Design and synthesis of TiO2/C nanosheets with a directional cascade carrier transfer

Directed transfer of carriers, akin to excited charges in photosynthesis, in semiconductors by structural design is challenging. Here, TiO₂ nanosheets with interlayered sp² carbon and titanium vacancies are obtained by low-temperature controlled oxidation calcination. The directed transfer of carriers from the excited position to Ti-vacancies to interlayered carbon is investigated and proven to greatly increase the charge transport efficiency. The TiO₂/C obtained demonstrates excellent photocatalytic and photoelectrochemical activity and significant lithium/sodium ion storage performance. Further theoretical calculations reveal that the directional excited position/Ti-vacancies/interlayered carbon facilitate the spatial inside-out cascade electron transfer, resulting in high charge transfer kinetics.

Directional charge transfer in TiO₂ nanosheets is achieved by design of TiO₂ lattice-Ti vacancy-interlayered sp² carbon at the interface.     

Graphene-carbon nanotubes modified graphite electrode for the determination of nicotinamide adenine dinucleotide and fabrication of alcohol biosensor

Through layer-by-layer adsorption (LBL) technique, the positively charged multiwalled carbon nanotubes (MWCNTs) and negatively charged graphene multilayer film were formed on graphite-poly(diallyldimethylammoniumchloride)-polystyrenesulphonate (Gr/PDDA/PSS) modified electrode. Due to large surface area and remarkable electrocatalytic properties of MWCNTs and graphene, the Gr/(PDDA/PSS-[MWCNTs-NH ₃ ⁺ -graphene-COO^?]₅) electrode exhibits potent electrocatalytic activity towards the electro-oxidation of nicotinamide adenine dinucleotide (NADH). A substantial decrease in the overpotential was observed at modified electrode, and the electrode showed high sensitivity to the electrocatalytic oxidation of NADH. The modified electrode was characterized by cyclic voltammetry and electrochemical impedance spectroscopy. The diffusion coefficient was calculated by chronocoulometry. Chronoamperometric studies showed the linear relationship between oxidation peak current and the concentration of NADH in the range 25–250?μM (R?=?0.999) with the detection limit of 0.1?μM (S/N?=?3). Further, dopamine, uric acid, acetaminophen and hydrogen peroxide do not interfere in the detection of NADH. The ability of MWCNTs and graphene to promote the electron transfer between NADH and the electrode exhibits a promising biocompatible platform for development of dehydrogenase-based amperometric biosensors. Alcohol dehydrogenase (ADH) was casted on Gr/(PDDA/PSS-[MWCNTs-NH ₃ ⁺ -graphene-COO^?]₅) electrode; the resulting biosensor showed rapid and high sensitive amperometric response to ethanol with the detection limit of 10?μM (S/N?=?3).     

Solvent-controlled ion-coupled charge transport in microporous metal chalcogenides

Interactions between ions and itinerant charges govern electronic processes ranging from the redox chemistry of molecules to the conductivity of organic semiconductors, but remain an open frontier in the study of microporous materials. These interactions may strongly influence the electronic behavior of microporous materials that confine ions and charges to length scales comparable to proton-coupled electron transfer. Yet despite mounting evidence that both solvent and electrolyte influence charge transport through ion–charge interactions in metal–organic frameworks, fundamental microscopic insights are only just beginning to emerge. Here, through electrochemical analysis of two open-framework chalcogenides TMA₂FeGe₄S₁₀ and TMA₂ZnGe₄S₁₀, we outline the key signatures of ion-coupled charge transport in band-type and hopping-type microporous conductors. Pressed-pellet direct-current and impedance techniques reveal that solvent enhances the conductivity of both materials, but for distinct mechanistic reasons. This analysis required the development of a fitting method that provides a novel quantitative metric of concerted ion–charge motion. Taken together, these results provide chemical parameters for a general understanding of electrochemistry in nanoconfined spaces and for designing microporous conductors and electrochemical methods used to evaluate them.

