Oxidation Chemistry of Bicarbonate and Peroxybicarbonate: Implications for Carbonate Management in Energy Storage.

Carbonate formation presents a major challenge to energy storage applications based on low-temperature CO2 electrolysis and recyclable metal-air batteries. While direct electrochemical oxidation of (bi)carbonate represents a straightforward route for carbonate management, knowledge of the feasibility and mechanisms of direct oxidation is presently lacking. Herein, we report the isolation and characterization of the bis(triphenylphosphine)iminium salts of bicarbonate and peroxybicarbonate, thus enabling the examination of their oxidation chemistry. Infrared spectroelectrochemistry combined with time-resolved infrared spectroscopy reveals that the photoinduced oxidation of HCO3- by an Ir(III) photoreagent results in the generation of the short-lived bicarbonate radical in less than 50 ns. The highly acidic bicarbonate radical undergoes proton transfer with HCO3- to furnish the carbonate radical anion and H2CO3, leading to the eventual release of CO2 and H2O, thus accounting for the appearance of H2O and CO2 in both electrochemical and photochemical oxidation experiments. The back reaction of the carbonate radical subsequently oxidizes the Ir(II) photoreagent, leading to carbonate. In the absence of this back reaction, dimerization of the carbonate radical provides entry into peroxybicarbonate, which we show undergoes facile oxidation to O2 and CO2. Together, the results reported identify tangible pathways for the design of catalysts for the management of carbonate in energy storage applications.

Reversible CO2 Capture and On-Demand Release by an Acidity-Matched Organic Photoswitch.

Separation of carbon dioxide (CO2) from point sources or directly from the atmosphere can contribute crucially to climate change mitigation plans in the coming decades. A fundamental practical limitation for the current strategies is the considerable energy cost required to regenerate the sorbent and release the captured CO2 for storage or utilization. A directly photochemically driven system that demonstrates efficient passive capture and on-demand CO2 release triggered by sunlight as the sole external stimulus would provide an attractive alternative. However, little is known about the thermodynamic requirements for such a process or mechanisms for modulating the stability of CO2-derived dissolved species by using photoinduced metastable states. Here, we show that an organic photoswitchable molecule of precisely tuned effective acidity can repeatedly capture and release a near-stoichiometric quantity of CO2 according to dark-light cycles. The CO2-derived species rests as a solvent-separated ion pair, and key aspects of its excited-state dynamics that regulate the photorelease efficiency are characterized by transient absorption spectroscopy. The thermodynamic and kinetic concepts established herein will serve as guiding principles for the development of viable solar-powered negative emission technologies.

Ring currents modulate optoelectronic properties of aromatic chromophores at 25 T.

The properties of organic molecules can be influenced by magnetic fields, and these magnetic field effects are diverse. They range from inducing nuclear Zeeman splitting for structural determination in NMR spectroscopy to polaron Zeeman splitting organic spintronics and organic magnetoresistance. A pervasive magnetic field effect on an aromatic molecule is the aromatic ring current, which can be thought of as an induction of a circular current of π-electrons upon the application of a magnetic field perpendicular to the π-system of the molecule. While in NMR spectroscopy the effects of ring currents on the chemical shifts of nearby protons are relatively well understood, and even predictable, the consequences of these modified electronic states on the spectroscopy of molecules has remained unknown. In this work, we find that photophysical properties of model phthalocyanine compounds and their aggregates display clear magnetic field dependences up to 25 T, with the aggregates showing more drastic magnetic field sensitivities depending on the intermolecular interactions with the amplification of ring currents in stacked aggregates. These observations are consistent with ring currents measured in NMR spectroscopy and simulated in time-dependent density functional theory calculations of magnetic field-dependent phthalocyanine monomer and dimer absorption spectra. We propose that ring currents in organic semiconductors, which commonly comprise aromatic moieties, may present new opportunities for the understanding and exploitation of combined optical, electronic, and magnetic properties.

How Radical Are "Radical" Photocatalysts? A Closed-Shell Meisenheimer Complex Is Identified as a Super-Reducing Photoreagent.

Super-reducing excited states have the potential to activate strong bonds, leading to unprecedented photoreactivity. Excited states of radical anions, accessed via reduction of a precatalyst followed by light absorption, have been proposed to drive photoredox transformations under super-reducing conditions. Here, we investigate the radical anion of naphthalene monoimide as a photoreductant and find that the radical doublet excited state has a lifetime of 24 ps, which is too short to facilitate photoredox activity. To account for the apparent photoreactivity of the radical anion, we identify an emissive two-electron reduced Meisenheimer complex of naphthalene monoimide, [NMI(H)]-. The singlet excited state of [NMI(H)]- is a potent reductant (-3.08 V vs Fc/Fc+), is long-lived (20 ns), and its emission can be dynamically quenched by chloroarenes to drive a radical photochemistry, establishing that it is this emissive excited state that is competent for reported C-C and C-P coupling reactivity. These results provide a mechanistic basis for photoreactivity at highly reducing potentials via singlet excited state manifolds and lays out a clear path for the development of exceptionally reducing photoreagents derived from electron-rich closed-shell anions.

