Accumulative Charge Separation in a Modular Quaterpyridine Bridging Ligand Platform and Multielectron Transfer Photocatalysis of π-Linked Dinuclear Ir(III)-Re(I) Complex for CO Reduction.

Four sterically distorted quaterpyridyl () ligandbridged Ir(III)-Re(I) heterometallic complexes (, , , and ), in which the position of the coupling pyridine unit of the two 2,2'-bipyridine ligands was varied (meta ()- or para ()-position), pypy-pypy ( = and , ; = and , ; = and , ; = and , ), were prepared, along with the fully π-conjugated Ir(III)-[π linker]-Re(I) complexes (π linker = 2,2'-bipyrimidine (), ; π linker = 2,5-di(pyridin-2-yl)pyrazine (), ) to elucidate the electron mediating and accumulative charge separation properties of the bridging π-linker in a bimetallic system (photosensitizer-π linker-catalytic center). From the photophysical and electrochemical studies, it was found that the quaterpyridyl () bridging ligand (BL), in which the two planar Ir/Re metalated bipyridine (bpy) ligands were connected but slightly canted relative to each other, linking the heteroleptic Ir(III) photosensitizer, [(C^N)Ir(bpy)], and catalytic Re(I) complex, (bpy)Re(CO)Cl, minimized the energy lowering of the BL, which hampers the forward photoinduced electron transfer (PET) process from [(C^N)Ir(N^N)] to (N^N)Re(CO)Cl ( = -(0.85-0.

Dynamics of Photoinduced Intramolecular and Intermolecular Electron Transfers in Ligand-Conjugated Ir(III)-Re(I) Photocatalysts.

We report the electron transfer (ET) dynamics in a series of Ir(III)-Re(I) photocatalysts where two bipyridyl ligands of Ir and Re moieties are conjugated at the ()- or ()-position of each side. Femtosecond transient absorption (TA) measurements identify the intramolecular ET (IET) dynamics from the Ir to Re moiety, followed by the formation of one-electron-reduced species (OERS) via the intermolecular ET with a sacrificial electron donor (SED). The IET rate depends on the bridging ligand (BL) structures (∼25 ps for BL vs ∼68 ps for BL), while the OERS formation happens on an even slower time scale (∼1.

Dynamics of Electron Transfers in Photosensitization Reactions of Zinc Porphyrin Derivatives.

Photocatalytic systems for CO reduction operate via complicated multi-electron transfer (ET) processes. A complete understanding of these ET dynamics can be challenging but is key to improving the efficiency of CO conversion. Here, we report the ET dynamics of a series of zinc porphyrin derivatives () in the photosensitization reactions where sequential ET reactions of occur with a sacrificial electron donor (SED) and then with TiO.

Multifaceted Excited State Dynamics of Coumarin Dyes Anchored on AlO Film.

The co-facially stacked dyes on semiconductor films serve as an alternative model to elucidate the photo-driven exciton dynamics occurring in a molecular assembly. In this study, we report the unique emission properties of coumarin dye adsorbed on the surface of the semiconductor film, measured by ultrafast time-resolved fluorescence. When a rigid coumarin derivative, 7-hydroxycoumarin-3-carboxylic acid (OHCCA), is anchored on the AlO film, the dye manifests dual emissions from the two lowest excited states.

Sustainable Carbon Dioxide Reduction of the P3HT Polymer-Sensitized TiO/Re(I) Photocatalyst.

In this study, a -type π-conjugated polymer chain, poly(3-hexylthiophene-2,5-diyl) (), was physically adsorbed onto -type TiO nanoparticles functionalized with a molecular CO reduction catalyst, (4,4-Y-bpy)Re(CO)Cl (ReP, Y = CHPO(OH)), to generate a new type of -heterogenized hybrid system (/TiO/ReP), and its photosensitizing properties were assessed in a heteroternary system for photochemical CO reduction. We found that immobilization on TiO facilitated photoinduced electron transfer (PET) from photoactivated * to the -type TiO semiconductor via rapid interfacial electron injection (∼65 ps) at the and TiO surface interface (* → TiO). With such effective charge separation, the heterogenization of onto TiO resulted in a steady electron supply toward the co-adsorbed Re(I) catalyst, attaining durable catalytic activity with a turnover number (TON) of ∼5300 over an extended time period of 655 h over five consecutive photoreactions, without deformation of the adsorbed polymer.

