Evaluating the contributions to conductivity in room temperature ionic liquids.

The conductivity of room temperature ionic liquids is not described adequately by the Nernst-Einstein equation, which accounts only for Brownian motion of the ions. We report on the conductivity of the ionic liquid 1-butyl-3-methylimidazolum bis(trifluoromethylsulfonyl) imide (BMIM TFSI), comparing the known conductivity of this RTIL to the diffusion constants of the cationic and anionic species over a range of length scales, using time-resolved fluorescence depolarization and fluorescence recovery after photobleaching (FRAP) measurements of chromophores in the RTIL. Our data demonstrate that the diffusional contribution to molar conductivity is ca. 50%. Another mechanism for the transmission of charged species in RTILs is responsible for the "excess" molar conductivity, and we consider possible contributions.

Structure-Dependence and Mechanistic Insights into the Piezoelectric Effect in Ionic Liquids.

We reported recently that two imidazolium room-temperature ionic liquids (RTILs) exhibit the direct piezoelectric effect (J. Phys. Chem. Lett., 2023, 14, 2731-2735). We have subsequently investigated several other RTILs with pyrrolidinium and imidazolium cations and tetrafluoroborate and bis(trifluoromethylsulfonyl)imide anions in an effort to gain insight into the generality and mechanism of the effect. All the RTILs studied exhibit the direct piezoelectric effect, with a magnitude (d33) and threshold force that depend on the structures of both the cation and anion. The structure-dependence and existence of a threshold force for the piezoelectric effect are consistent with a pressure-induced liquid-to-crystalline solid phase transition in the RTILs, and this is consistent with experimental X-ray diffraction data.

Permeability and Dynamics of a Monolayer are Mediated by ITO Support Surface-Modification.

Indium tin oxide (ITO) has been extensively used as a transparent conductor. The surface chemistry of ITO is amenable to reactions similar to those used to modify silica, but a long-standing issue has been understanding the density and robustness of the ITO surface-modification. We report on the formation of chemically bound Cd2+-complexed octadecylphosphonic acid (ODPA) monolayer formed on a Langmuir trough and deposited using Langmuir-Blodgett (LB) methodology onto an ITO surface, either in its native form or functionalized with phosphonate (RPO32-). The organization of the Langmuir monolayer depends on the pH and presence of Cd2+ in the aqueous subphase on which it is formed and on the functionalization of the ITO surface. We probe the permeability of the resulting LB-support interface electrochemically and the motional freedom characteristic of chromophores contained within the monolayer using fluorescence recovery after photobleaching (FRAP). Our data demonstrate that without modification of the ITO surface the monolayer is significantly permeable by the electrophores used (ferrocene and Ru3+), and surface modification to produce covalently bound phosphonate functionality results in a monolayer that is impermeable to the electrophores. FRAP studies reveal a relatively rigid monolayer aliphatic chain region for deposition on either native or modified ITO, suggesting direct Cd2+-ITO interactions.

Role of Sn(II) in Mediating the Formation and Organization of a Langmuir Monolayer.

The influence of the Sn(II) ion on the formation and morphology of an arachidic acid (AA) monolayer was investigated using Langmuir film formation technology, pressure-area (Π-A) isotherm measurements, and Brewster angle microscopy (BAM). Our findings indicate that AA Langmuir monolayers exhibit organization that depends on subphase pH and Sn2+ concentration. There are multiple equilibria that are relevant to the complexation of AA monolayers, and the balance of Sn(OH)n equilibria and Sn(AA)n equilibria gives rise to unusual monolayer structural effects. With Sn2+ in the subphase, the AA monolayer exhibits an isotherm characterized by the absence of a collapse point and with a pH-dependent change in isotherm shape not consistent with the formation of an ordered solid phase. The amphiphile headgroup equilibrium mediates the absence of collapse seen experimentally and the ability of the monolayer to retain organization at a surface pressure of ca. 70 mN/m. BAM images show that the morphology of the monolayer depends on the Sn2+ concentration, consistent with several species of Sn(AA)n, where n = 1, 2, or 3, contributing to the overall monolayer order.