Vibrational Dephasing along the Reaction Coordinate of an Electron Transfer Reaction.

The role of molecular vibration in photoinduced electron transfer (ET) reactions has been extensively debated in recent years. In this study, we investigated vibrational wavepacket dynamics in a model ET system consisting of an organic dye molecule as an electron acceptor dissolved in various electron donating solvents. By using broad band pump-probe (BBPP) spectroscopy with visible laser pulses of sub-10 fs duration, coherent vibrational wavepackets of naphthacene dye with frequencies spanning 170-1600 cm-1 were observed in the time domain. The coherence properties of 11 vibrational modes were analyzed by an inverse Fourier filtering procedure, and we discovered that the dephasing times of some vibrational coherences are reduced with increasing ET rates. Density functional theory calculations indicated that the corresponding vibrational modes have a large Huang-Rhys factor between the reactant and the product states, supporting the hypothesis that the loss of phase coherence along certain vibrational modes elucidates that those vibrations are coupled to the reaction coordinate of an ET reaction.

Transient Absorption Spectroscopy Offers Mechanistic Insights for an Iridium/Nickel-Catalyzed C-O Coupling.

We report mechanistic insights into an iridium/nickel photocatalytic C-O cross-coupling reaction from time-resolved spectroscopic studies. Using transient absorption spectroscopy, energy transfer from an iridium photocatalyst to a catalytically relevant Ni(II)(aryl) acetate acceptor was observed. Concentration-dependent lifetime measurements suggest the mechanism of the subsequent reductive elimination is a unimolecular process occurring on the long-lived excited state of the Ni(II) complex. We envision that our study of the productive energy-transfer-mediated pathway would encourage the development of new excited-state reactivities in the field of metallaphotocatalysis that are enabled by light harvesting.

Reduced Recombination and Capacitor-like Charge Buildup in an Organic Heterojunction.

Organic photovoltaic (OPV) efficiencies continue to rise, raising their prospects for solar energy conversion. However, researchers have long considered how to suppress the loss of free carriers by recombination-poor diffusion and significant Coulombic attraction can cause electrons and holes to encounter each other at interfaces close to where they were photogenerated. Using femtosecond transient spectroscopies, we report the nanosecond grow-in of a large transient Stark effect, caused by nanoscale electric fields of ∼487 kV/cm between photogenerated free carriers in the device active layer. We find that particular morphologies of the active layer lead to an energetic cascade for charge carriers, suppressing pathways to recombination, which is ∼2000 times less than predicted by Langevin theory. This in turn leads to the buildup of electric charge in donor and acceptor domains-away from the interface-resistant to bimolecular recombination. Interestingly, this signal is only experimentally obvious in thick films due to the different scaling of electroabsorption and photoinduced absorption signals in transient absorption spectroscopy. Rather than inhibiting device performance, we show that devices up to 600 nm thick maintain efficiencies of >8% because domains can afford much higher carrier densities. These observations suggest that with particular nanoscale morphologies the bulk heterojunction can go beyond its established role in charge photogeneration and can act as a capacitor, where adjacent free charges are held away from the interface and can be protected from bimolecular recombination.

Long-Lived Charge-Transfer States of Nickel(II) Aryl Halide Complexes Facilitate Bimolecular Photoinduced Electron Transfer.

Here we investigate the photophysics and photochemistry of Ni(II) aryl halide complexes common to cross-coupling and Ni/photoredox reactions. Computational and ultrafast spectroscopic studies reveal that these complexes feature long-lived 3MLCT excited states, implicating Ni as an underexplored alternative to precious metal photocatalysts. Moreover, we show that 3MLCT Ni(II) engages in bimolecular electron transfer with ground-state Ni(II), which enables access to Ni(III) in the absence of external oxidants or photoredox catalysts. As such, it is possible to facilitate Ni-catalyzed C-O bond formation solely by visible light irradiation, thus representing an alternative strategy for catalyst activation in Ni cross-coupling reactions.

Solvent-dependent photo-induced dynamics in a non-rigidly linked zinc phthalocyanine-perylenediimide dyad probed using ultrafast spectroscopy.

