Determining Excited-State Absorption Properties of a Quinoid Flavin by Polarization-Resolved Transient Spectroscopy.

As important naturally occurring chromophores, photophysical/chemical properties of quinoid flavins have been extensively studied both experimentally and theoretically. However, little is known about the transition dipole moment (TDM) orientation of excited-state absorption transitions of these important compounds. This aspect is of high interest in the fields of photocatalysis and quantum control studies. In this work, we employ polarization-associated spectra (PAS) to study the excited-state absorption transitions and the underlying TDM directions of a standard quinoid flavin compound. As compared to transient absorption anisotropy (TAA), an analysis based on PAS not only avoids diverging signals but also retrieves the relative angle for ESA transitions with respect to known TDM directions. Quantum chemical calculations of excited-state properties lead to good agreement with TA signals measured in magic angle configuration. Only when comparing experiment and theory for TAA spectra and PAS, do we find deviations when and only when the S0 → S1 of flavin is used as a reference. We attribute this to the vibronic coupling of this transition to a dark state. This effect is only observed in the employed polarization-controlled spectroscopy and would have gone unnoticed in conventional TA.

Two-dimensional fluorescence excitation spectroscopy: A novel technique for monitoring excited-state photophysics of molecular species with high time and frequency resolution.

We propose a novel UV/Vis femtosecond spectroscopic technique, two-dimensional fluorescence-excitation (2D-FLEX) spectroscopy, which combines spectral resolution during the excitation process with exclusive monitoring of the excited-state system dynamics at high time and frequency resolution. We discuss the experimental feasibility and realizability of 2D-FLEX, develop the necessary theoretical framework, and demonstrate the high information content of this technique by simulating the 2D-FLEX spectra of a model four-level system and the Fenna-Matthews-Olson antenna complex. We show that the evolution of 2D-FLEX spectra with population time directly monitors energy transfer dynamics and can thus yield direct qualitative insight into the investigated system. This makes 2D-FLEX a highly efficient instrument for real-time monitoring of photophysical processes in polyatomic molecules and molecular aggregates.

Isolating Pure Donor and Acceptor Signals by Polarization-Controlled Transient Absorption Spectroscopy.

The optical spectra of molecules are often highly congested, inhibiting definite assignment of features and dynamics. In this work, we demonstrate and apply a polarization-based strategy for the decomposition of time-resolved optical spectra to analyze the electronic structure and energy transfer in a molecular donor-acceptor (D-A) dyad. We choose a dyad with orthogonal transition dipole moments for D and A and high fluorescence quantum yield to show that polarization-controlled ultrafast transient absorption spectra can isolate the pure D and A parts of the total signal. This provides a strategy to greatly reduce spectral congestion in complex systems and thus allows for detailed studies of electronic structure and electronic energy transfer.

Transient absorption spectroscopy based on uncompressed hollow core fiber white light proves pre-association between a radical ion photocatalyst and substrate.

We present a hollow-core fiber (HCF) based transient absorption experiment, with capabilities beyond common titanium:sapphire based setups. By spectral filtering of the HCF spectrum, we provide pump pulses centered at 425 nm with several hundred nJ of pulse energy at the sample position. By employing the red edge of the HCF output for seeding CaF2, we obtain smooth probing spectra in the range between 320 and 900 nm. We demonstrate the capabilities of our experiment by following the ultrafast relaxation dynamics of a radical cationic photocatalyst to prove its pre-association with an arene substrate, a phenomenon that was not detectable previously by steady-state spectroscopic techniques. The detected preassembly rationalizes the successful participation of radical ionic photocatalysts in single electron transfer reactions, a notion that has been subject to controversy in recent years.

Probing Charge-Transfer Processes in a Covalently Linked [Ge9 ]-Cluster Imine Dyad.