Interactions between ions and itinerant charges govern electronic processes ranging from the redox chemistry of molecules to the conductivity of organic semiconductors, but remain an open frontier in the study of microporous materials.     

Converting molecular luminescence to ultralong room-temperature phosphorescence via the excited state modulation of sulfone-containing heteroaromatics

Manipulating the molecular orbital properties of excited states and the subsequent relaxation processes can greatly alter the emission behaviors of luminophores. Herein we report a vivid example of this, with luminescence conversion from thermally activated delayed fluorescence (TADF) to ultralong room-temperature phosphorescence (URTP) via a facile substituent effect on a rigid benzothiazino phenothiazine tetraoxide (BTPO) core. Pristine BTPO with multiple heteroatoms shows obvious intramolecular charge transfer (ICT) excited states with small exchange energy, featuring TADF. Via delicately functionalizing the BTPO core with peripheral moieties, the excited states of the BTPO derivatives become a hybridized local and charge transfer (HLCT) state in the S₁ state and a local excitation (LE) dominated HLCT state in the T₁ state, with enlarged energy bandgaps. Upon dispersion in a polymer matrix, the BTPO derivatives exhibit a persistent bright green afterglow with long lifetimes of up to 822 ms and decent quantum yields of up to 11.6%.

The decoration of a BTPO core results in a change in the luminescence nature from TADF to URTP. The phosphors in an amorphous PMMA matrix showed monomeric URTP with phosphorescence lifetimes of up to 822 ms and quantum yields of up to 11.6%.     

Two-dimensional heterostructures built from ultrathin CeO2 nanosheet surface-coordinated and confined metal–organic frameworks with enhanced stability and catalytic performance

Two-dimensional (2D) metal–organic framework (MOF) based heterostructures will be greatly advantageous to enhance catalytic performance because they increase the contact surface and charge transfer. Herein, a novel 2D heterostructure named CeO₂@NiFe-MOFs, in which monolayer NiFe-MOFs is coordinated with ceria (CeO₂) to improve catalytic and stability performance, is successfully constructed by the strategy of in situ growth on the surface of ultrathin CeO₂ nanosheets being functionalized with monolayer carboxylic acid groups. The 2D heterostructure possesses a sandwich structure, where monolayer NiFe-MOFs are coordinated to both the top and bottom surface of CeO₂ nanosheets via joining carboxylic acid groups. In particular, CeO₂ with robust coordination plays a significant role in the anchoring of carboxylic acid groups and binding strength of heterostructures. The 2D CeO₂@NiFe-MOF heterostructure with a joint effect of metal–ligand coordination not only presents good structural stability but also significantly enhances the oxygen evolution reaction (OER) efficiencies in comparison to bare NiFe-MOFs, achieving a current density of 20 mA cm⁻² at a low overpotential of 248 mV as well as durability for at least 40 h. Meanwhile, the electronics, optics, band gap energy and local strains of CeO₂ decorated with 2D NiFe-MOFs are different to the properties of bare CeO₂. Our study on the construction of an ultrathin CeO₂ surface-coordinated and confined MOF layer may pave a new way for novel 2D MOF composites/heterostructures or multi-functional 2D CeO₂ materials to be used in energy conversion or other fields.

A synthetic strategy to prepare 2D heterostructures from ultrathin CeO₂ surface-coordinated metal–organic framework was proposed, proving multiple effects of metal-coordinated interactions in 2D heterostructures.     

