Photo-induced Charge Separation of p-Tricyanovinyl-N,N-Dialkylanilines

In this paper,p-tricyanovinyl-N,N-dialkylanilines were synthesized as model compounds and through their spectroscopic behavior,the photo-induced electron transfer,charge separation were discussed and the aggregation in DMSO-H_2O system was investigated.     

Charge shift bonding concept in radical π-dimers

We show that pancake bonding in radical π-dimers display features of charge shift (CS) bonding. While the CS bonding concept has been developed to interpret the unusual aspects of σ-bonds around centers with a large number of lone pairs, such as F(2) and HOOH, we find a similar role played by the nonbonding or slightly bonding π-electron pairs in π-stacking radical dimers. Arguments and computational evidence indicate that the CS bonding concept developed by Shaik and Hiberty et al. captures essential features of the intermolecular bonding in radical π-dimers in which the overlap of the two radical centered singly occupied molecular orbitals (SOMOs) play a crucial role. By using the tetracyanoethylene anion dimer, [TCNE](2)(2-), as a model, we show that compared to CAS(2,2) calculations, significant binding contributions are recovered in the calculations simply by including selected intrapair excitations of the SOMO-SOMO bonding orbitals and the nonbonding π-orbitals. This observation is the basis for the analogy of chemical bonding between pancake bonded radical π-dimers and other charge shift bonded molecules, such as F(2). By extending the CS bonding concept to a new class of molecules, we find a novel application of the lone pair bond weakening effect (LPBWE) in which the doubly occupied π-orbitals play the role of lone pairs.     

Do Charge State Signatures Guarantee Protein Conformations?

The extent to which proteins in the gas phase retain their condensed-phase structure is a hotly debated issue. Closely related to this is the degree to which the observed charge state reflects protein conformation. Evidence from electron capture dissociation, hydrogen/deuterium exchange, ion mobility, and molecular dynamics shows clearly that there is often a strong correlation between the degree of folding and charge state, with the most compact conformations observed for the lowest charge states. In this article, we address recent controversies surrounding the relationship between charge states and folding, focussing also on the manipulation of charge in solution and its effect on conformation. 'Supercharging' reagents that have been used to effect change in charge state can promote unfolding in the electrospray droplet. However for several protein complexes, supercharging does not appear to perturb the structure in that unfolding is not detected. Consequently, a higher charge state does not necessarily imply unfolding. Whilst the effect of charge manipulation on conformation remains controversial, there is strong evidence that a folded, compact state of a protein can survive in the gas phase, at least on a millisecond timescale. The exact nature of the side-chain packing and secondary structural elements in these compact states, however, remains elusive and prompts further research.     

Excited-state Intramolecular Proton–transfer-induced Charge Transfer of Polyquinoline

The excited-state intramolecular proton–transfer-induced charge transfer of semirigid polyquinoline (PQH) is explored in 1,1,2,2-tetrachloroethane (TCE) and N-methyl-2-pyrrolidinone (MP) using picosecond time-resolved fluorescence spectroscopy. Reaction mechanisms are found to depend on the rotational conformations of PQH at the moment of excitation; whereas the trans-enolic form does not undergo intramolecular proton transfer within its excited-state lifetime, the cis-enolic form does within 15 ps to form a tautomeric zwitterion species. While the subsequent intramolecular charge transfer of the zwitterionic species to yield a tautomeric keto species takes place on time scales of 25 ps in TCE (ε = 8.50) and 62 ps in MP (ε = 32.55), its reverse reaction is also followed on time scales of 28 ps in TCE and 20 ps in MP. The lack of a kinetic isotope effect in both forward and reverse charge-transfer reactions support our proposed mechanisms.     

Charge transfer properties of Tröger base derivatives

Two triarylamine centers bridged through an aliphatic bridge feature unexpected charge transfer properties, bearing an important electronic coupling between them in the absence of a π linker; EPR, electrochemistry, electronic spectroscopy and first principles molecular calculations are combined to study the electronic structure of this compound.     

