Exchange-Mediated Transport in Battery Electrolytes: Ultrafast or Ultraslow?

Understanding the mechanisms of charge transport in batteries is important for the rational design of new electrolyte formulations. Persistent questions about ion transport mechanisms in battery electrolytes are often framed in terms of vehicular diffusion by persistent ion-solvent complexes versus structural diffusion through the breaking and reformation of ion-solvent contacts, i.e., solvent exchange events. Ultrafast two-dimensional (2D) IR spectroscopy can probe exchange processes directly via the evolution of the cross-peaks on picosecond time scales. However, vibrational energy transfer in the absence of solvent exchange gives rise to the same spectral signatures, hiding the desired processes. We employ 2D IR on solvent resonances of a mixture of acetonitrile isotopologues to differentiate chemical exchange and energy-transfer dynamics in a comprehensive series of Li+, Mg2+, Zn2+, Ca2+, and Ba2+ bis(trifluoromethylsulfonyl)imide electrolytes from the dilute to the superconcentrated regime. No exchange phenomena occur within at least 100 ps, regardless of the ion identity, salt concentration, and presence of water. All of the observed spectral dynamics originate from the intermolecular energy transfer. These results place the lower experimental boundary on the ion-solvent residence times to several hundred picoseconds, much slower than previously suggested. With the help of MD simulations and conductivity measurements on the Li+ and Zn2+ systems, we discuss these results as a continuum of vehicular and structural modalities that vary with concentration and emphasize the importance of collective electrolyte motions to ion transport. These results hold broadly applicable to many battery-relevant ions and solvents.

Decoding the 2D IR spectrum of the aqueous proton with high-level VSCF/VCI calculations.

The aqueous proton is a common and long-studied species in chemistry, yet there is currently intense interest devoted to understanding its hydration structure and transport dynamics. Typically described in terms of two limiting structures observed in gas-phase clusters, the Zundel H5O2 + and Eigen H9O4 + ions, the aqueous structure is less clear due to the heterogeneity of hydrogen bonding environments and room-temperature structural fluctuations in water. The linear infrared (IR) spectrum, which reports on structural configurations, is challenging to interpret because it appears as a continuum of absorption, and the underlying vibrational modes are strongly anharmonically coupled to each other. Recent two-dimensional IR (2D IR) experiments presented strong evidence for asymmetric Zundel-like motifs in solution, but true structure-spectrum correlations are missing and complicated by the anharmonicity of the system. In this study, we employ high-level vibrational self-consistent field/virtual state configuration interaction calculations to demonstrate that the 2D IR spectrum reports on a broad distribution of geometric configurations of the aqueous proton. We find that the diagonal 2D IR spectrum around 1200 cm-1 is dominated by the proton stretch vibrations of Zundel-like and intermediate geometries, broadened by the heterogeneity of aqueous configurations. There is a wide distribution of multidimensional potential shapes for the proton stretching vibration with varying degrees of potential asymmetry and confinement. Finally, we find specific cross peak patterns due to aqueous Zundel-like species. These studies provide clarity on highly debated spectral assignments and stringent spectroscopic benchmarks for future simulations.

Correction: Cyclopeptidic photosensitizer prodrugs as proteolytically triggered drug delivery systems of pheophorbide A: part II - co-loading of pheophorbide A and black hole quencher.

Correction for 'Cyclopeptidic photosensitizer prodrugs as proteolytically triggered drug delivery systems of pheophorbide A: part II - co-loading of pheophorbide A and black hole quencher' by Jordan Bouilloux et al., Photochem. Photobiol. Sci., 2018, 17, 1739-1748.

Correction: Cyclopeptidic photosensitizer prodrugs as proteolytically triggered drug delivery systems of pheophorbide A: part I - self-quenched prodrugs.

Correction for 'Cyclopeptidic photosensitizer prodrugs as proteolytically triggered drug delivery systems of pheophorbide A: part I - self-quenched prodrugs' by Jordan Bouilloux et al., Photochem. Photobiol. Sci., 2018, 17, 1728-1738.

Halogen-Bond Assisted Photoinduced Electron Transfer.