C60 donor dyads in which the carbon cage is covalently linked to an electron-donating unit have been discussed as one possibility for an electron-transfer system, and it has been shown that spherical [Ge9 ] cluster anions show a close relation to fullerenes with respect to their electronic structure. However, the optical properties of these clusters and of functionalized cluster derivatives are almost unknown. We now report on the synthesis of the intensely red [Ge9 ] cluster linked to an extended π-electron system. [Ge9 {Si(TMS)3 }2 {CH3 C=N}-DAB(II)Dipp ]- (1- ) is formed upon the reaction of [Ge9 {Si(TMS)3 }2 ]2- with bromo-diazaborole DAB(II)Dipp -Br in CH3 CN (TMS=trimethylsilyl; DAB(II)=1,3,2-diazaborole with an unsaturated backbone; Dipp=2,6-di-iso-propylphenyl). Reversible protonation of the imine entity in 1- yields the deep green, zwitterionic cluster [Ge9 {Si(TMS)3 }2 {CH3 C=N(H)}-DAB(II)Dipp ] (1-H) and vice versa. Optical spectroscopy combined with time-dependent density functional theory suggests a charge-transfer excitation between the cluster and the antibonding π* orbital of the imine moiety as the cause of the intense coloration. An absorption maximum of 1-H in the red region of the electromagnetic spectrum and the corresponding lowest-energy excited state at λ=669 nm make the compound an interesting starting point for further investigations targeting the design of photo-active cluster compounds.

Thermal site energy fluctuations in photosystem I: new insights from MD/QM/MM calculations.

Cyanobacterial photosystem I (PSI) is one of the most efficient photosynthetic machineries found in nature. Due to the large scale and complexity of the system, the energy transfer mechanism from the antenna complex to the reaction center is still not fully understood. A central element is the accurate evaluation of the individual chlorophyll excitation energies (site energies). Such an evaluation must include a detailed treatment of site specific environmental influences on structural and electrostatic properties, but also their evolution in the temporal domain, because of the dynamic nature of the energy transfer process. In this work, we calculate the site energies of all 96 chlorophylls in a membrane-embedded model of PSI. The employed hybrid QM/MM approach using the multireference DFT/MRCI method in the QM region allows to obtain accurate site energies under explicit consideration of the natural environment. We identify energy traps and barriers in the antenna complex and discuss their implications for energy transfer to the reaction center. Going beyond previous studies, our model also accounts for the molecular dynamics of the full trimeric PSI complex. Via statistical analysis we show that the thermal fluctuations of single chlorophylls prevent the formation of a single prominent energy funnel within the antenna complex. These findings are also supported by a dipole exciton model. We conclude that energy transfer pathways may form only transiently at physiological temperatures, as thermal fluctuations overcome energy barriers. The set of site energies provided in this work sets the stage for theoretical and experimental studies on the highly efficient energy transfer mechanisms in PSI.

Q-Band relaxation in chlorophyll: new insights from multireference quantum dynamics.

The ultrafast relaxation within the Q-bands of chlorophyll plays a crucial role in photosynthetic light-harvesting. Yet, despite being the focus of many experimental and theoretical studies, it is still not fully understood. In this paper we look at the relaxation process from the perspective of non-adiabatic wave packet dynamics. For this purpose, we identify vibrational degrees of freedom which contribute most to the non-adiabatic coupling. Using a selection of normal modes, we construct four reduced-dimensional coordinate spaces and investigate the wave packet dynamics on XMS-CASPT2 potential energy surfaces. In this context, we discuss the associated computational challenges, as many quantum chemical methods overestimate the Qx-Qy energy gap. Our results show that the Qx and Qy potential energy surfaces do not cross in an energetically accessible region of the vibrational space. Instead, non-adiabatic coupling facilitates ultrafast population transfer across the potential energy surface. Moreover, we can identify the excited vibrational eigenstates that take part in the relaxation process. We conclude that the Q-band system of chlorophyll a should be viewed as a strongly coupled system, where population is easily transferred between the x and y-polarized electronic states. This suggests that both orientations may contribute to the electron transfer in the reaction center of photosynthetic light-harvesting systems.

Photoinduced B-Cl Bond Fission in Aldehyde-BCl3 Complexes as a Mechanistic Scenario for C-H Bond Activation.