Complex Formation and Dissociation Dynamics on Amorphous Silica Surfaces.

Benzene complex formation and dissociation dynamics with silanols on the amorphous silica surfaces of nanoporous SiO, from a benzene/carbon tetrachloride solution, were measured by the growth of off-diagonal peaks in the two-dimensional infrared (2D IR) chemical exchange spectrum of the isolated Si-OD stretch. The presence of two types of isolated silanols, termed type I and II, was revealed, with dissociation time constants of 82 and 4.0 ps, respectively.

Influence of Vibronic Coupling on Ultrafast Singlet Fission in a Linear Terrylenediimide Dimer.

Singlet fission (SF) is a photophysical process capable of boosting the efficiency of solar cells. Recent experimental investigations into the mechanism of SF provide evidence for coherent mixing between the singlet, triplet, and charge transfer basis states. Up until now, this interpretation has largely focused on electronic interactions; however, nuclear motions resulting in vibronic coupling have been suggested to support rapid and efficient SF in organic chromophore assemblies.

Tuning the charge transfer character of the multiexciton state in singlet fission.

Intramolecular singlet fission (SF) produces the multiexciton correlated triplet pair state, (TT), prior to the formation of free triplet excitons. The nature of the multiexciton state is complex, as generation of the (TT) state may involve a charge transfer (CT) intermediate and has been shown to have both mixed electronic and spin characters. According to transient absorption spectroscopy, a linear terrylene-3,4:11,12-bis(dicarboximide) dimer (TDI) exhibits solvent-dependent excited-state dynamics.

Ancillary Ligand Effects on Heteroleptic Ir Dye in Dye-Sensitized Photocatalytic CO Reduction: Photoaccumulation of Charges on Arylated Bipyridine Ligand and Its Control on Catalytic Performance.

Herein, we report the synthesis, and photochemical and -physical properties, as well as the catalytic performance, of a series of heteroleptic Ir photosensitizers (IrPSs), [Ir(C^N) (N^N )] , possessing ancillary ligands that are varied with aryl-substituents on bipyridyl unit [C^N=(2-pyridyl)benzo[b]thiophen-3-yl (btp); N^N =4,4'-Y -bpy (Y=-Ph or -PhSi(Ph) ]. We found that the π-extension of bipyridyl ligand by aryl-substitution put bipyridyl ligand in use as an electron relay unit that performed charge accumulation before delivering to the catalytic center, greatly improving the overall CO -to-CO conversion activities. In a typical run, the aryl-substituted IrPS ( IrP-Ph )-sensitized homogeneous systems (IrPS+Re catalyst) gave a turnover number of 1340 (Φ =24.

Steric Interactions Impact Vibronic and Vibrational Coherences in Perylenediimide Cyclophanes.

Designing molecular systems that exploit vibronic coherence to improve light harvesting efficiencies relies on understanding how interchromophoric interactions, such as van der Waals forces and dipolar coupling, influence these coherences in multichromophoric arrays. However, disentangling these interactions requires studies of molecular systems with tunable structural relationships. Here, we use a combination of two-dimensional electronic spectroscopy and femtosecond stimulated Raman spectroscopy to investigate the role of steric hindrance between chromophores in driving changes to vibronic and vibrational coherences in a series of substituted perylenediimide (PDI) cyclophane dimers.

Imidazole and 1-Methylimidazole Hydrogen Bonding and Nonhydrogen Bonding Liquid Dynamics: Ultrafast IR Experiments.