The formation of a halogen-bond (XB) complex in the excited state was recently reported with a quadrupolar acceptor-donor-acceptor dye in two iodine-based liquids (J. Phys. Chem. Lett. 2017, 8, 3927-3932). The ultrafast decay of this excited complex to the ground state was ascribed to an electron transfer quenching by the XB donors. We examined the mechanism of this process by investigating the quenching dynamics of the dye in the S1 state using the same two iodo-compounds diluted in inert solvents. The results were compared with those obtained with a non-halogenated electron acceptor, fumaronitrile. Whereas quenching by fumaronitrile was found to be diffusion controlled, that by the two XB compounds is slower, despite a larger driving force for electron transfer. A Smoluchowski-Collins-Kimball analysis of the excited-state population decays reveals that both the intrinsic quenching rate constant and the quenching radius are significantly smaller with the XB compounds. These results point to much stronger orientational constraint for quenching with the XB compounds, indicating that electron transfer occurs upon formation of the halogen bond.

Looking at Photoinduced Charge Transfer Processes in the IR: Answers to Several Long-Standing Questions.

Because of its crucial role in many areas of science and technology, photoinduced electron transfer is the most investigated photochemical reaction. Despite this, several important questions remain open. We present recent efforts to answer some of them, which concern both inter- and intramolecular processes. The decisive factor that allowed these issues to be successfully addressed was the use of time-resolved infrared (TRIR) spectroscopy. Many different transient species, such as tight and loose ion pairs (TIPs and LIPs) and exciplexes, have been invoked to explain the dynamics of intermolecular photoinduced charge separation reactions (i.e., electron transfer between two neutral species) and the production of free ions. However, their structures are essentially unknown, and their exact roles in the reaction mechanism are unclear. Indeed, the commonly used transient electronic absorption spectroscopy does not give much structural insight and cannot clearly distinguish ion pairs from free ions, at least in the visible region. Unambiguous spectral signatures of TIPs, LIPs, and exciplexes could be observed in the IR using electron donor/acceptor (D/A) pairs with adequate vibrational marker modes. The ability to spectrally distinguish these intermediates allowed their dynamics to be disentangled and their roles to be determined. Structural information could be obtained using polarization-resolved TRIR spectroscopy. Our investigations reveal that moderately to highly exergonic reactions result in the formation of both TIPs and LIPs. TIPs are not only generated upon direct charge-transfer excitation of DA complexes, as usually assumed, but are also formed upon static quenching with reactant pairs at distances and orientations enabling charge separation without diffusion. On the other hand, dynamic quenching produces primarily LIPs. In the case of highly exergonic reactions, strong indirect evidence for the generation of ion pairs in an electronic excited state was found, accounting for the absence of an inverted region. Finally, weakly exergonic reactions produce predominantly exciplexes, which can evolve further into ion pairs or recombine to the neutral ground state. The high sensitivity of specific vibrational modes to the local electronic density was exploited to visualize the photoinduced charge flow in symmetric A-(π-D)2- and D-(π-A)2-type molecules developed for their two-photon absorption properties. The electronic ground state and Franck-Condon S1 state of these molecules are purely quadrupolar, but the strong solvatochromism of their fluorescence points to a highly dipolar relaxed S1 state. This has been explained in terms of excited-state symmetry breaking induced by solvent and/or structural fluctuations. However, real-time observation of this process was missing. Direct visualization of symmetry-breaking charge transfer was achieved using TRIR spectroscopy by monitoring vibrations localized in the two arms of these molecules. A transition from a purely quadrupolar state to a symmetry-broken state on the timescale of solvent relaxation could be clearly observed in polar solvents, indicating that symmetry breaking occurs primarily via solvent fluctuations. In the case of the D-(π-A)2 molecule, this breaking results in different basicities at the two A ends and consequently in different affinities for H-bonds, which in turn leads to the formation of an asymmetric tight H-bonded complex in highly protic solvents.

Cyclopeptidic photosensitizer prodrugs as proteolytically triggered drug delivery systems of pheophorbide A: part I - self-quenched prodrugs.

