Excited State Proton Transfer from Acidic Alcohols to a Quinoline Photobase Can Be Solvated by Non-Acidic Alcohol Solvents.

Photobases are a type of molecule that become more basic upon photoexcitation and can therefore be used to control proton transfer reactions with light. The solvation requirements for excited state proton transfer (ESPT) in photobase systems is poorly understood, which limits their applicability. Here, we investigate the solvation of the ESPT reaction using 5-methoxyquinoline (MeOQ), a well-studied photobase with an excited state pKa (pKa*) of approximately 15.1, as a model system. Previous studies have shown that, in addition to the acidic donor that donates a proton to the photoexcited MeOQ, an additional "auxiliary donor" is necessary to solvate the resulting alkoxide. We investigate whether a nonacidic hydrogen bond donor (an alcohol solvent that MeOQ cannot deprotonate in bulk) can act as the auxiliary donor for the MeOQ ESPT reaction. First, we use steady state spectroscopy, TCSPC, and electronic structure calculations to show that MeOQ can deprotonate the acidic donor 2,2,2-trifluoroethanol (TFE, pKa = 12.5) using ethanol as the auxiliary donor. We show that the degree of ESPT is largely predicted by the degree of ground state hydrogen bonding between the photobase and the acidic donor. Next, we study the deprotonation of the acidic donors TFE and 1,1,1,3,3,3-hexafluoroisopropanol (HFIP, pKa = 9.3) with MeOQ in a variety of nonacidic alcohol solvents of varying chain length and branching. MeOQ ESPT occurs to varying extents in all solvents, suggesting that all studied nonacidic alcohols can function as auxiliary donors. We show that the concentration of the acidic donor is strongly correlated with the degree of ESPT. These results are necessary fundamental steps toward the understanding of the photobase ESPT reaction and its wide application in a variety of chemical systems.

Modeling and Characterization of Exciplexes in Photoredox CO2 Reduction: Insights from Quantum Chemistry and Fluorescence Spectroscopy.

Interactions between excited-state arenes and amines can lead to the formation of structures with a distinct emission behavior. These excited-state complexes or exciplexes can reduce the ability of the arene to participate in other reactions, such as CO2 reduction, or increase the likelihood of degradation via Birch reduction. Exciplex geometries are necessary to understand photophysical behavior and probe degradation pathways but are challenging to calculate. We establish a detailed computational protocol for calculation, verification, and characterization of exciplexes. Using fluorescence spectroscopy, we first demonstrate the formation of exciplexes between excited-state oligo-(p-phenylene) (OPP), shown to successfully carry out CO2 reduction, and triethylamine. Time-dependent density functional theory is employed to optimize the geometries of these exciplexes, which are validated by comparing both emission energies and their solvatochromism with the experiment. Excited-state energy decomposition analysis confirms the predominant role played by charge transfer interactions in the red shift of emissions relative to the isolated excited-state OPP*. We find that although the exciplex emission frequency depends strongly on solvent dielectric, the extent of charge separation in an exciplex does not. Our results also suggest that the formation of solvent-separated ionic radical states upon complete electron transfer competes with exciplex formation in higher-dielectric solvents, thereby leading to reduced exciplex emission intensities in fluorescence experiments.

Kinetic Evidence for the Necessity of Two Proton Donor Molecules for Successful Excited State Proton Transfer by a Photobase.

Photobases are molecules that convert light to proton transfer drive and therefore have potential applications in many areas of chemistry. Previously, we studied the photobasicity of quinolines and explored their applications. While it is possible to tether a photobase near a target proton donor, for the sake of versatility it is desirable to explore their capability to deprotonate molecules dispersed in a solution. Previous evidence suggested that in this scenario at least two proton donors were necessary for successful excited state proton transfer: one to donate a proton and the second to stabilize the photogenerated donor anion. Here we report kinetic evidence from transient absorption (TA) and time-correlated single photon counting (TCSPC) in support of this hypothesis. We used 5-methoxyquinoline as the photobase and 2,2,2-trifluoroethanol (TFE), a low pKa alcohol, as the proton donor. A constant concentration of the photobase was used for a range of proton-donor dilutions spanning several orders of magnitude in an aprotic background solvent. Absorption spectra confirm that over most of the studied range the majority of the photobase population is hydrogen bonded to at least one donor. Short-pulse TA was used to measure the faster (2-500 ps) dynamics, while TSCPC was used to measure the slower (>500 ps) dynamics. The measured proton transfer time constants varied as a function of donor concentration over a wide range. A log-log plot of the proton transfer rate constant as a function of proton-donor concentration shows two regimes: nondiffusive at high donor concentrations where multiple proton donors are near the photobase and diffusive at low donor concentrations where proton donors are more dilute. The nondiffusive regime has a slope of approximately one, suggesting that the proton transfer process is dependent on one donor molecule in addition to the donor molecule already hydrogen bonded with the photobase. The diffusive regime reasonably follows diffusion kinetics. We propose a model for how the second proton-donor molecule may interact with the photogenerated alkoxide to stabilize it. This work highlights the importance of inducing irreversible changes, in this case solvation of the alkoxide, after proton transfer. Understanding of such details is likely to be important in applications of photobases.