Why Are Proteins Charged? Networks of Charge–Charge Interactions in Proteins Measured by Charge Ladders and Capillary Electrophoresis

Almost all proteins contain charged amino acids. While the function in catalysis or binding of individual charges in the active site can often be identified, it is less clear how to assign function to charges beyond this region. Are they necessary for solubility? For reasons other than solubility? Can manipulating these charges change the properties of proteins? A combination of capillary electrophoresis (CE) and protein charge ladders makes it possible to study the roles of charged residues on the surface of proteins outside the active site. This method involves chemical modification of those residues to generate a large number of derivatives of the protein that differ in charge. CE separates those derivatives into groups with the same number of modified charged groups. By studying the influence of charge on the properties of proteins using charge ladders, it is possible to estimate the net charge and hydrodynamic radius and to infer the role of charged residues in ligand binding and protein folding.     

Twisted Intramolecular Charge Transfer in Polydimethylsilylene Bearing Pyrenyl Groups

Polydimethylsilylenes bearing pyrenyl groups exhibit emissions fromtwisted intramolecular charge transfer state between the aromatic ring and thesilicon backbone both in polar and nonpolar solvents.     

“Anti-electrostatic” Halogen Bonding between Ions of Like Charge

Halogen bonding occurs between molecules featuring Lewis acidic halogen substituents and Lewis bases. It is often rationalized as a predominantly electrostatic interaction and thus interactions between ions of like charge (e. g., of anionic halogen bond donors with halides) seem counter-intuitive. Herein, we provide an overview on such complexes. First, theoretical studies are described and their findings are compared. Next, experimental evidences are presented in the form of crystal structure database analyses, recent examples of strong “anti-electrostatic” halogen bonding in crystals, and the observation of such interactions also in solution. We then compare these complexes to select examples of “counter-intuitive” adducts formed by other interactions, like hydrogen bonding. Finally, we comment on key differences between charge-transfer and electrostatic polarization.     

Charge transfer characteristics of F6TCNNQ–gold interface

The metal–organic interface between polycrystalline gold and hexafluorotetracyanonaphthoquinodimethane (F₆TCNNQ) was investigated by photoelectron spectroscopy with the focus on the charge transfer characteristics from the metal to the molecule. The valence levels, as well as the core levels of the heterojunction, indicate a full electron transfer and a change in the chemical environment. The changes are observed in the first F₆TCNNQ layers, whereas for further film growth, only neutral F₆TCNNQ molecules could be detected. New occupied states below the Fermi level were observed in the valence levels, indicating a lowest unoccupied molecular orbital (LUMO) occupation due to the charge transfer. A fitting of the spectra reveals the presence of a neutral and a charged F₆TCNNQ molecules, but no further species were present.     

Molecular-Orbital Delocalization Enhances Charge Transfer in π-Conjugated Organic Semiconductors

π-Conjugated organic semiconductors are promising materials for surface-enhanced Raman scattering (SERS)-active substrates based on the tunability of electronic structures and molecular orbitals. Herein, we investigate the effect of the temperature-mediated resonance-structure transitions of poly(3,4-ethylenedioxythiophene) (PEDOT) in poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT : PSS) films on the interactions between substrate and probe molecules, thereby affecting the SERS activity. Absorption spectroscopy and density functional theory calculations show that this effect occurs mainly due to delocalization of the electron distribution in molecular orbitals, effectively promoting the charge transfer between the semiconductor and probe molecules. In this work, we investigate for the first time the effect of electron delocalization in molecular orbitals on SERS activity, which will provide new design ideas for the development of highly sensitive SERS substrates.     