Herein, we report the synthesis of a new prodrug system consisting of regioselectively addressable functionalized templates bearing multiple pheophorbide A moieties for use in photodynamic therapy. These coupling reactions were achieved using copper-free "click" chemistry, namely a strain-promoted azide-alkyne cycloaddition. This new design was used to obtain well-defined quenched photosensitizer prodrugs with perfect knowledge of the number and position of loaded photosensitizers, providing structures bearing up to six photosentitizers and two PEG chains. These conjugates are ideally quenched in their native state regarding their fluorescence emission (up to 155 ± 28 times less fluorescent for an hexasubstituted conjugate than a monosubstituted non-quenched reference compound) or singlet oxygen production (decreased 8.7-fold in the best case) when excited. After 2 h of proteolytic activation, the fluorescence emission of a tetrasubstituted conjugate was increased 17-fold compared with the initial fluorescence emission.

Cyclopeptidic photosensitizer prodrugs as proteolytically triggered drug delivery systems of pheophorbide A: part II - co-loading of pheophorbide A and black hole quencher.

Previously, we have shown that the use of a cyclopeptidic carrier could be of great interest for the design of fully characterized prodrugs for further use in photodynamic therapy. In order to further optimize the design, we decided to modify the highly quenched conjugate uPA-cPPP4/5 by co-loading a long-distance fluorescence quencher. For this purpose we tethered two black hole quenchers (BHQ3) together with two pheophorbide A moities onto the same PEGylated backbone and assessed the modified photophysical properties. In addition, to prove the reliability of our concept, we designed two analogues, uPA-cPPQ2+2/5 and CathB-cPPQ2+2/5, by using two different peptidic linkers as substrates for uPA and cathepsin B, respectively. These two conjugates proved to be much more water-soluble than their analogues bearing only Phas. These conjugates are not only highly quenched in their native state with regard to their fluorescence emission (up to 850 ± 287 times less fluorescent for CathB-cPPQ2+2/5 as compared to the unquenched monosubstituted reference uPA-cPPP1/5), but also prevent singlet oxygen production (with a total quenching of the emission when the quenchers are co-loaded with photosensitizers) when the photosentistizers are excited. After proteolytic activation, these conjugates recover their photophysical properties in the same way as occurred for uPA-cPPP4/5, with up to a 120-fold increase in fluorescence emission for uPA-cPPQ2+2/5 after two hours of incubation with uPA.

Influence of the hydrogen-bond interactions on the excited-state dynamics of a push-pull azobenzene dye: the case of Methyl Orange.

The excited-state dynamics of the push-pull azobenzene Methyl Orange (MO) were investigated in several solvents and water/glycerol mixtures using a combination of ultrafast time-resolved fluorescence and transient absorption in both the UV-visible and the IR regions, as well as quantum chemical calculations. Optical excitation of MO in its trans form results in the population of the S2 ππ* state and is followed by internal conversion to the S1 nπ* state in ∼50 fs. The population of this state decays on the sub-picosecond timescale by both internal conversion to the trans ground state and isomerisation to the cis ground state. Finally, the cis form converts thermally to the trans form on a timescale ranging from less than 50 ms to several minutes. Significant differences depending on the hydrogen-bond donor strength of the solvents, quantified by the Kamlet Taft parameter α, were observed: compared to the other solvents, in highly protic solvents (α > 1), (i) the viscosity dependence of the S1 state lifetime is less pronounced, (ii) the S1 state lifetime is shorter by a factor of ≈1.5 for the same viscosity, (iii) the trans-to-cis photoisomerisation efficiency is smaller, and (iv) the thermal cis-to-trans isomerisation is faster by a factor of ≥103. These differences are explained in terms of hydrogen-bond interactions between the solvent and the azo nitrogen atoms of MO, which not only change the nature of the S1 state but also have an impact on the shape of ground- and excited-state potentials, and, thus, affect the deactivation pathways from the excited state.

Transient Glass Formation around a Quadrupolar Photoexcited Dye in a Strongly H-Bonding Liquid Observed by Transient 2D-IR Spectroscopy.