In this work, we characterize the energy and electron transfer kinetics of a zinc phthalocyanine-perylenediimide dyad (ZnPc-PDI) in various solvents using steady-state and tunable narrowband pump-probe spectroscopy. We fit the ultrafast data with global analysis techniques and find that upon excitation of the PDI moiety (pump pulse at 540 nm), the excitation energy transfer (EET) rate to the ZnPc moiety displays a solvent sensitivity that we attribute to changes in the relative equilibrium moiety orientation. We rationalize these observations by considering the nature of the non-rigid bridge used to link the two moieties as well as the degenerate nature of the Q band transitions in the ZnPc species. By tuning the pulse into resonance with the ZnPc Q band (685 nm) we can directly photo-induce an electron transfer (ET) process back to the PDI moiety. Employing the same global analysis, we find that the dynamics of the ultrafast electron transfer are completely kinetically controlled according to the Bixon-Jortner model of barrierless solvent-controlled curve crossing, while the recombination to reform the ground state is well-described using the static energetic picture according to Marcus theory.

Persistent Energetic Electrons in Methylammonium Lead Iodide Perovskite Thin Films.

In conventional semiconductor solar cells, carriers are extracted at the band edges and the excess electronic energy (E*) is lost as heat. If E* is harvested, power conversion efficiency can be as high as twice the Shockley-Queisser limit. To date, materials suitable for hot carrier solar cells have not been found due to efficient electron/optical-phonon scattering in most semiconductors, but our recent experiments revealed long-lived hot carriers in single-crystal hybrid lead bromide perovskites. Here we turn to polycrystalline methylammonium lead iodide perovskite, which has emerged as the material for highly efficient solar cells. We observe energetic electrons with excess energy ⟨E*⟩ ≈ 0.25 eV above the conduction band minimum and with lifetime as long as ∼100 ps, which is 2-3 orders of magnitude longer than those in conventional semiconductors. The energetic carriers also give rise to hot fluorescence emission with pseudo-electronic temperatures as high as 1900 K. These findings point to a suppression of hot carrier scattering with optical phonons in methylammonium lead iodide perovskite. We address mechanistic origins of this suppression and, in particular, the correlation of this suppression with dynamic disorder. We discuss potential harvesting of energetic carriers for solar energy conversion.

Trap states in lead iodide perovskites.

Recent discoveries of highly efficient solar cells based on lead iodide perovskites have led to a surge in research activity on understanding photo carrier generation in these materials, but little is known about trap states that may be detrimental to solar cell performance. Here we provide direct evidence for hole traps on the surfaces of three-dimensional (3D) CH3NH3PbI3 perovskite thin films and excitonic traps below the optical gaps in these materials. The excitonic traps possess weak optical transition strengths, can be populated from the relaxation of above gap excitations, and become more significant as dimensionality decreases from 3D CH3NH3PbI3 to two-dimensional (2D) (C4H9NH3I)2(CH3NH3I)(n-1)(PbI2)(n) (n = 1, 2, 3) perovskites and, within the 2D family, as n decreases from 3 to 1. We also show that the density of excitonic traps in CH3NH3PbI3 perovskite thin films grown in the presence of chloride is at least one-order of magnitude lower than that grown in the absence of chloride, thus explaining a widely known mystery on the much better solar cell performance of the former. The trap states are likely caused by electron-phonon coupling and are enhanced at surfaces/interfaces where the perovskite crystal structure is most susceptible to deformation.

Interplay of vibrational wavepackets during an ultrafast electron transfer reaction.

Electron transfer reactions facilitate energy transduction and photoredox processes in biology and chemistry. Recent findings show that molecular vibrations can enable the dramatic acceleration of some electron transfer reactions, and control it by suppressing and enhancing reaction paths. Here, we report ultrafast spectroscopy experiments and quantum dynamics simulations that resolve how quantum vibrations participate in an electron transfer reaction. We observe ballistic electron transfer (~30 fs) along a reaction coordinate comprising high-frequency promoting vibrations. Along another vibrational coordinate, the system becomes impulsively out of equilibrium as a result of the electron transfer reaction. This leads to the generation (by the electron transfer reaction, not the laser pulse) of a new vibrational coherence along this second reaction coordinate in a mode associated with the reaction product. These results resolve a complex reaction trajectory composed of multiple vibrational coordinates that, like a sequence of ratchets, progressively diminish the recurrence of the reactant state.

Polariton Decay in Donor-Acceptor Cavity Systems.

