation through Conformational Control in Copper Coordination Complexes.

The continued development of solar energy as a renewable resource necessitates new approaches to sustaining photodriven charge separation (CS). We present a bioinspired approach in which photoinduced conformational rearrangements at a ligand are translated into changes in coordination geometry and environment about a bound metal ion. Taking advantage of the differential coordination properties of CuI and CuII, these dynamics aim to facilitate intramolecular electron transfer (ET) from CuI to the ligand to create a CS state. The synthesis and photophysical characterization of CuCl(dpaaR) (dpaa = dipicolylaminoacetophenone, with R = H and OMe) are presented. These ligands incorporate a fluorophore that gives rise to a twisted intramolecular charge transfer (TICT) excited state. Excited-state ligand twisting provides a tetragonal coordination geometry capable of capturing CuII when an internal ortho-OMe binding site is present. NMR, IR, electron paramagnetic resonance (EPR), and optical spectroscopies, X-ray diffraction, and electrochemical methods establish the ground-state properties of these CuI and CuII complexes. The photophysical dynamics of the CuI complexes are explored by time-resolved photoluminescence and optical transient absorption spectroscopies. Relative to control complexes lacking a TICT-active ligand, the lifetimes of CS states are enhanced ∼1000-fold. Further, the presence of the ortho-OMe substituent greatly enhances the lifetime of the TICT* state and biases the coordination environment toward CuII. The presence of CuI decreases photoinduced degradation from 14 to <2% but does not result in significant quenching via ET. Factors affecting CS in these systems are discussed, laying the groundwork for our strategy toward solar energy conversion.

Lipid-Enhanced Photoprotection of LHCII in Membrane Nanodisc by Reducing Chlorophyll Triplet Production

Carotenoid (Car) quenching chlorophyll triplet state (3Chl a*), an unwanted photosensitizer yielding harmful reactive oxygen species, is crucial for the survival of oxygenic photosynthetic organisms. For the major light-harvesting complex of photosystem II (LHCII) in isolated form, 3Chl a* is deactivated via sub-nanosecond Chl-to-Car triplet excitation energy transfer by lutein in the central domain of LHCII; however, the mechanistic difference from LHCII in vivo remains to be explored. To investigate the intrinsic Car-photoprotection properties of LHCII in a bio-mimicking circumstance, we reconstituted trimeric spinach LHCII into the discoidal membrane of nanosize made from l-α-phosphatidylcholine and examined the triplet excited dynamics. Time-resolved optical absorption combined with circular dichroism spectroscopies revealed that, with reference to LHCII in buffer, LHCII in the membrane nanodisc shows appreciable conformational variation in the neoxanthin and the Lut621 domains and in the Chl a-terminal cluster owing to the lipid-protein interactions, which, in turn, alters the triplet population of Lut620 and Lut621 and their partition. Importantly, the unquenched 3Chl a* population in the complex was reduced by 60%, indicating that LHCII in the membrane adopts a conformation that is optimized for the alleviation of photoinhibition.

Influence of matrix composition and its fluctuations on excitation relaxation and emission spectrum of Ce ions in (Gdx Y1-x)3Al2Ga3O12:Ce scintillators

Cerium-doped mixed garnet-type single crystals (GdxY1-x)3Al2Ga3O12 with different yttrium content have been fabricated and studied as a prospective scintillating material enabling improvement of scintillation properties by tuning the composition of the matrix-building crystal. The influence of the matrix composition on the emitting Ce ion is studied using linear and time-resolved nonlinear optical absorption and time-resolved photoluminescence spectroscopy. The study of photoluminescence at resonant excitation revealed a composite origin of Ce3+ emission band. This behavior is interpreted by the contribution of Ce3+ ions located in inequivalent positions expected due to the disorder caused in the garnet-type lattice of a mixed crystal by compositional fluctuations. The substitution of gadolinium by yttrium in the lattice results not only in an emission blue shift and in decreased splitting of the lowest doublet 5d state of Ce3+ but also in an increased separation between the lowest doublet level 5d1 and the lowest triplet 5d3 level, as well as in changing the rates of intracenter and extracenter energy relaxation.

Generating Triplets in Organic Semiconductor Tetracene upon Photoexcitation of Transition Metal Dichalcogenide ReS2.

We studied the dynamics of transfer of photoexcited electronic states in a bilayer of the two-dimensional transition metal dichalcogenide ReS2 and tetracene, with the aim to produce triplets in the latter. This material combination was used as the band gap of ReS2 (1.5 eV) is slightly larger than the triplet energy of tetracene (1.25 eV). Using time-resolved optical absorption spectroscopy, transfer of photoexcited states from ReS2 to triplet states in tetracene was found to occur within 5 ps with an efficiency near 38%. This result opens up new possibilities for heterostructure design of two-dimensional materials with suitable organics to produce long-lived triplets. Triplets are of interest as sensitizers in a wide variety of applications including optoelectronics, photovoltaics, photocatalysis, and photon upconversion.