Intermolecular H-bonding dynamics around a photoexcited quadrupolar dye is directly observed using transient 2D-IR spectroscopy. Upon solvent-induced symmetry breaking, the H-bond accepting abilities of the two nitrile end-groups change drastically, and in extremely protic (superprotic) solvents, a tight H-bond complex forms at one end. The time evolution of the 2D C≡N lineshape in methanol points to rapid, 2-3 ps, spectral diffusion due to fluctuations of the H-bonding network. Similar behavior is observed in a superprotic solvent shortly after photoexcitation of the dye. However, at later times, the completely inhomogeneous band does not exhibit spectral diffusion for at least 5 ps, pointing to a glass-like environment around one side of the dye. About half of the excited dyes show this behavior attributed to the tight H-bond complex, whereas the others are loosely bound. A weak cross peak indicates partial exchange between these excited state subpopulations.

Direct Observation of a Photochemical Alkyne-Allene Reaction and of a Twisted and Rehybridized Intramolecular Charge-Transfer State in a Donor-Acceptor Dyad.

The excited-state dynamics of an aniline-triazine electron donor-acceptor dyad with an alkyne spacer has been investigated using a combination of ultrafast broadband mid-IR and visible transient absorption and fluorescence spectroscopies. The transient IR data reveal the occurrence of an efficient alkyne to allene isomerization of the spacer with a time constant increasing from a few hundreds of femtoseconds to a few picoseconds with solvent viscosity. This process is faster than the vibrational cooling of the Franck-Condon excited state, indicative of nonequilibrium dynamics. The transient electronic absorption and fluorescence data evidence that this transformation is accompanied by a charge separation between the donor and the acceptor subunits. The allene character of the spacer implies an orthogonal orientation of the donor and acceptor moieties, similar to that proposed for twisted intramolecular charge-transfer states. Such states are often invoked in the excited-state dynamics of donor-acceptor dyads, but their involvement could never be unambiguously evidenced spectroscopically. The alkyne-allene isomerization involves not only a torsional motion but also a bending of the molecule due to the sp to sp2 rehybridization of one of the alkyne carbon atoms. This twisted and rehybridized intramolecular charge transfer ("TRICT") state decays back to the planar and linear alkyne ground state on a time scale decreasing from a few hundred to ten picoseconds upon going from weakly to highly polar solvents. The different solvent dependencies reveal that the dynamics of the allene buildup are controlled by the structural changes, whereas the decay is limited by the charge recombination step.

A simple model of solvent-induced symmetry-breaking charge transfer in excited quadrupolar molecules.

A simple model has been developed to describe the symmetry-breaking of the electronic distribution of AL-D-AR type molecules in the excited state, where D is an electron donor and AL and AR are identical acceptors. The origin of this process is usually associated with the interaction between the molecule and the solvent polarization that stabilizes an asymmetric and dipolar state, with a larger charge transfer on one side than on the other. An additional symmetry-breaking mechanism involving the direct Coulomb interaction of the charges on the acceptors is proposed. At the same time, the electronic coupling between the two degenerate states, which correspond to the transferred charge being localised either on AL or AR, favours a quadrupolar excited state with equal amount of charge-transfer on both sides. Because of these counteracting effects, symmetry breaking is only feasible when the electronic coupling remains below a threshold value, which depends on the solvation energy and the Coulomb repulsion energy between the charges located on AL and AR. This model allows reproducing the solvent polarity dependence of the symmetry-breaking reported recently using time-resolved infrared spectroscopy.

Direct Visualization of Excited-State Symmetry Breaking Using Ultrafast Time-Resolved Infrared Spectroscopy.

Most symmetric quadrupolar molecules designed for two-photon absorption behave as dipolar molecules in the S1 electronic excited state. This is usually explained by a breakup of the symmetry in the excited state. However, the origin of this process and its dynamics are still not fully understood. Here, excited-state symmetry breaking in a quadrupolar molecule with a D-π-A-π-D motif, where D and A are electron donating and accepting units, is observed in real time using ultrafast transient infrared absorption spectroscopy. The nature of the relaxed S1 state was found to strongly depend on the solvent polarity: (1) in nonpolar solvents, it is symmetric and quadrupolar; (2) in weakly polar media, the quadrupolar state observed directly after excitation transforms to a symmetry broken S1 state with one arm bearing more excitation than the other; and (3) in highly polar solvents, the excited state evolves further to a purely dipolar S1 state with the excitation localized entirely on one arm. The time scales associated with the transitions between these states coincide with those of solvation dynamics, indicating that symmetry breaking is governed by solvent fluctuations.