The dynamics of imidazole (IM) and 1-methylimidazole (1-MeIM) in the liquid phase at 95 °C were studied by IR polarization selective pump-probe and two-dimensional IR (2D IR) spectroscopies. The two molecules are very similar structurally except that IM can be simultaneously a hydrogen bond donor and acceptor and therefore forms extended hydrogen-bonded networks. The broader IR absorption spectrum and a shorter vibrational lifetime of the vibrational probe, selenocyanate anion (SeCN), in IM vs 1-MeIM indicate that stronger hydrogen bonding exists between SeCN and IM.

Influence of Water on Carbon Dioxide and Room Temperature Ionic Liquid Dynamics: Supported Ionic Liquid Membrane vs the Bulk Liquid.

The influence of water on the dynamics of a room temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf), and CO in the RTIL was studied in the bulk liquid and a supported ionic liquid membrane (SILM) using two-dimensional infrared (IR) and IR polarization selective pump-probe spectroscopies. In the water-saturated bulk EmimNTf, the complete orientational randomization and structural spectral diffusion (SSD) of CO became faster than in the dry EmimNTf. In the poly(ether sulfone) SILM, only the longer time components of the SSD became faster in the water-saturated RTIL; the complete orientational randomization remained similar to the dry RTIL in the SILM.

Carbon Dioxide in a Supported Ionic Liquid Membrane: Structural and Rotational Dynamics Measured with 2D IR and Pump-Probe Experiments.

Supported ionic liquid membranes (SILMs) are porous membranes impregnated with ionic liquids (ILs) and used as advanced carbon capture materials. Here, two-dimensional infrared (2D IR) and IR polarization selective pump-probe (PSPP) spectroscopies were used to investigate CO reorientation and spectral diffusion dynamics in SILMs. The SILM contained 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonly)imide in the poly(ether sulfone) membrane with average pore size of ∼350 nm.

First Evidence of Vibrationally Driven Bimolecular Reactions in Solution: Reactions of Br Atoms with Dimethylsulfoxide and Methanol.

We present evidence for vibrational enhancement of the rate of bimolecular reactions of Br atoms with dimethylsulfoxide (DMSO) and methanol (CHOH) in the condensed phase. The abstraction of a hydrogen atom from either of these solvents by a Br atom is highly endoergic: 3269 cm for DMSO and 1416 or 4414 cm for CHOH, depending on the hydrogen atom abstracted. Thus, there is no thermal abstraction reaction at room temperature.

Dynamics of a Room Temperature Ionic Liquid in Supported Ionic Liquid Membranes vs the Bulk Liquid: 2D IR and Polarized IR Pump-Probe Experiments.

Supported ionic liquid membranes (SILMs) are membranes that have ionic liquids impregnated in their pores. SILMs have been proposed for advanced carbon capture materials. Two-dimensional infrared (2D IR) and polarization selective IR pump-probe (PSPP) techniques were used to investigate the dynamics of reorientation and spectral diffusion of the linear triatomic anion, SeCN, in poly(ether sulfone) (PES) membranes and room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf).

Comparative Study of Cl-Atom Reactions in Solution Using Time-Resolved Vibrational Spectroscopy.

A Cl atom can react with 2,3-dimethylbutane (DMB), 2,3-dimethyl-2-butene (DMBE), and 2,5-dimethyl-2,4-hexadiene (DMHD) in solution via a hydrogen-abstraction reaction. The large exoergicity of the reaction between a Cl atom and alkenes (DMBE and DMHD) makes vibrational excitation of the HCl product possible, and we observe the formation of vibrationally excited HCl (v = 1) for both reactions. In CCl4, the branching fractions of HCl (v = 1), Γ (v = 1), for the Cl-atom reactions with DMBE and DMHD are 0.

Polyphenols differentially inhibit degranulation of distinct subsets of vesicles in mast cells by specific interaction with granule-type-dependent SNARE complexes.