Structure and excited-state dynamics of dimeric copper(i) photosensitizers investigated by time-resolved X-ray and optical transient absorption spectroscopy.

Time-resolved X-ray (tr-XAS) and optical transient absorption (OTA) spectroscopy in the picosecond time scale coupled with Density Functional theory (DFT) and X-ray absorption near-edge structure (XANES) calculations are applied to study three homoleptic Cu(i) dimeric chromophores with ethyl and longer propyl spacers, denoted as [Cu2(mphenet)2]Cl2 (C1), [Cu2(mphenet)2](ClO4)2 (C2) and [Cu2(mphenpr)2](ClO4)2 (C3) (where mphenet = 1,2-bis(9-methyl-1,10-phenanthrolin-2-yl)ethane and mphenpr = 1,3-bis(9-methyl-1,10-phenanthrolin-2-yl)propane). Tr-XAS analysis after light illumination at ∼ 100 ps illustrate the formation of a flattened triplet excited state in all 3 complexes. Optical transient absorption (OTA) analysis for C1 monitored in water and C2 and C3 measured in acetonitrile reveals distinct excited-state lifetimes of 169 ps, 670 ps and 1600 ps respectively. These differences are associated to changes in the solvent (comparing C1 and C2) and the flexibility of the ligand to adapt after Cu flattening upon excitation (C2 and C3). Our results are important for the improved structural dynamics of these types of Cu-based dimeric compounds, and can guide the integration of these chromophores into more complex solar energy conversion schemes.

Tracking the Light-Induced Excited-State Dynamics and Structural Configurations of an Extraordinarily Long-Lived Metastable State at Room Temperature.

Time-resolved X-ray (Tr-XAS) and optical transient absorption (OTA) spectroscopy on the pico-microsecond timescale coupled with density functional theory calculations are applied to study the light-induced spin crossover processes of a Fe-based macrocyclic complex in solution. Tr-XAS analysis after light illumination shows the formation of a seven-coordinated high-spin quintet metastable state, which relaxes to a six-coordinated high-spin configuration before decaying to the ground state. Kinetic analysis of the macrocyclic complex reveals an unprecedented long-lived decay lifetime of approximately 42.6 μs. Comparative studies with a non-macrocyclic counterpart illustrate a significantly shortened approximately 568-fold decay lifetime of about 75 ns, and highlight the importance of the ligand arrangement in stabilizing the reactivity of the excited state. Lastly, OTA analysis shows the seven-coordinated high-spin state to be formed within approximately 6.2 ps. These findings provide a complete understanding of the spin crossover reaction and relaxation pathways of the macrocyclic complex, and reveal the importance of a flexible coordination environment for their rational design.

Improvement of the timing properties of Ce-doped oxyorthosilicate LYSO scintillating crystals

The aim of this work has been to improve the time resolution of radiation detectors for future high-energy physics experiments and medical imaging applications. Ce-doped oxyorthosilicate Lu2SiO5:Ce (LSO) and mixed oxyorthosilicate Lu1.6Y0.4SiO5:Ce (LYSO) have been investigated as prospective scintillators for such high-time-resolution applications. A differential optical absorption technique with sub-picosecond time resolution upon selective excitation of Ce3+ ions to different excited states has been adopted to study carrier dynamics in these scintillators, and coincidence time resolution measured using 511 keV γ-quanta has been exploited to test their timing properties. A delay in population of the emitting level of Ce3+ has been observed, and is interpreted in terms of electron trapping, which is more pronounced in mixed yttrium-containing LYSO crystals due to composition fluctuations. It is shown that the delay, which affects the luminescence response time, can be eliminated by co-doping of LYSO:Ce with calcium at concentrations as low as 5 ppm. The faster kinetics of electron transfer correlates with a better coincidence time resolution. Thermalization and spatial distribution of non-equilibrium carriers has been studied theoretically to link the results obtained by the time-resolved differential optical absorption technique with the behavior of the non-equilibrium carriers generated by irradiation.

The Reactions of O2 and NO with Mixed-Valence ba3 Cytochrome c Oxidase from Thermus thermophilus

Earlier CO flow-flash experiments on the fully reduced Thermus thermophilus ba3 (Tt ba3) cytochrome oxidase revealed that O2 binding was slowed down by a factor of 10 in the presence of CO (Szundi et al., 2010, PNAS 107, 21010–21015). The goal of the current study is to explore whether the long apparent lifetime (∼50 ms) of the CuB+-CO complex generated upon photolysis of the CO-bound mixed-valence Tt ba3 (Koutsoupakis et al., 2019, Acc. Chem. Res. 52, 1380–1390) affects O2 and NO binding and the ability of CuB to act as an electron donor during O-O bond splitting. The CO recombination, NO binding, and the reaction of mixed-valence Tt ba3 with O2 were investigated by time-resolved optical absorption spectroscopy using the CO flow-flash approach and photolabile O2 and NO carriers. No electron backflow was detected after photolysis of the mixed-valence CO-bound Tt ba3. The rate of O2 and NO binding was two times slower than in the fully reduced enzyme in the presence of CO and 20 times slower than in the absence of CO. The purported long-lived CuB+-CO complex did not prevent O-O bond splitting and the resulting PM formation, which was significantly faster (5–10 times) than in the bovine heart enzyme. We propose that O2 binding to heme a3 in Tt ba3 causes CO to dissociate from CuB+ in a concerted manner through steric and/or electronic effects, thus allowing CuB+ to act as an electron donor in the mixed-valence enzyme. The significantly faster O2 binding and O-O bond cleavage in Tt ba3 compared to analogous steps in the aa3 oxidases could reflect evolutionary adaptation of the enzyme to the microaerobic conditions of the T. thermophilus HB8 species.