In concert with carbonyl compounds, Lewis acids have been identified as a versatile class of photocatalysts. Thus far, research has focused on activation of the substrate, either by changing its photophysical properties or by modifying its photochemistry. In this work, we expand the established mode of action by demonstrating that UV photoexcitation of a Lewis acid-base complex can lead to homolytic cleavage of a covalent bond in the Lewis acid. In a study on the complex of benzaldehyde and the Lewis acid BCl3, we found evidence for homolytic B-Cl bond cleavage leading to formation of a borylated ketyl radical and a free chlorine atom only hundreds of femtoseconds after excitation. Both time-dependent density functional theory and transient absorption experiments identify a benzaldehyde-BCl2 cation as the dominant species formed on the nanosecond time scale. The experimentally validated B-Cl bond homolysis was synthetically exploited for a BCl3-mediated hydroalkylation reaction of aromatic aldehydes (19 examples, 42-76% yield). It was found that hydrocarbons undergo addition to the C═O double bond via a radical pathway. The photogenerated chlorine radical abstracts a hydrogen atom from the alkane, and the resulting carbon-centered radical either recombines with the borylated ketyl radical or adds to the ground-state aldehyde-BCl3 complex, releasing a chlorine atom. The existence of a radical chain was corroborated by quantum yield measurements and by theory. The photolytic mechanism described here is based on electron transfer between a bound chlorine and an aromatic π-system on the substrate. Thereby, it avoids the use of redox-active transition metals.

Understanding Carotenoid Dynamics via the Vibronic Energy Relaxation Approach.

Carotenoids are an integral part of natural photosynthetic complexes, with tasks ranging from light harvesting to photoprotection. Their underlying energy deactivation network of optically dark and bright excited states is extremely efficient: after excitation of light with up to 2.5 eV of photon energy, the system relaxes back to ground state on a time scale of a few picoseconds. In this article, we summarize how a model based on the vibrational energy relaxation approach (VERA) explains the main characteristics of relaxation dynamics after one-photon excitation with special emphasis on the so-called S* state. Lineshapes after two-photon excitation are beyond the current model of VERA. We outline this future line of research in our article. In terms of experimental method development, we discuss which techniques are needed to better describe energy dissipation effects in carotenoids and within the first solvation shell.

Reduced Molecular Flavins as Single-Electron Reductants after Photoexcitation.

Flavoenzymes mediate a multitude of chemical reactions and are catalytically active both in different oxidation states and in covalent adducts with reagents. The transfer of such reactivity to the organic laboratory using simplified molecular flavins is highly desirable, and such applications in (photo)oxidation reactions are already established. However, molecular flavins have not been used for the reduction of organic substrates yet, although this activity is known and well-studied for DNA photolyase enzymes. We report a catalytic method using reduced molecular flavins as photoreductants and γ-terpinene as a sacrificial reductant. Additionally, we present our design for air-stable, reduced flavin catalysts, which is based on a conformational bias strategy and circumvents the otherwise rapid reduction of O2 from air. Using our catalytic strategy, we were able to replace superstoichiometric amounts of the rare-earth reductant SmI2 in a 5-exo-trig cyclization of substituted barbituric acid derivatives. Such flavin-catalyzed reductions are anticipated to be beneficial for other transformations as well and their straightforward synthesis indicates future use in stereo- as well as site-selective transformations.

Correlated spectral fluctuations quantified by line shape analysis of fifth-order two-dimensional electronic spectra.

Correlated spectral fluctuations were suggested to coordinate excitation transport inside natural light harvesting complexes. We demonstrate the capacities of 2D line shapes from fifth-order coherent electronic signals (R5-2D) to report on such fluctuations in molecular aggregates and present a stochastic approach to fluctuations in correlated site and bi-exciton binding energies in the optical dynamics of Frenkel excitons. The model is applied to R5-2D line shapes of a homodimer, and we show that the peak tilt dynamics are a measure for site energy disorder, inter-site correlation, and the strength of bi-exciton binding energy fluctuations.

The central role of the metal ion for photoactivity: Zn- vs. Ni-Mabiq.

