Observation of a Long-lived Electronic Coherence Modulated by Vibrational Dynamics in Molecular Nd3+ -Complexes at Room Temperature.

Temporally delayed, phase-locked coherent pairs of near IR femtosecond laser pulses were employed to study electronic coherences in molecular Nd3+ -complexes at room temperature. Dissolved and solid complexes were studied under a confocal microscope set-up with fluorescence detection. The observed electronic coherence on a few hundred femtoseconds time scale is modulated by additional coherent wave packet dynamics, which we attribute mainly to be vibrational in nature. In future, the complexes may serve as prototypes for possible applications in quantum information technology.

Photoinduced Metallonitrene Formation by N2 Elimination from Azide Diradical Ligands.

Transition-metal nitrides/nitrenes are highly promising reagents for catalytic nitrogen-atom-transfer reactivity. They are typically prepared in situ upon optically induced N2 elimination from azido precursors. A full exploitation of their catalytic potential, however, requires in-depth knowledge of the primary photo-induced processes and the structural/electronic factors mediating the N2 loss with birth of the terminal metal-nitrogen core. Using femtosecond infrared spectroscopy, we elucidate here the primary molecular-level mechanisms responsible for the formation of a unique platinum(II) nitrene with a triplet ground state from a closed-shell platinum(II) azide precursor. The spectroscopic data in combination with quantum-chemical calculations provide compelling evidence that product formation requires the initial occupation of a singlet excited state with an anionic azide diradical ligand that is bound to a low-spin d8 -configured PtII ion. Subsequent intersystem crossing generates the Pt-bound triplet azide diradical, which smoothly evolves into the triplet nitrene via N2 loss in a near barrierless adiabatic dissociation. Our data highlight the importance of the productive, N2 -releasing state possessing azide ππ* character as a design principle for accessing efficient N-atom-transfer catalysts.

A Unified View on Varied Ultrafast Dynamics of the Primary Process in Microbial Rhodopsins.

All-trans to 13-cis photoisomerization of the protonated retinal Schiff base (PRSB) chromophore is the primary step that triggers various biological functions of microbial rhodopsins. While this ultrafast primary process has been extensively studied, it has been recognized that the relevant excited-state relaxation dynamics differ significantly from one rhodopsin to another. To elucidate the origin of the complicated ultrafast dynamics of the primary process in microbial rhodopsins, we studied the excited-state dynamics of proteorhodopsin, its D97N mutant, and bacteriorhodopsin by femtosecond time-resolved absorption (TA) spectroscopy in a wide pH range. The TA data showed that their excited-state relaxation dynamics drastically change when pH approaches the pKa of the counterion residue of the PRSB chromophore in the ground state. This result reveals that the varied excited-state relaxation dynamics in different rhodopsins mainly originate from the difference of the ground-state heterogeneity (i.e., protonation/deprotonation of the PRSB counterion).

Ultrafast Dynamics of Photochemical Nitrile Imine Formation.

The chemical reactivity of nitrile imines is of great utility in organic synthesis with applications rapidly expanding into the materials and life sciences. Yet, our understanding of the electronic and molecular structures of nitrile imines remains incomplete and the elementary mechanism of their photoinduced generation is entirely unknown. Here, femtosecond infrared spectroscopy after 266 nm-excitation of 2,5-diphenyltetrazole has been carried out to temporally resolve the formation and structural relaxation dynamics of the nascent diphenylnitrile imine in liquid solution under ambient conditions. The infrared-spectroscopic evolution is interpreted by an initial sequence of intersystem crossings within 250 fs followed by the cleavage of N2 with formation of a structurally relaxed nitrile imine on the adiabatic ground-state singlet surface within a few tens of picoseconds. The infrared spectrum supports the notion of a "floppy" nitrile imine molecule whose equilibrium character ranges from fully propargylic to fully allenic in the room temperature liquid solution.

Ultrafast Photo-ion Probing of the Ring-Opening Process in Trans-Stilbene Oxide.

The ultrafast photo-induced ring opening of the oxirane derivative trans-stilbene oxide has been studied through the use of ultrafast UV/UV pump-probe spectroscopy by using photo-ion detection. Single- and multiphoton probe paths and final states were identified through comparisons between UV power studies and synchrotron-based vacuum ultraviolet (VUV) single-photon ionization studies. Three major time-dependent features of the parent ion (sub-450 fs decay, (1.5±0.2) ps, and >100 ps) were observed. These decays are discussed in conjunction with the primary ring-opening mechanism of stilbene oxide, which occurs through C-C dissociation in the oxirane ring. The appearance of fragments relating to the masses of dehydrogenated diphenylmethane (167 amu) and dehydrogenated methylbenzene (90 amu) were also investigated. The appearance of the 167 amu fragment could suggest an alternative ultrafast ring-opening pathway via the dissociation of one of the C-O bonds within the oxirane ring.