Enhanced delocalization is beneficial for absorbing molecules in organic solar cells, and in particular bilayer devices, where excitons face small diffusion lengths as a barrier to reaching the charge-generating donor-acceptor interface. As hybrid light-matter states, polaritons offer exceptional delocalization which could be used to improve the efficiency of bilayer organic photovoltaics. Polariton delocalization can aid in delivering excitons to the donor-acceptor interface, but the subsequent charge transfer event must compete with the fast decay of the polariton. To evaluate the viability of polaritons as tools to improve bilayer organic solar cells, we studied the decay of the lower polariton in three cavity systems: a donor only, a donor-acceptor bilayer, and a donor-acceptor blend. Using several spectroscopic techniques, we identified an additional decay pathway through charge transfer for the polariton in the bilayer cavity, demonstrating charge transfer from the polariton is fast enough to outcompete the decay to the ground state.

Entropy Reorders Polariton States.

The main result is that the long-range phase coherence of the polariton states formed by strong coupling between a photon mode in a cavity and an ensemble of molecules leads to exceptionally low entropy of the upper and lower polariton states, starkly contrasting with the dark states. That result means that spectroscopy does not correctly order the free energy of the excited states because there is a significant entropic contribution to the free energy, which turns out to comparable to the electronic energy gap between the lower polariton state and the dark-state manifold. The reordered states, according to their free energy, is important to predict the potential of polariton states for reactivity, to predict spontaneous photophysical dynamics, or to understand their decoherence. The entropic contribution adds to the polariton electronic gap, rendering states surprisingly more reactive than anticipated from the input excitation energy. This apparently "additional" reactivity, evident from the thermodynamics, suggests how the low entropy of highly coherent states can be exploited as a resource.

Asymmetric redox-neutral radical cyclization catalysed by flavin-dependent 'ene'-reductases.

Flavin-dependent 'ene'-reductases (EREDs) are exquisite catalysts for effecting stereoselective reductions. Although these reactions typically proceed through a hydride transfer mechanism, we recently found that EREDs can also catalyse reductive dehalogenations and cyclizations via single electron transfer mechanisms. Here, we demonstrate that these enzymes can catalyse redox-neutral radical cyclizations to produce enantioenriched oxindoles from α-haloamides. This transformation is a C-C bond-forming reaction currently unknown in nature and one for which there are no catalytic asymmetric examples. Mechanistic studies indicate the reaction proceeds via the flavin semiquinone/quinone redox couple, where ground-state flavin semiquinone provides the electron for substrate reduction and flavin quinone oxidizes the vinylogous α-amido radical formed after cyclization. This mechanistic manifold was previously unknown for this enzyme family, highlighting the versatility of EREDs in asymmetric synthesis.

Active-Site Environmental Factors Customize the Photophysics of Photoenzymatic Old Yellow Enzymes.

The development of non-natural photoenzymatic systems has reinvigorated the study of photoinduced electron transfer (ET) within protein active sites, providing new and unique platforms for understanding how biological environments affect photochemical processes. In this work, we use ultrafast spectroscopy to compare the photoinduced electron transfer in known photoenzymes. 12-Oxophytodienoate reductase 1 (OPR1) is compared to Old Yellow Enzyme 1 (OYE1) and morphinone reductase (MR). The latter enzymes are structurally homologous to OPR1. We find that slight differences in the amino acid composition of the active sites of these proteins determine their distinct electron-transfer dynamics. Our work suggests that the inside of a protein active site is a complex/heterogeneous dielectric network where genetically programmed heterogeneity near the site of biological ET can significantly affect the presence and lifetime of various intermediate states. Our work motivates additional tunability of Old Yellow Enzyme active-site reorganization energy and electron-transfer energetics that could be leveraged for photoenzymatic redox approaches.

Ultrafast Dynamics of Nonrigid Zinc-Porphyrin Arrays Mimicking the Photosynthetic "Special Pair".

Conjugated porphyrin arrays are heavily investigated as efficient molecular systems for photosynthesis and photocatalysis. Recently, a series of one-, two-, and six-zinc-porphyrin arrays, noncovalently linked through benzene-based hubs, have been synthesized with the aim of mimicking the structure and function of the bacteriochlorophyll "special pair" in photosynthetic reaction centers. The excitonically coupled porphyrin subunits are expected to activate additional excited state relaxation channels with respect to the monomer. Here, we unveil the appearance of such supramolecular electronic interactions using ultrafast transient absorption spectroscopy with sub-25 fs time resolution. Upon photoexcitation of the Soret band, we resolve energy trapping within ∼150 fs in a delocalized dark excitonic manifold. Moreover, excitonic interactions promote an additional fast internal conversion from the Q-band to the ground state with an efficiency of up to 60% in the hexamer. These relaxation pathways appear to be common loss channels that limit the lifetime of the exciton states in noncovalently bound molecular aggregates.