Fast Structural Dynamics in Concentrated HCl Solutions: From Proton Hopping to the Bulk Viscosity.

Concentrated acid solutions, particularly HCl, have been studied extensively to examine the proton hopping and infrared spectral signatures of hydronium ions. Much less attention has been given to the structural dynamics of concentrated HCl solutions. Here, we apply optical heterodyne detected-optical Kerr effect (OHD-OKE) measurements to examine HCl concentration-dependent dynamics from moderate (0.8 m) to very high (15.5 m) concentrations and compare the results to the dynamics of NaCl solutions, as Na+ is similar in size to the hydronium cation. Both HCl and NaCl OHD-OKE signals decay as triexponentials at all concentrations, in contrast to pure water, which decays as a biexponential. Two remarkable features of the HCl dynamics are the following: (1) the bulk viscosity is linearly related to the slowest decay constant, t3, and (2) the concentration-dependent proton hopping times, determined by ab initio MD simulations and 2D IR chemical exchange experiments, both obtained from the literature, fall on the same line as the slowest structural dynamics relaxation time, t3, within experimental error. The structural dynamics of hydronium/chloride/water clusters, with relaxation times t3, are responsible for the concentration dependence of microscopic property of proton hopping and the macroscopic bulk viscosity. The slowest time constant (t3), which does not have a counterpart in pure water, is 3 ps at 0.8 m and increases by a factor of ∼2 by 15.5 m. The two fastest HCl decay constants, t1 and t2, are similar to those of pure water and increase mildly with the concentration.

Ethynylphenyl-Derivatized Free Base Porphyrins: Anodic Oxidation Processes and Covalent Grafting onto Glassy Carbon Electrodes.

In six of seven cases, direct anodic oxidation of the ethynyl group of an ethynylphenyl-derivatized free-base porphyrin gave modified glassy carbon electrodes in which the porphyrin was strongly surface-bound, most likely in a perpendicular geometry through covalent attachment of the ethynyl group to a surface carbon atom. The porphyrins each contained an ethynylphenyl group in one meso position and varied in the groups present in the other three meso positions. Electrografted 5,10,15,20-tetrakis(ethynylphenyl)porphyrin, H21, which has ethynyl moieties in all four meso positions, has well-defined surface voltammetry and grows to multilayer levels upon repeated cyclic voltammetry (CV) deposition scans. Multilayering was not observed to the same degree for monoethynylphenyl-substituted porphyrins and became progressively less for porphyrins having groups in the 15-meso position that were more protective against ethynyl radical attack. Clean molecular monolayer-level coverage was observed for 5-ethynylphenyl-10,20-bis(3-methoxyphenyl)-15-hexylporphyrin, H25. Owing to the fact that the ethynyl oxidation potential (1.1 to 1.5 V vs ferrocene) is more positive than that of the second macrocycle oxidation, the longevities and follow-up reactions of the porphyrin dications were also studied by CV, chemical oxidation, and optical spectroscopy in homogeneous solution. The primary follow-up products of the doubly oxidized porphyrins, whether surface-bound or in solution, were pyrrole-protonated species that were easily reduced back to the neutral porphyrin.

General Method for the Synthesis of Functionalized Tetrabenzo[8]circulenes.

Functionalized derivatives of the saddle-shaped molecule tetrabenzo[8]circulene were successfully synthesized through a Diels-Alder/oxidative cyclodehydrogenation approach. This methodology improves on our previously reported synthesis, affording products containing both electron-rich and electron-poor functional groups from readily available starting materials in a more efficient manner. The optoelectronic effects that result from the introduction of this functionality are presented and briefly discussed.

Water-in-Salt: Fast Dynamics, Structure, Thermodynamics, and Bulk Properties.

We present concentration-dependent dynamics of highly concentrated LiBr solutions and LiCl temperature-dependent dynamics for two high concentrations and compare the results to those of prior LiCl concentration-dependent data. The dynamical data are obtained using ultrafast optical heterodyne-detected optical Kerr effect (OHD-OKE). The OHD-OKE decays are composed of two pairs of biexponentials, i.e., tetra-exponentials. The fastest decay (t1) is the same as pure water's at all concentrations within error, while the second component (t2) slows slightly with concentration. The slower components (t3 and t4), not present in pure water, slow substantially, and their contributions to the decays increase significantly with increasing concentration, similar to LiCl solutions. Simulations of LiCl solutions from the literature show that the slow components arise from large ion/water clusters, while the fast components are from ion/water structures that are not part of large clusters. Temperature-dependent studies (15-95 °C) of two high LiCl concentrations show that decreasing the temperature is equivalent to increasing the room temperature concentration. The LiBr and LiCl concentration dependences and the two LiCl concentrations' temperature dependences all have bulk viscosities that are linearly dependent on τcslow, the correlation time of the slow dynamics (weighted averages of t3 and t4). Remarkably, all four viscosity vs 1/τCslow plots fall on the same line. Application of transition state theory to the temperature-dependent data yields the activation enthalpies and entropies for the dynamics of the large ion/water clusters, which underpin the bulk viscosity.