Disentangling Multiple Effects on Excited-State Intramolecular Charge Transfer among Asymmetrical Tripartite PPI-TPA/PCz Triads.

By utilizing the bipolarity of 1,2-diphenylphenanthroimidazole (PPI), two types of asymmetrical tripartite triads (PPI-TPA and PPI-PCz) were designed with triphenylamine (TPA) and 9-phenylcarbazole (PCz). These triads are deep-blue luminescent materials with a high fluorescence quantum yield of nearly 100 %. To trace the photophysical behaviors of these triads, their excited-state evolution channels and interchromophoric interactions were investigated by ultrafast time-resolved transient absorption and excited-state theoretical calculations. The results suggest that the electronic nature, asymmetrical tripartite structure, and electron-hole distance of these triads, as well as solvent polarity, determine the lifetime of intramolecular charge transfer (ICT). Interestingly, PPI-PCz triads show anti-Kasha ICT, and the charge-transfer direction among the triads is adjustable. For the PPI-TPA triad, the electron is transferred from TPA to PPI, whereas for the PPI-PCz triad the electron is pushed from PPI to PCz. Exploration of the excited-state ICT in these triads may pave the way to design better luminescent materials in the future.

Fluorescence-Detected Pump-Probe Spectroscopy.

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

Spin-Controlled Binding of Carbon Dioxide by an Iron Center: Insights from Ultrafast Mid-Infrared Spectroscopy.

The influence of the spin on the mode of binding between carbon dioxide (CO2 ) and a transition-metal (TM) center is an entirely open question. Herein, we use an iron(III) oxalato complex with nearly vanishing doublet-sextet gap, and its ultrafast photolysis, to generate TM-CO2 bonding patterns and determine their structure in situ by femtosecond mid-infrared spectroscopy. The formation of the nascent TM-CO2 species according to [L4 FeIII (C2 O4 )]+ + hν → [L4 Fe(CO2 )]+ + CO2 , with L4 =cyclam, is evidenced by the coincident appearance of the characteristic asymmetric stretching absorption of the CO2 -ligand between 1600 cm-1 and 1800 cm-1 and that of the free CO2 -co-fragment near 2337 cm-1 . On the high-spin surface (S=5/2), the product complex features a bent carbon dioxide radical anion ligand that is O-"end-on"-bound to the metal. In contrast, on the intermediate-spin and low-spin surfaces, the product exhibits a "side-on"-bound, bent carbon dioxide ligand that has either a partial open-shell (for S=3/2) or fully closed-shell character (for S=1/2).

Hydrogen-Bond Free Energy of Local Biological Water.

Here, we propose an experimental methodology based on femtosecond-resolved fluorescence spectroscopy to measure the hydrogen (H)-bond free energy of water at protein surfaces under isothermal conditions. A demonstration was conducted by installing a non-canonical isostere of tryptophan (7-azatryptophan) at the surface of a coiled-coil protein to exploit the photoinduced proton transfer of its chromophoric moiety, 7-azaindole. The H-bond free energy of this biological water was evaluated by comparing the rates of proton transfer, sensitive to the hydration environment, at the protein surface and in bulk water, and it was found to be higher than that of bulk water by 0.4 kcal mol-1 . The free-energy difference is dominated by the entropic cost in the H-bond network among water molecules at the hydrophilic and charged protein surface. Our study opens a door to accessing the energetics and dynamics of local biological water to give insight into its roles in protein structure and function.

Hot Branching Dynamics in a Light-Harvesting Iron Carbene Complex Revealed by Ultrafast X-ray Emission Spectroscopy.

Iron N-heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub-ps X-ray spectroscopy study of an FeII NHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot 3 MLCT state, from the initially excited 1 MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the 3 MC state, in competition with vibrational relaxation and cooling to the relaxed 3 MLCT state. The relaxed 3 MLCT state then decays much more slowly (7.6 ps) to the 3 MC state. The 3 MC state is rapidly (2.2 ps) deactivated to the ground state. The 5 MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the 3 MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition-metal complexes for similar ultrafast decays to optimize photochemical performance.