Anti-allergic effects of dietary polyphenols were extensively studied in numerous allergic disease models, but the molecular mechanisms of anti-allergic effects by polyphenols remain poorly understood. In the present study, we show that the release of granular cargo molecules, contained in distinct subsets of granules of mast cells, is specifically mediated by two sets of SNARE (soluble N-ethylmaleimide-sensitive factor attachment protein receptor) proteins, and that various polyphenols differentially inhibit the formation of those SNARE complexes. Expression analysis of RBL-2H3 cells for 11 SNARE genes and a lipid mixing assay of 24 possible combinations of reconstituted SNAREs indicated that the only two active SNARE complexes involved in mast cell degranulation are Syn (syntaxin) 4/SNAP (23 kDa synaptosome-associated protein)-23/VAMP (vesicle-associated membrane protein) 2 and Syn4/SNAP-23/VAMP8.

pH-responsive high-density lipoprotein-like nanoparticles to release paclitaxel at acidic pH in cancer chemotherapy.

Background: Nanoparticles undergoing physicochemical changes to release enclosed drugs at acidic pH conditions are promising vehicles for antitumor drug delivery. Among the various drug carriers, high-density lipoprotein (HDL)-like nanoparticles have been shown to be beneficial for cancer chemotherapy, but have not yet been designed to be pH-responsive.

Methods And Results: In this study, we developed a pH-responsive HDL-like nanoparticle that selectively releases paclitaxel, a model antitumor drug, at acidic pH.

Photoisomerization and relaxation dynamics of a structurally modified biomimetic photoswitch.

Recent experimental and theoretical studies on N-alkylated indanylidene pyrroline Schiff bases (NAIP) show that these compounds exhibit biomimetic photoisomerization analogous to that in the chromophore of rhodopsin. The NAIP compounds studied previously isomerize rapidly and often evolve coherently on the ground-electronic surface after reaction. We present the results of transient electronic absorption spectroscopy on dMe-OMe-NAIP, a newly synthesized NAIP analogue that differs from other NAIP compounds in the substituents on its pyrrolinium ring.

SNARE-wedging polyphenols as small molecular botox.

Most cosmetic and therapeutic applications of Clostridium botulinum neurotoxin (BoNT) are related to muscle paralysis caused by the blocking of neurotransmitter release at the neuromuscular junction. BoNT specifically cleaves SNARE proteins at the nerve terminal and impairs neuroexocytosis. Recently, we have shown that several polyphenols inhibit neurotransmitter release from neuronal PC12 cells by interfering with SNARE complex formation.

Neutral radical and singlet biradical forms of meso-free, -keto, and -diketo hexaphyrins(1.1.1.1.1.1): effects on aromaticity and photophysical properties.

We have investigated the electronic structures and photophysical properties of 5,10,20,25-tetrakis(pentafluorophenyl)-substituted hexaphyrin(1.1.1.

Solvent-dependent aromatic versus antiaromatic conformational switching in meso-(heptakis)pentafluorophenyl [32]heptaphyrin.

We have investigated conformational switching dynamics of meso-heptakis(pentafluorophenyl) [32]heptaphyrin(1.1.1.

Dissection of SNARE-driven membrane fusion and neuroexocytosis by wedging small hydrophobic molecules into the SNARE zipper.

Neuronal SNARE proteins mediate neurotransmitter release at the synapse by facilitating the fusion of vesicles to the presynaptic plasma membrane. Cognate v-SNAREs and t-SNAREs from the vesicle and the plasma membrane, respectively, zip up and bring about the apposition of two membranes attached at the C-terminal ends. Here, we demonstrate that SNARE zippering can be modulated in the midways by wedging with small hydrophobic molecules.

Aromaticity and photophysical properties of various topology-controlled expanded porphyrins.

Recently, expanded porphyrins have come to the forefront in the research field of aromaticity, and been recognized as the most appropriate molecular system to study both Hückel and Möbius aromaticity because their molecular topologies can be easily changed and controlled by various methods. Along with this advantage, many efforts have been devoted to the exploration of the aromaticity-molecular topology relationship based on electronic structures in expanded porphyrins so that further insight into the aromaticity--a very attractive field for chemists--can be provided. In this tutorial review, we describe the recent developments of various topology-controlled expanded porphyrins and their photophysical properties, in conjunction with the topological transformation between Hückel and Möbius aromaticity by various conformational control methods, such as synthetic methods, temperature control, and protonation.