Donor-acceptor preassociation, excited state solvation threshold, and optical energy cost as challenges in chemical applications of photobases.

Photobases are molecules with increased pKa in the excited state that can serve to transduce light energy into proton removal capability. They can be used to control chemical reactions using light, such as removing protons from a catalytic site in reactions that are rate-limited by proton transfer. We identify and explore several major challenges toward their practical applications. Two important challenges are the need for pre-association (or ground state hydrogen bonding) between the proton donor and the photobase, and the need for excited state solvation of the photogenerated products. We investigate these two challenges with the photobase 5-methoxyquinoline as the proton acceptor and a low-pKa alcohol, 2,2,2-trifluoroethanol, as the proton donor. We vary the concentration of the donor in a background non-hydrogen-bonding solvent. Using absorption spectroscopy, we have identified that the donor-acceptor concentration ratio must exceed 100 : 1 to achieve appreciable ground state hydrogen bonding. Interestingly, emission spectroscopy reveals that the onset of ground state hydrogen bonding does not guarantee successful excited state proton transfer. It takes an additional order of magnitude increase in donor-acceptor ratio to achieve that goal, revealing that it is necessary to have excess donor molecules to reach the solvation threshold for the photogenerated products. The next challenge is reducing the large ground-excited state energy gap, which often requires UV photons to drive proton transfer. We show experimental and computational data comparing the photobasicity and optical energy gap for a few N-aromatic heterocyclic photobases. In general, we find that reducing the energy gap by increasing the conjugation size necessarily reduces photobasicity, while adding substituents of varying electron-withdrawing strength allows some fine-tuning of this effect. The combination of these two factors provide a preliminary design space for creating new photobasic molecules.

Photodriven Deprotonation of Alcohols by a Quinoline Photobase.

Control of proton transfer is relevant to many areas in chemistry, particularly in catalysis where the kinetics of (de)protonation reactions are often rate limiting. Photobases, which are molecules with enhanced basicity in the excited state, allow for control of proton transfer with light and have the potential to be used as functional units in catalytic systems. Alcohols are the feedstock in many catalytic reactions, where their deprotonation or dehydrogenation is often important. We report that the photobase 5-methoxyquinoline can deprotonate a series of alcohols upon excitation by light. We measure both the thermodynamic limits and the relevant kinetics of this process. A series of alcohols and water spanning the p Ka range of 12.5-16.5 were used as the proton donors. First, we show evidence from absorption and emission spectroscopy that photoexcited 5-methoxyquinoline deprotonates all donors more acidic than methanol and fails to deprotonate donors that are more basic. Interestingly, in methanol a quasi-equilibrium between the protonated and unprotonated forms of the photobase is established in the excited state, suggesting that the excited state p Ka of the photobase is near the p Ka of methanol (15.5). Second, using ultrafast transient absorption spectroscopy, we find that the time constants for excited state proton transfer range from a few picoseconds to tens of picoseconds, with faster speeds for the more acidic donors. Such a correlation between the thermodynamic drive and kinetics suggests that the same mechanism is responsible for proton transfer throughout the series. These results are necessary fundamental steps for applying photobases in potential applications such as deprotonation of alcohols for catalytic and synthetic purposes, optical regulation of pH, and transfer of protons in redox reactions.

Proton Capture Dynamics in Quinoline Photobases: Substituent Effect and Involvement of Triplet States.

Converting light into chemical energy often occurs through redox reactions that require transfer of several electrons and protons. Using light to control proton transfer has the potential for driving otherwise unfavorable protonation reactions or producing transient pH changes. Photoacids and photobases are fundamental functional elements that could serve this purpose. Previously, we have reported the thermodynamic drive for proton removal in a series of quinoline photobases using Forster cycle analysis of the singlet states. Because the existence of thermodynamic drive does not imply that the molecules can indeed capture protons in the excited state, in this work we report the kinetics of proton removal from water by 5-R-quinolines, R = {NH2, OCH3, H, Cl, Br, CN}, using ultrafast transient absorption spectroscopy. We found that the time constants and mechanisms of proton capture from water are highly sensitive to the substituent. In some cases, proton transfer occurs within the singlet manifold, whereas in some others intersystem crossing competes with this process. We have evidence that the triplet states are also capable of proton capture in two of the compounds. This renders the excited state proton transfer process more complicated than can be captured by the linear free energy relationships inferred from the energetics of the singlet states. We have measured proton capture times in this family to be in the range of several tens of picoseconds with no discernible trend with respect to the Hammett parameter of the substituents. This wide range of mechanisms is attributed to the high density of excited electronic states in the singlet and triplet manifolds. The ordering between these states is expected to change by substituent, solvent, and hydrogen bonding, thus making the rate of intersystem crossing and proton transfer very sensitive to these parameters. These results are necessary fundamental steps to assess the capabilities of photobases in prospective applications such as photomediated proton removal in redox reactions, steady state optical regulation of local pH, and pOH jump kinetics experiments.