Coherent Vibration and Femtosecond Dynamics of the Platinum Complex Oligomers upon Intermolecular Bond Formation in the Excited State.

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

Observation of Photoelectron Circular Dichroism Using a Nanosecond Laser.

Photoelectron circular dichroism (PECD) is a fascinating phenomenon both from a fundamental science aspect but also due to its emerging role as a highly sensitive analytic tool for chiral recognition in the gas phase. PECD has been studied with single-photon as well as multi-photon ionization. The latter has been investigated in the short pulse limit with femtosecond laser pulses, where ionization can be thought of as an instantaneous process. In this contribution, we demonstrate that multi-photon PECD still can be observed when using an ultra-violet nanosecond pulse to ionize chiral showcase fenchone molecules. Compared to femtosecond ionization, the magnitude of PECD is similar, but the lifetime of intermediate molecular states imprints itself in the photoelectron spectra. Being able to use an industrial nanosecond laser to investigate PECD furthermore reduces the technical requirements to apply PECD in analytical chemistry.

Effect of Second-Order Spin-Orbit Coupling on the Interaction between Spin States in Spin-Crossover Systems.

The second-order spin-orbit coupling is evaluated in two transition-metal complexes to establish the effect on the deactivation mechanism of the excited low-spin state in systems that undergo spin transitions under the influence of light. We compare the standard perturbational approach to calculate the second-order interaction with a variational strategy based on the effective Hamiltonian theory and show that the former one can only be applied in some special cases and even then gives results that largely overestimate the interaction. The combined effect of geometry distortions and second-order spin-orbit coupling leads to sizeable interactions for states that are nearly uncoupled in the symmetric (average) structure of the complex. This opens the possibility of a direct deactivation from the singlet and triplet states of the metal-to-ligand charge-transfer manifold to the final high-spin state as suggested from the interpretation of experimental data but so far not supported by theoretical descriptions of the light-induced spin crossover.

Ultrafast Dynamics of a Fluorescent Tetrazolium Compound in Solution.

Tetrazolium salts are exploited in various fields of research by virtue of their low reduction potentials. Increasingly, associated applications also attend to the photochemical and luminescence properties of these systems. Here, we investigate the photoinduced dynamics of phenyl-benzo[c]tetrazolo-cinnolinium chloride (PTC), one of the very few known fluorescent tetrazolium compounds, by using time-correlated single-photon counting, femtosecond fluorescence upconversion, and ultrafast transient absorption spectroscopy. PTC is generated photochemically by ultraviolet illumination of 2,3,5-triphenyl-tetrazolium chloride (TTC) in various alcohols. Time-resolved fluorescence measurements on PTC with different excitation wavelengths disclose biphasic solvation and vibrational relaxation dynamics. Depending on the solvent, the emission behavior of PTC is characterized by quantum yields on the order of several tens of percent and corresponding excited-state lifetimes of several hundreds of picoseconds. The radiative rate is basically constant for the studied alcohols, whereas the rate of the competing non-radiative process is sensitive to the solvent polarity. Hence, we discuss the possible involvement of intermediate radicals and further presumptive reaction pathways pursued after photoexcitation of PTC.

An Iron Complex with a Bent, O-Coordinated CO2 Ligand Discovered by Femtosecond Mid-Infrared Spectroscopy.

The activation of carbon dioxide by transition metals is widely recognized as a key step for utilizing this greenhouse gas as a renewable feedstock for the sustainable production of fine chemicals. However, the dynamics of CO2 binding and unbinding to and from the ligand sphere of a metal have never been observed in the time domain. The ferrioxalate anion is used in aqueous solution as a unique model system for these dynamics and femtosecond UV-pump mid-infrared-probe spectroscopy is applied to explore its photoinduced primary processes in a time-resolved fashion. Following optical excitation, a neutral CO2 molecule is expelled from the complex within about 500 fs to generate a highly intriguing pentacoordinate ferrous dioxalate that carries a bent carbon dioxide radical anion ligand, that is, a reductively activated form of CO2 , which is end-on-coordinated to the metal center by one of its two oxygen atoms.

Characterization of Tin/Ethylene Glycol Solar Nanofluids Synthesized by Femtosecond Laser Radiation.