Symmetry-Breaking Charge Transfer and Hydrogen Bonding: Toward Asymmetrical Photochemistry.

Symmetry-breaking charge transfer upon photoexcitation of a linear A-π-D-π-A molecule (D and A being electron donating and accepting groups) could be visualized using ultrafast time-resolved infrared spectroscopy by monitoring the CN stretching modes on the A units. Whereas in apolar solvents, the S1 state remains symmetric and quadrupolar, symmetry breaking occurs within ca. 100 fs in polar solvents as shown by the presence of two CN bands, instead of one in apolar solvents, with a splitting that increases with polarity. In protic solvents, symmetry breaking is significantly amplified by H-bonding interactions, which are the strongest at the CN group with the highest basicity. In strongly protic solvents, the two CN bands transform in about 20 ps into new bands with a larger splitting, and the lifetime of the S1 state is substantially reduced. This is attributed to the formation of an excited asymmetric tight H-bond complex.

Characterization of Acetonitrile Isotopologues as Vibrational Probes of Electrolytes.

Acetonitrile has emerged as a solvent candidate for novel electrolyte formulations in metal-ion batteries and supercapacitors. It features a bright local C≡N stretch vibrational mode whose infrared (IR) signature is sensitive to battery-relevant cations (Li+, Mg2+, Zn2+, Ca2+) both in pure form and in the presence of water admixture across a full possible range of concentrations from the dilute to the superconcentrated regime. Stationary and time-resolved IR spectroscopy thus emerges as a natural tool to study site-specific intermolecular interactions from the solvent perspective without introducing an extrinsic probe that perturbs solution morphology and may not represent the intrinsic dynamics in these electrolytes. The metal-coordinated acetonitrile, water-separated metal-acetonitrile pair, and free solvent each have a distinct vibrational signature that allows their unambiguous differentiation. The IR band frequency of the metal-coordinated acetonitrile depends on the ion charge density. To study the ion transport dynamics, it is necessary to differentiate energy-transfer processes from structural interconversions in these electrolytes. Isotope labeling the solvent is a necessary prerequisite to separate these processes. We discuss the design principles and choice of the CD313CN label and characterize its vibrational spectroscopy in these electrolytes. The Fermi resonance between 13C≡N and C-D stretches complicates the spectral response but does not prevent its effective utilization. Time-resolved two-dimensional (2D) IR spectroscopy can be performed on a mixture of acetonitrile isotopologues and much can be learned about the structural dynamics of various species in these formulations.

From Networked to Isolated: Observing Water Hydrogen Bonds in Concentrated Electrolytes with Two-Dimensional Infrared Spectroscopy.

Superconcentrated electrolytes have emerged as a promising class of materials for energy storage devices, with evidence that high voltage performance is possible even with water as the solvent. Here, we study the changes in the water hydrogen bonding network induced by the dissolution of lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) in concentrations ranging from the dilute to the superconcentrated regimes. Using time-resolved two-dimensional infrared spectroscopy, we observe the progressive disruption of the water-water hydrogen bond network and the appearance of isolated water molecules interacting only with ions, which can be identified and spectroscopically isolated through the intermolecular cross-peaks between the water and the TFSI- ions. Analyzing the vibrational relaxation of excitations of the H2O stretching mode, we observe a transition in the dominant relaxation path as the bulk-like water vanishes and is replaced by ion-solvation water with the rapid single-step relaxation of delocalized stretching vibrations into the low frequency modes being replaced by multistep relaxation through the intramolecular H2O bend and into the TFSI- high frequency modes prior to relaxing to the low frequency structural degrees of freedom. These results definitively demonstrate the absence of vibrationally bulk-like water in the presence of high concentrations of LiTFSI and especially in the superconcentrated regime, while additionally revealing aspects of the water hydrogen bond network that have been difficult to discern from the vibrational spectroscopy of the neat liquid.