Mutually exclusive hole and electron transfer coupling in cross stacked acenes

The topology of frontier molecular orbitals (FMOs) induces highly sensitive charge transfer coupling with variation in the intermolecular arrangement. A consistent optoelectronic property correlated to a specific aggregate architecture independent of the nature of the monomer is a rare phenomenon. Our theoretical investigation on stacked dimeric systems of linear [n]acenes (n = 2–5) and selected non-linear acenes with a D_2h point group reveals that the Greek cross (+) stacked orientation, irrespective of the molecular candidate, exhibits mutually exclusive hole and electron transfer couplings. The deactivation of either hole or electron transfer coupling is a consequence of the zero inter-orbital overlap between the highest occupied molecular orbitals (HOMOs) or lowest unoccupied molecular orbitals (LUMOs) of the monomers possessing gerade symmetry. In the Greek cross (+) stacked alignment, the (4n + 2) π-electronic acene systems with an odd number of benzenoids exhibit exclusive electron transfer coupling, while the even numbered acenes exhibit selective hole transfer coupling. The trend is reversed for representative 4n π-electronic acene systems. The effect of mutually exclusive charge transfer coupling in the hopping regime of charge transport was evaluated using semiclassical Marcus theory, and selective charge carrier mobility was exhibited by the Greek cross (+) stacks of the considered acene candidates. Additionally, the characteristic charge transfer coupling of the orthogonal acene stacks resulted in negligible short-range exciton coupling, inciting null exciton splitting at short interplanar distances. Engineering chromophores in precise angular orientations ensuring characteristic emergent properties can have tremendous potential in the rational design of advanced optoelectronic materials.

Acenes in the Greek cross (+) stack orientation exhibit selective hole and electron transfer coupling based on gerade symmetry in frontier molecular orbitals.     

Inverse kinetic isotope effects in the charge transfer reactions of ammonia with rare gas ions

In the absence of experimental data, models of complex chemical environments rely on predicted reaction properties. Astrochemistry models, for example, typically adopt variants of capture theory to estimate the reactivity of ionic species present in interstellar environments. In this work, we examine astrochemically-relevant charge transfer reactions between two isotopologues of ammonia, NH₃ and ND₃, and two rare gas ions, Kr⁺ and Ar⁺. An inverse kinetic isotope effect is observed; ND₃ reacts faster than NH₃. Combining these results with findings from an earlier study on Xe⁺ (Petralia et al., Nat. Commun., 2020, 11, 1), we note that the magnitude of the kinetic isotope effect shows a dependence on the identity of the rare gas ion. Capture theory models consistently overestimate the reaction rate coefficients and cannot account for the observed inverse kinetic isotope effects. In all three cases, the reactant and product potential energy surfaces, constructed from high-level ab initio calculations, do not exhibit any energetically-accessible crossing points. Aided by a one-dimensional quantum-mechanical model, we propose a possible explanation for the presence of inverse kinetic isotope effects in these charge transfer reaction systems.

Inverse kinetic isotope effects are observed in the charge transfer reactions of rare gas ions with ammonia molecules.     

Hexafluoroisobutylation of enolates through a tandem elimination/allylic shift/hydrofluorination reaction

The isobutyl side chain is a highly prevalent hydrophobic group in drugs, and it notably constitutes the side chain of leucine. Its replacement by a hexafluorinated version containing two CF₃ groups may endow the target compound with new and advantageous properties, yet this modification remains overlooked due to the absence of a general and practical synthetic methodology. Herein, we report the first general method to introduce the hexafluoroisobutyl group into ketoesters, malonates, 1,3-diketones, Schiff base esters and malononitrile. We demonstrated that the reaction occurs through an elimination/allylic shift/hydrofluorination cascade process which efficiently overcomes the usual fluoride β-elimination observed with α-CF₃-vinyl groups. We showed that with alkali metal bases, a pentafluorinated alkene is obtained predominantly, whereas the use of tetrabutylammonium fluoride (TBAF) allows hydrofluorination to occur. This tandem process represents a conceptually new pathway to synthesize bis-trifluoromethylated compounds. This methodology was applied to the multigram-scale synthesis of enantiopure (S)-5,5,5,5′,5′,5′-hexafluoroleucine.

Hexafluoroisobutylation of ketoesters, malonates, diketones, Schiff base esters and malononitrile is reported. The reaction involves an elimination/allylic shift/hydrofluorination cascade process that efficiently overcomes the usual S_N2′ mechanism.     