Photoredox catalysts are integral components of artificial photosystems, and have recently emerged as powerful tools for catalysing numerous organic reactions. However, the development of inexpensive and efficient earth-abundant photoredox catalysts remains a challenge. We here present the photochemical and photophysical properties of a Ni-Mabiq catalyst ([NiII(Mabiq)]OTf (1); Mabiq = 2-4:6-8-bis(3,3,4,4-tetramethyldihydropyrrolo)-10-15-(2,2-biquinazolino)-[15]-1,3,5,8,10,14-hexaene1,3,7,9,11,14-N6)-and of a Zn-containing analogue ([ZnII(Mabiq)OTf] (2))-using steady state and time resolved optical spectroscopy, time-dependent density functional theory (TDDFT) calculations, and reactivity studies. The Ni and Zn complexes exhibit similar absorption spectra, but markedly different photochemical properties. These differences arise because the excited states of 2 are ligand-localized, whereas metal-centered states account for the photoactivity of 1. The distinct properties of the Ni and Zn complexes are manifest in their behavior in the photo-driven aza-Henry reaction and oxidative coupling of methoxybenzylamine.

Activation of 2-Cyclohexenone by BF3 Coordination: Mechanistic Insights from Theory and Experiment.

Lewis acids have recently been recognized as catalysts enabling enantioselective photochemical transformations. Mechanistic studies on these systems are however rare, either due to their absorption at wavelengths shorter than 260 nm, or due to the limitations of theoretical dynamic studies for larger complexes. In this work, we overcome these challenges and employ sub-30-fs transient absorption in the UV, in combination with a highly accurate theoretical treatment on the XMS-CASPT2 level. We investigate 2-cyclohexenone and its complex to boron trifluoride and analyze the observed dynamics based on trajectory calculations including non-adiabatic coupling and intersystem crossing. This approach explains all ultrafast decay pathways observed in the complex. We show that the Lewis acid remains attached to the substrate in the triplet state, which in turn explains why chiral boron-based Lewis acids induce a high enantioselectivity in photocycloaddition reactions.

Intraband dynamics and exciton trapping in the LH2 complex of Rhodopseudomonas acidophila.

Over the last several decades, the light-harvesting protein complexes of purple bacteria have been among the most popular model systems for energy transport in excitonic systems in the weak and intermediate intermolecular coupling regime. Despite this extensive body of scientific work, significant questions regarding the excitonic states and the photo-induced dynamics remain. Here, we address the low-temperature electronic structure and excitation dynamics in the light-harvesting complex 2 of Rhodopseudomonas acidophila by two-dimensional electronic spectroscopy. We find that, although at cryogenic temperature energy relaxation is very rapid, exciton mobility is limited over a significant range of excitation energies. This points to the presence of a sub-200 fs, spatially local energy-relaxation mechanism and suggests that local trapping might contribute substantially more in cryogenic experiments than under physiological conditions where the thermal energy is comparable to or larger than the static disorder.

Anharmonic Molecular Motion Drives Resonance Energy Transfer in peri-Arylene Dyads.

Spectral and dynamical properties of molecular donor-acceptor systems strongly depend on the steric arrangement of the constituents with exciton coupling J as a key control parameter. In the present work we study two peri-arylene based dyads with orthogonal and parallel transition dipoles for donor and acceptor moieties, respectively. We show that the anharmonic multi-well character of the orthogonal dyad's intramolecular potential explains findings from both stationary and time-resolved absorption experiments. While for a parallel dyad, standard quantum chemical estimates of J at 0 K are in good agreement with experimental observations, J becomes vanishingly small for the orthogonal dyad, in contrast to its ultrafast experimental transfer times. This discrepancy is not resolved even by accounting for harmonic fluctuations along normal coordinates. We resolve this problem by supplementing quantum chemical approaches with dynamical sampling of fluctuating geometries. In contrast to the moderate Gaussian fluctuations of J for the parallel dyad, fluctuations for the orthogonal dyad are found to follow non-Gaussian statistics leading to significantly higher effective J in good agreement with experimental observations. In effort to apply a unified framework for treating the dynamics of optical coherence and excitonic populations of both dyads, we employ a vibronic approach treating electronic and selected vibrational degrees on an equal footing. This vibronic model is used to model absorption and fluorescence spectra as well as donor-acceptor transport dynamics and covers the more traditional categories of Förster and Redfield transport as limiting cases.

Time-domain photocurrent spectroscopy based on a common-path birefringent interferometer.

