Excited-state symmetry breaking is an ultrasensitive tool for probing microscopic electric fields.

Microscopic electric fields are increasingly found to play a pivotal role in catalysis of enzymatic and chemical reactions. Currently, the vibrational Stark effect is the main experimental method used to measure them. Here, we demonstrate how excited-state symmetry breaking can serve as a much more sensitive tool to assess these fields.

Excited-State Symmetry Breaking and Localization in a Noncentrosymmetric Electron Donor-Acceptor-Donor Molecule.

Electronic excitation in quadrupolar conjugated molecules rapidly localizes on a single electron donor-acceptor (DA) branch when in polar environments. The loss of center of inversion upon this excited-state symmetry breaking (ES-SB) can be monitored by exploiting the relaxation of the exclusion rules for IR and Raman vibrational transitions. Here, we compare ES-SB in a right-angled () and a centrosymmetric () DAD dyes using time-resolved IR spectroscopy.

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.

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.

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, Mg, Zn, Ca) 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.

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 (HO, DO, MeOH and EtOH) and aprotic (DMSO) solvents utilizing a broadband fluorescence technique with sub-200 fs time resolution.

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.

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 HO and Eigen HO 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.

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.

Solvent tuning of photochemistry upon excited-state symmetry breaking.

The nature of the electronic excited state of many symmetric multibranched donor-acceptor molecules varies from delocalized/multipolar to localized/dipolar depending on the environment. Solvent-driven localization breaks the symmetry and traps the exciton in one branch. Using a combination of ultrafast spectroscopies, we investigate how such excited-state symmetry breaking affects the photochemical reactivity of quadrupolar and octupolar A-(π-D) molecules with photoisomerizable A-π-D branches.

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 ( , , 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 S state using the same two iodo-compounds diluted in inert solvents.

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.

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.

Ground-State Structural Disorder and Excited-State Symmetry Breaking in a Quadrupolar Molecule.

The influence of torsional disorder around the ethynyl π-bridges of a linear D-π-A-π-D molecule on the nature of its S excited state was investigated using ultrafast time-resolved infrared spectroscopy. By tuning the pump wavelength throughout the S ← S absorption band, subpopulations with different extents of asymmetry could be excited. In nonpolar solvents, the equilibrated S state is symmetric and quadrupolar independently of the initial degree of distortion.

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.

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-cPPP 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.

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.

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 S ππ* state and is followed by internal conversion to the S 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.

Excited-State Symmetry Breaking in a Quadrupolar Molecule Visualized in Time and Space.

The influence of the length of the push-pull branches of quadrupolar molecules on their excited-state symmetry breaking was investigated using ultrafast time-resolved IR spectroscopy. For this, the excited-state dynamics of an A-π-D-π-A molecule was compared with those of an ADA analogue, where the same electron donor (D) and acceptor (A) subunits are directly linked without a phenylethynyl π-spacer. The spatial distribution of the excitation was visualized in real time by monitoring C≡C and C≡N vibrational modes localized in the spacer and acceptor units, respectively.

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.

Direct local solvent probing by transient infrared spectroscopy reveals the mechanism of hydrogen-bond induced nonradiative deactivation.

The fluorescence quenching of organic dyes H-bonding interactions is a well-known phenomenon. However, the mechanism of this Hydrogen-Bond Induced Nonradiative Deactivation (HBIND) is not understood. Insight into this process is obtained by probing in the infrared the O-H stretching vibration of the solvent after electronic excitation of a dye with H-bond accepting cyano groups.

Influence of Solvent Relaxation on Ultrafast Excited-State Proton Transfer to Solvent.

A thorough understanding of the microscopic mechanism of excited-state proton transfer (ESPT) and the influence of the solvent environment on its dynamics are of great fundamental interest. We present here a detailed investigation of an ESPT to solvent (DMSO) using time-resolved broadband fluorescence and transient absorption spectroscopies. All excited-state species are resolved spectrally and kinetically using a global target analysis based on the two-step Eigen-Weller model.

Solute-Solvent Interactions and Excited-State Symmetry Breaking: Beyond the Dipole-Dipole and the Hydrogen-Bond Interactions.

Symmetry breaking of the excited state of a linear quadrupolar acceptor-donor-acceptor molecule was investigated using time-resolved infrared spectroscopy in 55 solvents allowing the influence of several solute-solvent interactions to be examined separately. No symmetry breaking was found in nonpolar solvents irrespective of their refractive index, indicating that differences in dispersion interactions between the two arms of the molecule do not suffice to induce an asymmetric distribution of the excitation. However, symmetry breaking was observed in nondipolar but quadrupolar solvents like benzene to an extent that can be as large as that found in medium dipolar solvents like THF.

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 A-D-A type molecules in the excited state, where D is an electron donor and A and A 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.