Effect of one ligand substitution on charge transfer and optical properties in mer-Alq3: a theoretical study

In tris(8-hydroxyquinolinato)aluminum (mer-Alq3) position for substitution plays an important role. We explain the push–pull effect on the charge transfer and optical properties, if only one of the ligand among three ligands of meridianal isomer of mer-Alq3 has been substituted. To check this effect, we substituted A-ligand with electron-donating group at position 4 and electron-withdrawing group at position 6. We designed 4-methyl-6-chloro-(8-hydroxyquino)bis(8-hydroxyquinolinato)aluminum (1), 4-methyl-6-cyano-(8-hydroxyquino)bis(8-hydroxyquinolinato)aluminum (2), 4-amino-6-chloro-(8-hydroxyquino)bis(8-hydroxyquinolinato)aluminum (3), and 4-amino-6-cyano-(8-hydroxyquino)bis(8-hydroxyquinolinato)aluminum (4) derivatives of mer-Alq3. All the studied derivatives in the ground (S₀) and first excited (S₁) states have been optimized at the B3LYP/6-31G* and CIS/6-31G* level of theory, respectively. We have designed green light-emitting materials like mer-Alq3 and blue light-emitting materials. These derivatives are good candidates for comparable/better charge carrier mobility as mer-Alq3.     

Asymmetrically bridged aroyl-S,N-ketene acetal-based multichromophores with aggregation-induced tunable emission

Asymmetrically bridged aroyl-S,N-ketene acetals and aroyl-S,N-ketene acetal multichromophores can be readily synthesized in consecutive three-, four-, or five-component syntheses in good to excellent yields by several successive Suzuki-couplings of aroyl-S,N-ketene acetals and bis(boronic)acid esters. Different aroyl-S,N-ketene acetals as well as linker molecules yield a library of 23 multichromophores with substitution and linker pattern-tunable emission properties. This allows control of different communication pathways between the chromophores and of aggregation-induced emission (AIE) and energy transfer (ET) properties, providing elaborate aggregation-based fluorescence switches.

A library of 23 asymmetrically linked aroyl-S,N-ketene acetal solid-state emissive multichromophores accessed by one-pot multicomponent reactions exhibits AIE- and AIEE-active behavior as well as dual emission and potential energy transfer.     

A high mass loading electrode based on ultrathin Co<Subscript>3</Subscript>S<Subscript>4</Subscript> nanosheets for high performance supercapacitor

There is a growing need for the electrode with high mass loading of active materials, where both high energy and high power densities are required, in current and near-future applications of supercapacitor. Here, an ultrathin Co₃S₄ nanosheet decorated electrode (denoted as Co₃S₄/NF) with mass loading of 6 mg cm^?2 is successfully fabricated by using highly dispersive Co₃O₄ nanowires on Ni foam (NF) as template. The nanosheets contained lots of about 3～5 nm micropores benefiting for the electrochemical reaction and assembled into a three-dimensional, honeycomb-like network with 0.5～1 μm mesopore structure for promoting specific surface area of electrode. The improved electrochemical performance was achieved, including an excellent cycliability of 10,000 cycles at 10 A g^?1 and large specific capacitances of 2415 and 1152 F g^?1 at 1 and 20 A g^?1, respectively. Impressively, the asymmetric supercapacitor assembled with the activated carbon (AC) and Co₃S₄/NF electrode exhibits a high energy density of 79 Wh kg^?1 at a power density of 151 W kg^?1, a high power density of 3000 W kg^?1 at energy density of 30 Wh kg^?1 and 73 % retention of the initial capacitance after 10,000 charge-discharge cycles at 2 A g^?1. More importantly, the formation process of the ultrathin Co₃S₄ nanosheets upon reaction time is investigated, which is benefited from the gradual infiltration of sulfide ions and the template function of ultrafine Co₃O₄ nanowires in the anion-exchange reaction.

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Graphical abstract The ultrathin 2D Co₃S₄ nanosheets fabricated on 3D Ni foam and the formation process of the ultrathin Co₃S₄ nanosheets upon reaction times has been investigated. At the same time, the Co₃S₄/NF electrode displays an outstanding specific capacitance of 2420 F g^?1 at 1 A g^?1 with high mass loading of 6 mg cm^?2.