We present diffraction-limited photocurrent (PC) microscopy in the visible spectral range based on broadband excitation and an inherently phase-stable common-path interferometer. The excellent path-length stability guarantees high accuracy without the need for active feedback or post-processing of the interferograms. We illustrate the capabilities of the setup by recording PC spectra of a bulk GaAs device and compare the results to optical transmission data.

Quantum biology revisited.

Photosynthesis is a highly optimized process from which valuable lessons can be learned about the operating principles in nature. Its primary steps involve energy transport operating near theoretical quantum limits in efficiency. Recently, extensive research was motivated by the hypothesis that nature used quantum coherences to direct energy transfer. This body of work, a cornerstone for the field of quantum biology, rests on the interpretation of small-amplitude oscillations in two-dimensional electronic spectra of photosynthetic complexes. This Review discusses recent work reexamining these claims and demonstrates that interexciton coherences are too short lived to have any functional significance in photosynthetic energy transfer. Instead, the observed long-lived coherences originate from impulsively excited vibrations, generally observed in femtosecond spectroscopy. These efforts, collectively, lead to a more detailed understanding of the quantum aspects of dissipation. Nature, rather than trying to avoid dissipation, exploits it via engineering of exciton-bath interaction to create efficient energy flow.

Magnetic pulses enable multidimensional optical spectroscopy of dark states.

The study and manipulation of low dipole moment quantum states have been challenging due to their inaccessibility by conventional spectroscopic techniques. Controlling the spin in such states requires unfeasible strong magnetic fields to overcome typical decoherence rates. However, the advent of terahertz technology and its application in magnetic pulses opens up a new scenario. In this article, we focus on an electron-hole pair model to demonstrate that it is possible to control the precession of the spins and to modify the transition rates to different spin states. Enhancing transitions from a bright state to a dark state with different spins means that the latter can be revealed by ordinary spectroscopy. We propose a modification of the standard two-dimensional spectroscopic scheme in which a three pulse sequence is encased in a magnetic pulse. Its role is to drive transitions between a bright and a dark spin state, making the latter susceptible to spectroscopic investigation.

The full dynamics of energy relaxation in large organic molecules: from photo-excitation to solvent heating.

In some molecular systems, such as nucleobases, polyenes or the active ingredients of sunscreens, substantial amounts of photo-excitation energy are dissipated on a sub-picosecond time scale, raising questions such as: where does this energy go or among which degrees of freedom it is being distributed at such early times? Here we use transient absorption spectroscopy to track excitation energy dispersing from the optically accessible vibronic subsystem into the remaining vibrational subsystem of the solute and solvent. Monitoring the flow of energy during vibrational redistribution enables quantification of local molecular heating. Subsequent heat dissipation away from the solute molecule is characterized by classical thermodynamics and molecular dynamics simulations. Hence, we present a holistic approach that tracks the internal temperature and vibronic distribution from the act of photo-excitation to the restoration of the global equilibrium. Within this framework internal vibrational redistribution and vibrational cooling are emergent phenomena. We demonstrate the validity of the framework by examining a highly controversial example, carotenoids. We show that correctly accounting for the local temperature unambiguously explains their energetically and temporally congested spectral dynamics without the ad hoc postulation of additional 'dark' states. An immediate further application of this approach would be to monitor the excitation and thermal dynamics of pigment-protein systems.

Single-molecule excitation-emission spectroscopy.

Single-molecule spectroscopy (SMS) provides a detailed view of individual emitter properties and local environments without having to resort to ensemble averaging. While the last several decades have seen substantial refinement of SMS techniques, recording excitation spectra of single emitters still poses a significant challenge. Here we address this problem by demonstrating simultaneous collection of fluorescence emission and excitation spectra using a compact common-path interferometer and broadband excitation, which is implemented as an extension of a standard SMS microscope. We demonstrate the technique by simultaneously collecting room-temperature excitation and emission spectra of individual terrylene diimide molecules and donor-acceptor dyads embedded in polystyrene. We analyze the resulting spectral parameters in terms of optical lineshape theory to obtain detailed information on the interactions of the emitters with their nanoscopic environment. This analysis finally reveals that environmental fluctuations between the donor and acceptor in the dyads are not correlated.