Ionic Liquids Exhibit the Piezoelectric Effect.

The piezoelectric effect was discovered over a century ago, and it has found wide application since that time. The direct piezoelectric effect is the production of charge upon application of force to a material, and the converse piezoelectric effect is a change in the material dimension(s) upon the application of a potential. To date, piezoelectric effects have been observed only in solid-phase materials. We report here the observation of the direct piezoelectric effect in room-temperature ionic liquids (RTILs). The RTILs 1-butyl-3-methyl imidazolium bis(trifluoromethyl-sulfonyl)imide (BMIM+TFSI-) and 1-hexyl-3-methyl imidazolium bis(trifluoromethylsulfonyl) imide (HMIM+TFSI-) produce a potential upon the application of force when confined in a cell, with the magnitude of the potential being directly proportional to the force applied. The effect is one order of magnitude smaller than that seen in quartz. This is the first report to our knowledge of the direct piezoelectric effect in a neat liquid. Its discovery has fundamental implications about the organization and dynamics in ionic liquids and invites theoretical treatment.

Relating the Induced Free Charge Density Gradient in a Room-Temperature Ionic Liquid to Molecular-Scale Organization.

We report on dilution-dependent changes in the local environments of chromophores incorporated into room-temperature ionic liquid (RTIL)-molecular solvent binary systems where the ionic liquid cation and molecular solvent possess the same alkyl chain length. We have used the RTIL 1-decyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (DMPyrr+TFSI-) and the molecular solvent 1-decanol. Perylene was used as a non-polar probe, and cresyl violet (CV+) was used as a polar probe chromophore. We observe that in both regions there is a change in the chromophore local environments with increasing 1-decanol content. The changes in the nonpolar regions of the binary RTIL-molecular solvent system occur at a lower 1-decanol concentration than changes in the polar regions. Both chromophores reorient as oblate rotors in this binary system, allowing detailed information on the relative values of the Cartesian components of the rotational diffusion constants to be extracted from the experimental data. The induced free charge density gradient, ρf, known to exist in RTILs, persists to high 1-decanol content (1-decanol mole fraction of 0.75), with the structural details of the gradient being reflected in depth-dependent changes in the Cartesian components of the rotational diffusion constants of CV+. This is the first time that changes in molecular organization have been correlated with ρf.

Cation structure-dependence of the induced free charge density gradient in imidazolium and pyrrolidinium ionic liquids.

We report on the structure-dependence and magnitude of the induced free charge density gradient (ρf) seen in room-temperature ionic liquids (RTILs) with imidazolium and pyrrolidinium cations. We characterize the spatially-resolved rotational diffusion dynamics of a trace-level cationic chromophore to characterize ρf in three different pyrrolidinium RTILs and two imidazolium RTILs. Our data show that the magnitude of ρf depends primarily on the alkyl chain length of RTIL cation and the persistence length of ρf is independent of RTILs' cation structure. These findings collectively suggest that mesoscopic structure in RTILs plays a significant role in allowing charge density gradients to form.

Cation structure-dependence of the Pockels effect in aprotic ionic liquids.

We report on the dependence of surface charge-induced birefringence (the Pockels effect) in room temperature ionic liquids (RTILs) with different cation constituents. The induced birefringence is related to the induced free charge density gradient (ρf) in the RTIL. The RTILs are confined in a lens-shaped cell and the surface charge density of the concave cell surface is controlled by the current passed through the surface ITO film. We find that, in all cases, the induced birefringence is proportional to the surface charge density and that the change in refractive index nearest the ITO surface can be on the order of 20%. Our findings indicate that the induced birefringence depends more sensitively on the cation aliphatic substituent length than on the identity of the charge-carrying headgroup.

Quantitating the Binding Energy of Metal Ions to Langmuir-Blodgett Monolayers: The Copper(II)-Octadecylphosphonic Acid System.