     

Total synthesis of nahuoic acid A via a putative biogenetic intramolecular Diels–Alder (IMDA) reaction

Inspired by the biogenetic proposal of an intramolecular Diels–Alder (IMDA) cycloaddition, the total synthesis of natural product nahuoic acid A, a cofactor-competitive inhibitor of the epigenetic enzyme lysine methyl transferase SETD8, has been carried out. A non-conjugated pentaenal precursor was synthesized with high levels of stereoselectivity at seven stereogenic centers and with the appropriate control of double bond geometries. Although the IMDA reaction of the non-conjugated pentaenal using Me₂AlCl for catalysis at −40 °C selectively afforded the trans-fused diastereomer corresponding to the Re-endo mode of cycloaddition, under thermal reaction conditions it gave rise to a mixture of diastereomers, that preferentially formed through the exo mode, including the cis-fused angularly-methylated octahydronaphthalene diastereomer precursor of nahuoic acid A. The natural product could be obtained upon oxidation and overall deprotection of the hydroxyl groups present in the Si-exo IMDA diastereomer.

The total synthesis of natural product nahuoic acid A, a cofactor-competitive inhibitor of the epigenetic enzyme lysine methyl transferase SETD8, has been carried out based on the biogenetic proposal of an intramolecular Diels–Alder (IMDA) cycloaddition.     

Biohybrid photosynthetic charge accumulation detected by flavin semiquinone formation in ferredoxin-NADP+ reductase

Flavin chemistry is ubiquitous in biological systems with flavoproteins engaged in important redox reactions. In photosynthesis, flavin cofactors are used as electron donors/acceptors to facilitate charge transfer and accumulation for ultimate use in carbon fixation. Following light-induced charge separation in the photosynthetic transmembrane reaction center photosystem I (PSI), an electron is transferred to one of two small soluble shuttle proteins, a ferredoxin (Fd) or a flavodoxin (Fld) (the latter in the condition of Fe-deficiency), followed by electron transfer to the ferredoxin-NADP⁺ reductase (FNR) enzyme. FNR accepts two of these sequential one electron transfers, with its flavin adenine dinucleotide (FAD) cofactor becoming doubly reduced, forming a hydride which is then passed onto the substrate NADP⁺ to form NADPH. The two one-electron potentials (oxidized/semiquinone and semiquinone/hydroquinone) are similar to each other with the FNR protein stabilizing the hydroquinone, making spectroscopic detection of the intermediate semiquinone state difficult. We employed a new biohybrid-based strategy that involved truncating the native three-protein electron transfer cascade PSI → Fd → FNR to a two-protein cascade by replacing PSI with a molecular Ru(ii) photosensitizer (RuPS) which is covalently bound to Fd and Fld to form biohybrid complexes that successfully mimic PSI in light-driven NADPH formation. RuFd → FNR and RuFld → FNR electron transfer experiments revealed a notable distinction in photosynthetic charge accumulation that we attribute to the different protein cofactors [2Fe2S] and flavin. After freeze quenching the two-protein systems under illumination, an intermediate semiquinone state of FNR was readily observed with cw X-band EPR spectroscopy. The increased spectral resolution from selective deuteration allowed EPR detection of inter-flavoprotein electron transfer. This work establishes a biohybrid experimental approach for further studies of photosynthetic light-driven electron transfer chain that culminates at FNR and highlights nature''s mechanisms that couple single electron transfer chemistry to charge accumulation, providing important insight for the development of photon-to-fuel schemes.

One electron at a time, photosynthetic biohybrids enable charge accumulation via the flavin semiquinone of ferredoxin-NADP⁺ reductase.     