Dynamics of Acrylamide Hydrogels, Polymers, and Monomers in Water Measured with Optical Heterodyne-Detected Optical Kerr Effect Spectroscopy.

The ultrafast dynamics of acrylamide monomers (AAm), polyacrylamide (PAAm), and polyacrylamide hydrogels (PAAm-HG) in water were studied using optical heterodyne-detected optical Kerr effect (OHD-OKE) spectroscopy. Previous ultrafast infrared (IR) measurements of the water dynamics showed that at the same concentration of the acrylamide moiety, AAm, PAAm, and PAAm-HG exhibited identical water dynamics and that these dynamics slowed with increasing concentration. In contrast to the IR measurements, OHD-OKE experiments measure the dynamics of both the water and the acrylamide species, which occur on different time scales. In this study, the dynamics of all the acrylamide systems slowed with increasing concentration. We found that AAm exhibits tetraexponential decays, the longest component of which followed Debye-Stokes-Einstein behavior except for the highest concentration, 40% (w/v). Low concentrations of PAAm followed a single power law decay, while high concentrations of PAAm and all concentrations of PAAm-HG decayed with two power laws. The highest concentrations, 25% and 40%, of PAAm and PAAm-HG showed nearly identical dynamics. We interpreted this result as reflecting a similar extent of chain-chain interactions. At low concentrations, PAAm displays non-Markovian, single-chain dynamics (single power law), but PAAm displays entangled chain-chain interactions at high concentrations (two power laws). PAAm-HG has chain-chain interactions at all concentrations that arise from the cross-linking. At high concentrations, the dynamics of the entangled of PAAm become identical within error as those of the cross-linked PAAm-HG.

Dynamics of Concentrated Aqueous Lithium Chloride Solutions Investigated with Optical Kerr Effect Experiments.

We report the dynamics of concentrated lithium chloride aqueous solutions over a range of moderate to high concentrations. Concentrations (1-29 to 1-3.3 LiCl-water) were studied in which, at the highest concentrations, there are far too few water molecules to solvate the ions. The measurements were made with optically heterodyne-detected optical Kerr effect experiments, a non-resonant technique able to observe dynamics over a wide range of time scales and signal amplitudes. While the pure water decay is a biexponential, the LiCl-water decays are tetra-exponentials at all concentrations. The faster two decays arise from water dynamics, while the slower two decays reflect the dynamics of the ion-water network. The fastest decay (t1) is the same as pure water at all concentrations. The second decay (t2) is also the same as that of pure water at the lower concentrations, and then, it slows with increasing concentration. The slower dynamics (t3 and t4), which do not have counterparts in pure water, arise from ion-water complexes and, at the highest concentrations, an extended ion-water network. Comparisons are made between the concentration dependence of the observed dynamics and simulations of structural changes from the literature, which enable the assignment of dynamics to specific ion-water structures. The concentration dependences of the bulk viscosity and the ion-water network dynamics are directly correlated. The correlation provides an atomistic-level understanding of the viscosity.

Proton Transfer Dynamics in the Aprotic Proton Accepting Solvent 1-Methylimidazole.

The dynamics of proton transfer to the aprotic solvent 1-methylimidazole (MeIm, proton acceptor) from the photoacid 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS) was investigated using fast fluorescence measurements. The closely related molecule, 8-methoxypyrene-1,3,6-trisulfonic acid trisodium salt (MPTS), which is not a photoacid, was also studied for comparison. Following optical excitation, the wavelength-dependent population dynamics of HPTS in MeIm resulting from the deprotonation process were collected over the entire fluorescence emission window. Analysis of the time-dependent fluorescence spectra revealed four distinct fluorescence bands that appear and decay on different time scales. We label these four states as protonated (P), associated I (AI), associated II (AII), and deprotonated (D). We find that the simple kinetic scheme of P → AI → AII → D is not consistent with the data. Instead, the kinetic scheme that describes the data has P decaying into AI, which mainly goes on to deprotonation (D), but AI can also feed into AII. AII can return to AI or decay to the ground state, but does not deprotonate within experimental error. Quantum chemistry and excited state QM/MM Born-Oppenheimer molecular dynamics simulations indicate that AI and AII are two H-bonding conformations of MeIm to the HPTS hydroxyl, axial, and equatorial, respectively.