Solar energy is available over wide geographical areas and its harnessing is becoming an essential tool to satisfy the ever-increasing demand for energy with minimal environmental impact. Solar nanofluids are a novel solar receiver concept for efficient harvesting of solar radiation based on volumetric absorption of directly irradiated nanoparticles in a heat transfer fluid. Herein, the fabrication of a solar nanofluid by pulsed laser ablation in liquids was explored. This study was conducted with the ablation of bulk tin immersed in ethylene glycol with a femtosecond laser. Laser irradiation promotes the formation of tin nanoparticles that are collected in the ethylene glycol as colloids, creating the solar nanofluid. The ability to trap incoming electromagnetic radiation, thermal conductivity, and the stability of the solar nanofluid in comparison with conventional synthesis methods is enhanced.

Selection of a Single Isotope of Multiply Charged Xenon (A Xez+ , A=128-136, z=1-6) by Using a Bradbury-Nielsen Ion Gate.

The inclusion of an ion gate in a tandem mass spectrometer allows a specific precursor ion to be selected, and the fragment ions are then used for structure analysis and to investigate chemical reactions. However, the performance of an ion gate has been judged simply by whether or not the target ion was selected. In this study, we designed, manufactured, constructed, and characterized a Bradbury-Nielsen ion gate (BNG). The actual ion selection ability, i.e. the gate function, of the BNG was measured for isotopes of Xez+ (z=1-6). The gate function of the BNG was 36.5±0.5 ns in width and 3-13 ns in rise and fall times. The BNG provides a simple way to select multiply charged molecular cations of small organic molecules as well as large molecules such as proteins and peptides.

The Femtochemistry of a Ferracyclobutadiene.

The eminent role of metallacyclobutadienes as catalytic intermediates in organic synthesis and polymer chemistry is widely acknowledged. In contrast, their photochemistry is as yet entirely unexplored. Herein, the photo-induced primary processes of a ferracyclobutadiene tricarbonyl complex in solution are revealed by femtosecond mid-infrared spectroscopy. The time-resolved vibrational spectra expose an ultrafast substitution of a basal CO ligand by a solvent molecule in a consecutive dissociation-association mechanism. Following optical excitation, the system relaxes non-radiatively to the triplet ground state from which a CO is expelled. Since the triplet state is bound with respect to Fe-CO cleavage, the dissociation can only occur from vibrationally excited states. The excitation energy, vibrational relaxation, and intersystem crossing to the singlet ground state control the primary quantum yield for formation of the ferracyclic dicarbonyl-solvent product complex.

Pump-Probe Fragmentation Action Spectroscopy: A Powerful Tool to Unravel Light-Induced Processes in Molecular Photocatalysts.

We present a proof of concept that ultrafast dynamics combined with photochemical stability information of molecular photocatalysts can be acquired by electrospray ionization mass spectrometry combined with time-resolved femtosecond laser spectroscopy in an ion trap. This pump-probe "fragmentation action spectroscopy" gives straightforward access to information that usually requires high purity compounds and great experimental efforts. Results of gas-phase studies on the electronic dynamics of two supramolecular photocatalysts compare well to previous findings in solution and give further evidence for a directed electron transfer, a key process for photocatalytic hydrogen generation.

Competitive Excimer Formation and Energy Transfer in Zr-Based Heterolinker Metal-Organic Frameworks.

The spectroscopy and dynamics of a series of Zr-based MOFs in dichloromethane suspension are reported. These Zr-NADC MOFs were constructed by using different mixtures of 2,6-naphthalenedicarboxylate (NDC) and 4-amino-2,6-naphthalenedicarboxylate (NADC) as organic linkers. The fraction of NADC relative to NDC in these heterolinker MOFs ranges from 2 to 35 %. The results indicate two competitive photoprocesses: NDC excimer formation and an energy transfer (ET) from excited NDC linkers to NADC linkers. Increasing the fraction of NADC linkers in the Zr-NADC nanostructure decreases the mean time constant of NDC excimer formation, while the NADC emission intensity experiences a drop at the highest fraction of this linker in the MOF. The first observation is explained by an increase in the energy-transfer probability between the two linkers, and the second by emission quenching in the NADC linkers due to ultrafast charge transfer assisted by the amino group. Femtosecond time-resolved emission studies showed that the ET process (recorded as decaying and rising components) from excited NDC to NADC takes place in 1.2 ps. Direct excitation of the NADC linkers (at 410 nm) shows a decaying, but not rising, component of 250-480 fs, which could reflect the formation of a nonemissive charge-separation state. The results show that by using MOFs having heterolinkers it is possible to trigger and tune excimer formation and ET processes.