Direct detection of spin polarization in photoinduced charge transfer through a chiral bridge

It is well assessed that the charge transport through a chiral potential barrier can result in spin-polarized charges. The possibility of driving this process through visible photons holds tremendous potential for several aspects of quantum information science, e.g., the optical control and readout of qubits. In this context, the direct observation of this phenomenon via spin-sensitive spectroscopies is of utmost importance to establish future guidelines to control photo-driven spin selectivity in chiral structures. Here, we provide direct proof that time-resolved electron paramagnetic resonance (EPR) can be used to detect long-lived spin polarization generated by photoinduced charge transfer through a chiral bridge. We propose a system comprising CdSe quantum dots (QDs), as a donor, and C₆₀, as an acceptor, covalently linked through a saturated oligopeptide helical bridge (χ) with a rigid structure of ∼10 Å. Time-resolved EPR spectroscopy shows that the charge transfer in our system results in a C₆₀ radical anion, whose spin polarization maximum is observed at longer times with respect to that of the photogenerated C₆₀ triplet state. Notably, the theoretical modelling of the EPR spectra reveals that the observed features may be compatible with chirality-induced spin selectivity, but the electronic features of the QD do not allow the unambiguous identification of the CISS effect. Nevertheless, we identify which parameters need optimization for unambiguous detection and quantification of the phenomenon. This work lays the basis for the optical generation and direct manipulation of spin polarization induced by chirality.

Our work provides a first attempt to directly detect the spin polarisation of Chiral-Induced Spin Selectivity (CISS) effect by studying the photoinduced electron transfer in a CdSe Quantum Dot-chiral bridge-fullerene derivative (QD–χ–C₆₀) system.     

Facilitated transport of palladium(II) across polymer inclusion membrane with ammonium ionic liquid as effective carrier

This work focuses on the application of polymer inclusion membrane (PIM) with tricaprylmethylammonium thiosalicylate, [A336][TS] (TOMATS), a thiol-containing task-specific ionic liquid for the transport of Pd(II) ions from aqueous solutions. 0.3 M thiourea in 0.1 M hydrochloric acid was found the most effective stripping phase in the transport of Pd(II) from membrane phase containing TOMATS. Separation of Pd(II) ions was also carried out from hydrochloric acid solution containing Pt(IV), Fe(III), Ni(II), and Mn(II). Pd(II) ions were preferably transported in the presence of these metal ions. The separation coefficients followed the order: S _Pd/Pt < S _Pd/Fe < S _Pd/Ni < S _Pd/Mn. [A336][TS] proved to be an excellent ion carrier for Pd(II) from hydrochloric acid solution. The results also showed that transport efficiency of the PIM was reproducible and it can be useful for the development of the simple and highly effective method of Pd(II) recovery from leach liquor of spent catalysts.     

Electrochemiluminescence DNA biosensor based on the use of gold nanoparticle modified graphite-like carbon nitride

The authors describe an electrochemiluminescent (ECL) DNA biosensor that is based on the use of gold nanoparticles (AuNPs) modified with graphite-like carbon nitride nanosheets (g-C₃N₄ NSs) and carrying a DNA probe. In parallel, nanoparticles prepared from gold-platinum (Au/Pt) alloy and carbon nanotubes (CNTs) were placed on a glassy carbon electrode (GCE). Once the g-C₃N₄ NHs hybridize with DNA-modified AuNPs, they exhibit strong and stable cathodic ECL activity. The Au/Pt-CNTs were prepared by electrochemical deposition of Au/Pt on the surface of the CNTs in order to warrant good electrical conductivity. On hybridization of immobilized capture probe (S₁), target DNA (S₂) and labeled signal probe (S₃), a sandwich-type DNA complex is formed that produces a stable ECL emission at a typical applied voltage of ?1.18 V and in the presence of peroxodisulfate. Under optimized conditions, the method has a response to target DNA that is linearly related to the logarithm of its concentration in the range between 0.04 f. and 50 pM, with a 0.018 f. detection limit.

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Graphical abstract Schematic presentation of an electrochemiluminescent DNA biosensor based on two-dimensional graphite-like carbon nitride nanosheets (g-C₃N₄ NSs) hybridized with gold nanoparticles. Abbreviations: MCH: 6-mercapto-1-hexanol; S1: Capture probe; S2: target DNA. 