Charge transfer across the water/nitrobenzene interface by three-electrode system

A droplet of aqueous solution containing a certain molar ratio of redox couple is first attached onto a platinum electrode surface, then the resulting drop electrode is immersed into the organic solution containing very hydrophobic electrolyte. Combined with reference and counter electrodes, a classical three-electrode system has been constructed. Ion transfer (IT) and electron transfer (ET) are investigated systematically using three-electrode voltammetry. Potassium ion transfer and electron transfer between potassium ferricyanide in the aqueous phase and ferrocene in nitrobenzene are observed with potassium ferricyanide/potassium ferrocyanide as the redox couple. Meanwhile, the transfer reactions of lithium, sodium, potassium, proton and ammonium ions are obtained with ferric sulfate/ferrous sulfate as the redox couple. The formal transfer potentials and the standard Gibbs transfer energy of these ions are evaluated and consistent with the results obtained by a four-electrode system and other methods.     

Uncommon Intramolecular Charge Transfer Effect and Its Potential Application in OLED Emitters

Planarized intramolecular charge transfer(PLICT)state can facilitate the fluorescence process thanks to the relative excellent planarity.Recently,we have discovered that the excited state quinone-conformation induced planarization(ESQIP)occurring on tetraphenylpyrazine(TPP)based derivatives could furnish them with PLICT feature.Unlike to the well-known intramolecular charge transfer,strengthening the electron-donating nature on the donor(D)moiety did not impair the PLICT.The calculation results showed that planarization of the TPP based compounds scarcely accompanied with energy wastage while amount of energy was required for the torsion on geometries.In the polar solvents,the energy consumption for planarization could further decrease,but that for twisting structure would increase.To take advantage of the transformation of the frontier orbitals'distribution,the PLICT type materials would perform a potential application on organic light-emitting diodes(OLEDs).     

High Charge Mobility of a Perylene Bisimide Dye with Hydrogen-bond Formation Group

Charge carrier mobility is one of the most important parameters concerning the performance of organic electronic devices1.High mobility usually leads to high calculation speed in computer and high short-circuit current in organic solar cells.Unfortunately,the intrinsic charge mobilities for organic semiconductors are of orders of magnitude lower than amorphous silicon.As a promising n-type organic semiconductor,N,N′-n-alkyl-perylene bisimides have shown their electron mobility to be up to10-…     

Formation and Photoelectrochemical Properties of Charge Transfer Complexes between Fullerene and Metallophthalocyanine

Fullerelleshavegeneratedarapidlygrowingandactiveresearchareabecauseoftheirunusualstructureandphysico-chemicalproperties.Fullerenes(C,.,.C,,)havehigherelectrollaffinity(2.75ev),soitiswellkllownthattheyareexcellentelectronacceptorsandhavealargenumberofcolljugatedrsbondswhichmayleadtolargenon-linearpolarizabilities'.C,,.,isreportedtoformchargetranstbrcomplexes(CTC)withappropriateelectrondonors,forexample,polymolecularPVK,y-cyclodextrin,aromaticandaliphaticammes'-3.Thecharge-transferinteraction…     

Effect of Amines on the Surface Charge Properties of Iron Oxides

Specific studies detailing the effects of amines, used as pH control agents for corrosion inhibition in power plants, on the surface charge of iron oxides provide data to assess the mechanism of how these amines impact deposition rate. The current study was undertaken in order to determine accurately the dissociation constants of the relevant amines at Pressurized Water Reactor (PWR) operating conditions and to investigate the effect of sorption of two of these amines (morpholine and dimethylamine) by magnetite. The acid-dissociation equilibria of morpholine (MOR), dimethylamine (DMA) and ethanolamine (ETA) were measured potentiometrically with a hydrogen-electrode concentration cell (HECC) from 0 to 290 °C in sodium trifluoromethanesulfonate (NaTr) solutions at ionic strengths up to 1 mol⋅kg⁻¹. Magnetite surface titrations were performed at an ionic strength of 0.03 mol⋅kg⁻¹ (NaTr medium) in the presence or absence of morpholine and dimethylamine buffers over a wide range of pH and total amine concentrations at 150–250 °C. D.A. Palmer is retired.