We report on the formation and organization of a Cu2+-complexed octadecylphosphonic acid (ODPA) monolayer formed by Langmuir-Blodgett deposition. The formation of the Cu-complexed monolayer is seen to depend sensitively on the subphase pH and Cu2+ concentration, and it is possible to form a monolayer containing the regions of complexed and free ODPA. From the pressure-area isotherm data for these monolayers, we determine the equilibrium constant and free energy of formation for the Cu2+-ODPA complex, ΔG = -22.5 kJ/mol.

The effect of dilution on induced free charge density gradients in room temperature ionic liquids.

We report on changes in the magnitude and length scale of the induced free charge density gradient, ρf, in three imidazolium room temperature ionic liquids (RTILs) with dilution by methanol and acetonitrile. Using depth- and time-resolved fluorescence measurements of cresyl violet rotational diffusion, we find that ρf persists in RTILs to varying degrees depending on RTIL and diluent identity, and in all cases the functional form of ρf is not a smooth monotonic diminution in either magnitude or persistence length with increasing diluent, but a stepwise collapse. This finding is consistent with changes in the bulk RTIL as a function of dilution seen using rotational diffusion measurements that show the rotating entity in bulk RTILs exhibits a larger effective hydrodynamic volume than would be expected based on bulk viscosity data for the diluted RTILs. This excess hydrodynamic volume can be understood in the context of aggregation of RTIL ion pairs in the diluted RTIL system. The size of the aggregates is seen to depend on RTIL identity and diluent, and in all cases aggregate size increases with increasing dilution. This finding is consistent with the ρf dependence on dilution data. The collapse of ρf is seen to correlate with the onset of RTIL ion pair dimer formation, a condition that may facilitate dissociated RTIL ion mobility in the binary system.

Intramolecular Relaxation Dynamics Mediated by Solvent-Solute Interactions of Substituted Fluorene Derivatives. Solute Structural Dependence.

Several fluorene derivatives exhibit excited-state reactivity and relaxation dynamics that remain to be understood fully. We report here the spectral relaxation dynamics of two fluorene derivatives to evaluate the role of structural modification in the intramolecular relaxation dynamics and intermolecular interactions that characterize this family of chromophores. We have examined the time-resolved spectral relaxation dynamics of two compounds, NCy-FR0 and MK-FR0, in protic and aprotic solvents using steady-state and time-resolved emission spectroscopy and quantum chemical computations. Both compounds exhibit spectral relaxation characteristics similar to those seen in FR0, indicating that hydrogen bonding interactions between the chromophore and solvent protons play a significant role in determining the relaxation pathways available to three excited electronic states.

Excited-State Dynamics of a Substituted Fluorene Derivative. The Central Role of Hydrogen Bonding Interactions with the Solvent.

Substituted fluorene structures have demonstrated unusual photochemical properties. Previous reports on the substituted fluorene Schiff base FR0-SB demonstrated super photobase behavior with a ΔpKb of ∼14 upon photoexcitation. In an effort to understand the basis for this unusual behavior, we have examined the electronic structure and relaxation dynamics of the structural precursor of FR0-SB, the aldehyde FR0, in protic and aprotic solvents using time-resolved fluorescence spectroscopy and quantum chemical calculations. The calculations show three excited singlet states in relatively close energetic proximity. The spectroscopic data are consistent with relaxation dynamics from these electronic states that depend on the presence and concentration of solvent hydroxyl functionality. These results underscore the central role of solvent hydrogen bonding to the FR0 aldehyde oxygen in mediating the relaxation dynamics within this molecule.

Controlling Quantum Interference between Virtual and Dipole Two-Photon Optical Excitation Pathways Using Phase-Shaped Laser Pulses.

Two-photon excitation (TPE) proceeds via a "virtual" pathway, which depends on the accessibility of one or more intermediate states, and, in the case of non-centrosymmetric molecules, an additional "dipole" pathway involving the off-resonance dipole-allowed one-photon transitions and the change in the permanent dipole moment between the initial and final states. Here, we control the quantum interference between these two optical excitation pathways by using phase-shaped femtosecond laser pulses. We find enhancements by a factor of up to 1.75 in the two-photon-excited fluorescence of the photobase FR0-SB in methanol after taking into account the longer pulse duration of the shaped laser pulses. Simulations taking into account the different responses of the virtual and dipole pathways to external fields and the effect of pulse shaping on two-photon transitions are found to be in good agreement with our experimental measurements. The observed quantum control of TPE in the condensed phase may lead to an enhanced signal at a lower intensity in two-photon microscopy, multiphoton-excited photoreagents, and novel spectroscopic techniques that are sensitive to the magnitude of the contributions from the virtual and dipole pathways to multiphoton excitations.