     

Synthesis of organometallic Ru(II) and Fe(II) complexes containing fused rings hemi-helical ligands as chromophores. Evaluation of non-linear optical properties by HRS

A new family of three-legged piano stool structured organometallic compounds containing the fragment η⁵-cyclopentadienyl-ruthenium(II)/iron(II) has been synthesized to evaluate the existence of electronic metal to ligand charge transfer upon coordination of the novel benzodithiophene ligands (BDT), benzo[1,2-b;4,3-b′]dithiophen-2-carbonitrile (L1) and benzo[1,2-b;4,3-b′]dithiophen-2′nitro-2-carbonitrile (L2). All the compounds were characterized by ¹H, ¹³C, ³¹P NMR, IR and UV-Vis. spectroscopies and their electrochemistry studied by cyclic voltammetry. The X-ray structures of [Ru(η⁵-C₅H₅)(PPh₃)₂(NCC₁₀H₅S₂)][PF₆] (1Ru), [Ru(η⁵-C₅H₅)(PPh₃)₂(NCC₁₀H₅S₂)][CF₃SO₃] (1′Ru), [Ru(η⁵-C₅H₅)(DPPE)(NCC₁₀H₅S₂)][PF₆] 2Ru and [Fe(η⁵-C₅H₅)(DPPE)(NCC₁₀H₅S₂)][PF₆] (2Fe) were determined by X-ray diffraction showing centric crystallization on groups and P2₁/n, respectively.Quadratic hyperpolarizabilities (β) of some of the complexes (2Fe, 2Ru and 3Fe) have been determined by hyper-Rayleigh scattering (HRS) measurements at a fundamental wavelength of 1500 nm, to minimize the probability of fluorescence due to two-photon absorption and to reduce the effect of resonance enhancement, in order to estimate static β values.     

Rational design of donor–π–acceptor n-butyl-1,8-naphthalimide-cored branched molecules as charge transport and luminescent materials for organic light-emitting diodes

Four D–π–A bipolar molecules with n-butyl-1,8-naphthalimide (BNI) fragments as acceptors, acetylenes as π-spacers, and different aromatic groups as donors have been designed to explore their optical, electronic, and charge transport properties as charge transport and luminescent materials for organic light-emitting diodes (OLEDs). The frontier molecular orbitals (FMOs) and local density of states analysis have turned out that the vertical electronic transitions of absorption and emission are characterized as intramolecular charge transfer (ICT). The calculated results show that their optical and electronic properties are affected by the different donors of the bipolar molecules. Our results suggest that D–π–A 1,8-naphthalimide derivatives with donors triphenylamine (1), 1-nitrobenzene (2), anisole (3), and 4-phenylbenzo[c][1,2,5]thiadiazole (4) fragments are expected to be promising luminescent materials. Furthermore, 2–4 are expected to be promising candidates for both electron and hole transport materials as well as potential ambipolar charge transport material, whereas BNI and 1 can serve as hole transfer materials only. We have also predicted the mobility of 4 with better performance in three different space groups. On the basis of investigated results, we proposed a rational way for the design of charge transport and/or luminescent materials simultaneously.     

Electron transport properties of thermoelectrics based on layered substituted transition metal dichalcogenides

Temperature dependences of the electrical conductivity are studied in the range 4.2’300 K and Seebeck coefficient at room temperature of bulk samples of tungsten dichalcogenide polycrystals with niobium substitutions for tungsten and selenium substitutions for sulfur – W_1–x Nb _x (S_1–y Se _y )₂. The two-dimensionalization of electron transport properties is detected at niobium concentrations x ≥ 0.1 in W_1–x Nb _x S₂ and x ≥ 0.05 in W_1–x Nb _x Se₂. In samples with additional partial selenium substitution for sulfur the electron transport remains three-dimensional. At room temperature the Seebeck coefficient (at equal electrical conductivities) is several times higher in the samples with quasi-two-dimensional transport than in the samples with three-dimensional transport. The calculation of the power factor at room temperature shows its nine times increase.