Mercury ions complexation with a series of heterocyclic derivatives of 3-hydroxychromone: spectral effects and prospects for ultrasensitive Hg2+ probing.

Complexation of three 3-hydroxychromone derivatives bearing a nitrogen-containing heterocyclic moiety in the position 2 of the chromone bicycle - benzimidazole, quinoline, and 2,5-diphenyloxazole, with mercury(II) ions is reported. Formation of chelate complexes with the metal cations coordinated with the cavity formed by 3-OH and 4-C═O groups was shown, as well as the possibility of side moiety heteroatom participation in binding of metal ions. High sensitivity to mercury of 2,5-diphenyloxazole-substituted 3-hydroxychromone was elucidated, allowing to detect Hg(2+) below the maximum permissible concentration for drinking water. This makes the above-mentioned compound a prospective basis for development of sensors for ultralow mercury concentration detection in water. Unusual fluorescence ignition of 2-(quinolin-2-yl)-3-hydroxychromone at low Hg(2+) concentrations, rarely observed for heavy metals ions complexation with organic fluorescent ligands, was discussed.

Crossover from hydrogen to chemical bonding.

Hydrogen bonds (H-bonds) can be interpreted as a classical electrostatic interaction or as a covalent chemical bond if the interaction is strong enough. As a result, short strong H-bonds exist at an intersection between qualitatively different bonding descriptions, with few experimental methods to understand this dichotomy. The [F-H-F]- ion represents a bare short H-bond, whose distinctive vibrational potential in water is revealed with femtosecond two-dimensional infrared spectroscopy. It shows the superharmonic behavior of the proton motion, which is strongly coupled to the donor-acceptor stretching and disappears on H-bond bending. In combination with high-level quantum-chemical calculations, we demonstrate a distinct crossover in spectroscopic properties from conventional to short strong H-bonds, which identify where hydrogen bonding ends and chemical bonding begins.

Broadband fluorescence reveals mechanistic differences in excited-state proton transfer to protic and aprotic solvents.

Excited-state proton transfer (ESPT) to solvent is often explained according to the two-step Eigen-Weller model including a contact ion pair (CIP*) as an intermediate, but general applicability of the model has not been thoroughly examined. Furthermore, examples of the spectral identification of CIP* are scarce. Here, we report on a detailed investigation of ESPT to protic (H2O, D2O, MeOH and EtOH) and aprotic (DMSO) solvents utilizing a broadband fluorescence technique with sub-200 fs time resolution. The time-resolved spectra are decomposed into contributions from the protonated and deprotonated species and a clear signature of CIP* is identified in DMSO and MeOH. Interestingly, the CIP* intermediate is not observable in aqueous environment although the dynamics in all solvents are multi-exponential. Global analysis based on the Eigen-Weller model is satisfactory in all solvents, but the marked mechanistic differences between aqueous and organic solvents cast doubt on the physical validity of the rate constants obtained.

Vibrational Probe of Aqueous Electrolytes: The Field Is Not Enough.

In this work, we study the vibrational solvatochromism and dynamics of dilute acetone as a carbonyl probe in simple aqueous electrolytes as a function of salt composition and concentration. We observe a linear dependence of the redshift of the CO stretch mode as a function of concentration for each salt, with the magnitude of the effect scaling with the charge densities of the cations. Using molecular dynamics (MD) simulations, we compare the observed spectral shifts with the electrostatic field distributions imparted on the acetone O, comparing a fixed-charge model and a polarizable model, and find that the experimentally observed frequencies scale linearly with the electric field for a given salt, but there remains a substantial component of the solvatochromism that depends on the identity of the cation and apparently cannot be explained by the electrostatic fields alone. Finally, we use ultrafast 2D IR spectroscopy to study the salt dependence of the solvation dynamics. We observe an anomalous nonmonotonic dependence of the time scale of the dynamics on the salt concentration, which cannot be reproduced by the fluctuations in the electrostatic field determined from MD simulations. These results point to the importance of both electrostatic and nonelectrostatic effects in the vibrational solvatochromism and dynamics in this apparently simple model system.