Selective Excited-State Dynamics in a Unique Set of Rationally Designed Ni Porphyrins

In this work, we report the design and photophysical properties of a unique class of Ni porphyrins, in which the tert-butyl benzene substituents at the meso positions of the macrocycle were tethered by ethers with alkyl linkers. This not only results in the permanently locked ruf distortion of the macrocycle but also enables the engineering of the degree of distortion through varying the length of alkyl linkers, which addressed the complication of uncertainty in the specific structural distortions that has long plagued the porphyrin photophysical community. Using advanced time-resolved optical and X-ray absorption spectroscopy, we observed tunability in the excited-state relaxation pathway depending on the degree of distortion and characterized the associated transient intermediate structure. These findings provide a new avenue to afford accessibility to a wide range of excited-state properties in nonplanar porphyrins.

Energy Landscapes in Photochemical Dissociation of Small Peroxides.

Organic peroxides are known to have important roles in many chemical and biochemical processes such as intermediates in the oxidation of various hydrocarbons, as initiators of free-radical polymerization and cross-linking agents, etc. Consequently, the study of the organic peroxides and their radicals are of fundamental interest and importance. Although several reaction pathways after dissociation of organic peroxides have been successfully identified using time-resolved optical absorption spectroscopy, interpretation of the data can be complicated due to spectral overlap of parent molecules, intermediates, and products. Therefore, a reliable theoretical framework is necessary in case of complex or less studied systems. In this study, we investigated the plausible thermal dissociation pathways of diethyl peroxide, ditert butyl peroxide, and dicumyl peroxide by density functional theory with M06-2X hybrid functional and compared its results to coupled cluster single double and perturbative triple, CCSD(T), level energies. Our results indicate that methyl radical elimination is the main dissociation mechanism for all of the studied peroxides after O-O bond cleavage which has been also observed in experiments. The resulting relative energies of the M06-2X functional were found to have reasonable accuracy in comparison with the CCSD(T) method. We also show that time-dependent density functional theory (TD-DFT) with the M06-2X functional provides a suitable guide for interpretation of time-resolved optical absorption spectra of peroxides. The experimental transient absorption spectra of dicumyl peroxide are interpreted using the theoretically predicted pathways and transient radical species. Both results agree within experimental resolution and accuracy. We propose that the traditionally assigned visible absorption is not due to the cumuloxyl radical and the photodissociation of dicumyl peroxide involves other pathways with extremely short-lived radicals.

Photoinduced flavin-tryptophan electron transfer across vesicle membranes generates magnetic field sensitive radical pairs

ABSTRACTDue to the photobiology of the flavoproteins DNA photolyase and cryptochrome, electron transfer reactions between flavins and tryptophan are of significant biological relevance. In addition, electron transfer across vesicle membranes has also seen much attention. In this work, we study the electron transfer reaction between flavins and tryptophan across lipid bilayer membranes in 1,2-dipalmitoyl-sn-glycero-3-phosphocholine small unilamellar vesicles using time-resolved optical absorption microspectroscopy and magnetically affected reaction yield spectroscopy. We demonstrate that riboflavin tetrabutyrate is embedded in the vesicle bilayer and can undergo electron transfer with tryptophan molecules in either the inner water pool or the bulk solution. Remarkably, flavin mononucleotide encapsulated in the inner water pool can undergo electron transfer across the vesicle bilayer to generate a magnetically sensitive radical pair with tryptophan molecules located in the bulk solution. The observed kinetics suggest that back electron transfer occurs between radical pairs generated by diffusive reencounter, either in the vesicle surface water or via electron hopping through degenerate electron exchange.

Direct Observation of Node-to-Node Communication in Zeolitic Imidazolate Frameworks.

Zeolitic imidazolate frameworks (ZIFs) with open-shell transition metal nodes represent a promising class of highly ordered light harvesting antennas for photoenergy applications. However, their charge transport properties within the framework, the key criterion to achieve efficient photoenergy conversion, are not yet explored. Herein, we report the first direct evidence of a charge transport pathway through node-to-node communication in both ground state and excited state ZIFs using the combination of paramagnetic susceptibility measurements and time-resolved optical and X-ray absorption spectroscopy. These findings provide unprecedented new insights into the photoactivity and charge transport nature of ZIF frameworks, paving the way for their novel application as light harvesting arrays in diverse photoenergy conversion devices.