Translational Diffusion Dynamics in Divalent Metal-Phosphonate Monolayers.

Self-assembled monolayers are attractive for surface modification due to their ease of synthesis and the range of chemical functionality that can be applied. Metal-phosphonate monolayer properties can be controlled through the metal ions that can be used in their formation. The organization and fluid properties of these monolayers can be understood in the context of their thermodynamic properties and the association and dissociation kinetics that proceed at the metal-phosphonate complex. In this work, four different M(II)-phosphonate monolayers were synthesized and the diffusional behavior of free and tethered chromophores was evaluated using fluorescence recovery after photobleaching measurements. The ω-terminal group identity of the metal-phosphonate monolayer was varied to determine its effect on monolayer dynamics.

Ceramide-mediation of diffusion in supported lipid bilayers.

The fluidity and compositional heterogeneity of the mammalian plasma membrane play deterministic roles in a variety of membrane functions. Designing model bilayer systems allows for compositional control over these properties. Ceramide is a phospholipid capable of extensive headgroup-region hydrogen bonding, and we report here on the role of ceramide in planar model bilayers. We use fluorescence recovery after photobleaching (FRAP) to obtain translational diffusion constants of two chromophores in supported model bilayers composed of cholesterol, 1,2-dioleoyl-sn-phosphatidylcholine (DOPC), sphingomyelin, and ceramide. FRAP data for perylene report on the acyl chain region of the model bilayer and FRAP data for 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine-N-(lissamine rhodamine B sulfonyl) sense diffusional dynamics in the bilayer headgroup region. Dynamics in the headgroup region exhibit anomalous diffusion behavior that is characteristic of spatially heterogeneous media.

Effects of ethanol and n-butanol on the fluidity of supported lipid bilayers.

The interactions of molecules such as short-chain alcohols with the mammalian plasma membrane are thought to play a role in anesthetic effects. We have examined the concentration-dependent effects of ethanol and n-butanol on the fluidity of planar model lipid bilayer structures supported on mica. The supported model bilayer was composed of 1,2-dioleoyl-sn-phosphatidylcholine (DOPC), cholesterol, and sphingomyelin, and the bilayers were formed by vesicle fusion from extruded unilamellar vesicles (133 nm diameter, polydispersity index of 0.17). Controlled amounts of ethanol and n-butanol were added during vesicle deposition. Translational diffusion constants were obtained utilizing fluorescence recovery after photobleaching (FRAP) measurements on the micrometer scale with perylene as the fluorophore. The translational diffusion constants increased and then decreased with increasing ethanol concentration, with the bilayer structure degrading at ca. 0.8 M ethanol. A similar trend was observed for n-butanol at lower alcohol concentrations owing to greater interactions with phospholipid bilayer constituents. For n-butanol, the integrity of the planar bilayer structure deteriorated at ca. 0.4 M n-butanol. The results are consistent with bilayer interdigitation.

Charge-Induced Birefringence in a Room-Temperature Ionic Liquid.

We have reported previously on the existence of a surface charge-induced free charge density gradient (ρf) in room-temperature ionic liquids (RTILs) with a characteristic persistence length of ca. 50 µm [Ma, K. Langmuir 2016, 32, 9507-9512]. The free charge density gradient is related to the dielectric response of the RTIL. We report here on the existence of a surface charge-induced gradient in the RTIL refractive index and quantify the relationship between the index gradient and ρf. Because ρf is uniaxial, the induced refractive index gradient is manifested as an induced birefringence. The RTIL sample holder has a curved surface such that the RTIL can function as a lens, and ρf is controlled by the surface charge density (σs) of the (concave) RTIL support. Current passed through an indium-doped tin oxide (ITO) surface layer on the support surface controls σs. The far-field image of light passed through the RTIL lens as a function of σs is used to measure the charge-induced changes of n in the RTIL. We demonstrate a modulation of the refractive index on the order of 15%, proportional to σs. This report places the relationship between ρf and RTIL dielectric response on a quantitative footing and suggests the utility of RTILs for electro-optic applications.

Isoenergetic two-photon excitation enhances solvent-to-solute excited-state proton transfer.

Two-photon excitation (TPE) is an attractive means for controlling chemistry in both space and time. Since isoenergetic one- and two-photon excitations (OPE and TPE) in non-centrosymmetric molecules are allowed to reach the same excited state, it is usually assumed that they produce similar excited-state reactivity. We compare the solvent-to-solute excited-state proton transfer of the super photobase FR0-SB following isoenergetic OPE and TPE. We find up to 62% increased reactivity following TPE compared to OPE. From steady-state spectroscopy, we rule out the involvement of different excited states and find that OPE and TPE spectra are identical in non-polar solvents but not in polar ones. We propose that differences in the matrix elements that contribute to the two-photon absorption cross sections lead to the observed enhanced isoenergetic reactivity, consistent with the predictions of our high-level coupled-cluster-based computational protocol. We find that polar solvent configurations favor greater dipole moment change between ground and excited states, which enters the probability for TPE as the absolute value squared. This, in turn, causes a difference in the Franck-Condon region reached via TPE compared to OPE. We conclude that a new method has been found for controlling chemical reactivity via the matrix elements that affect two-photon cross sections, which may be of great utility for spatial and temporal precision chemistry.

Steric effects in light-induced solvent proton abstraction.

The significance of solvent structural factors in the excited-state proton transfer (ESPT) reactions of Schiff bases with alcohols is reported here. We use the super photobase FR0-SB and a series of primary, secondary, and tertiary alcohol solvents to illustrate the steric issues associated with solvent to photobase proton transfer. Steady-state and time-resolved fluorescence data show that ESPT occurs readily for primary alcohols, with a probability proportional to the relative -OH concentration. For secondary alcohols, ESPT is greatly diminished, consistent with the barrier heights obtained using quantum chemistry calculations. ESPT is not observed in the tertiary alcohol. We explain ESPT using a model involving an intermediate hydrogen-bonded complex where the proton is "shared" by the Schiff base and the alcohol. The formation of this complex depends on the ability of the alcohol solvent to achieve spatial proximity to and alignment with the FR0-SB* imine lone pair stabilized by the solvent environment.

Proton Abstraction Mediates Interactions between the Super Photobase FR0-SB and Surrounding Alcohol Solvent.

We report on the motional and proton transfer dynamics of the super photobase FR0-SB in the series of normal alcohols C1 (methanol) through C8 (n-octanol) and ethylene glycol. Steady-state and time-resolved fluorescence data reveal that the proton abstraction dynamics of excited FR0-SB depend on the identity of the solvent and that the transfer of the proton from solvent to FR0-SB*, forming FR0-HSB+*, fundamentally alters the nature of interactions between the excited molecule and its surroundings. In its unprotonated state, solvent interactions with FR0-SB* are consistent with slip limit behavior, and in its protonated form, intermolecular interactions are consistent with a much stronger interaction of FR0-HSB+* with the deprotonated solvent RO-. We understand the excited-state population dynamics in the context of a kinetic model involving a transition state wherein FR0-HSB+* is still bound to the negatively charged alkoxide, prior to solvation of the two charged species. Data acquired in ethylene glycol confirm the hypothesis that the rotational diffusion dynamics of FR0-SB* are largely mediated by solvent viscosity while proton transfer dynamics are mediated by the lifetime of the transition state. Taken collectively, our results demonstrate that FR0-SB* extracts solvent protons efficiently and in a predictable manner, consistent with a ca. 3-fold increase in dipole moment upon photoexcitation as determined by ab initio calculations based on the equation-of-motion coupled-cluster theory.