Effect of Poly（Ether Urethane） Introduction on the Performance of Polymer Electrolyte for All-Solid-State Dye-Sensitized Solar Cells

The introduction of poly（ether urethane） （PEUR） into polymer electrolyte based on poly（ethylene oxide）, LiI and I2, has significantly increased the ionic conductivity by nearly two orders of magnitudes. An increment of I3- diffusion coefficient is also observed. All-solid-state dye-sensitized solar cells are constructed using the polymer electrolytes. It was found that PEUR incorporation has a beneficial effect on the enhancement of open circuit voltage VOC by shifting the band edge of TiO2 to a negative value. Scanningelectron microscope images indicate the perfect interfacial contact between the TiO2 electrode and the blend electrolyte.

Spontaneous Symmetry Breaking of Iridium and Ruthenium Metallophosphors for the Constructions of Chiral Light-Harvesting Systems

Symmetry breaking for chirality generation and lightharvesting for solar energy conversion are two momentous topics in natural systems.The construction of a chiral light-harvesting system completely based on symmetry breaking is a formidable challenge.Here,we report the spontaneous chiral symmetry breaking(CSB)of two iridium and ruthenium metallophosphors(IrD and RuA)with the assistance of achiral solvents.The subtle noncovalent intermolecular interactions between complexes and polar solvents play a vital role in the crystallization of homochiral molecules and the resulting CSB.Utilizing a molecular doping strategy,transferred,ampli-fied,and inverted circularly polarized luminescence(CPL)was achieved in the binary microcrystals(MCs)composed of chiral/achiral IrD and achiral/chiral RuA,with large dissymmetry factors(glum,up to 0.06)and enhanced emission quantum yields(over 35%).The use of only 0.05%of chiral RuA in the lattice of achiral IrD led to the chiral amplification with glum of 1×10−2 and morphology transition,while inverted and white CPL were obtained in MCs containing monodispersed chiral RuA in the lattice cavities of another polymorphic crystal of IrD.Diffuse reflection circular dichroism measurements gave information on the chirality transfer mechanisms behind these spin-related chiroptical properties.

Circularly polarized phosphorescence and photon transport of micro/nanocrystals of ruthenium and iridium complexes with chiral anions

Materials with efficient circularly polarized phosphorescences(CPPs) are of potential use in advanced data encryption and anticounterfeiting, bioimaging, optoelectronic devices and so forth. Herein, a simple method is presented for the preparations of CPP-active micro/nanocrystals with large luminescence dissymmetry factors(glum), high phosphorescence quantum efficiencies(Φ_(P)) and tunable emission colors. Diastereomeric Ir^(Ⅲ) and Ru^(Ⅱ) complexes with chiral(±)-camphorsulfonate counter-anions are readily synthesized and assembled into crystalline microrods, microplates or nanofibers with ordered morphologies. The chirality information of chiral counter-anions is efficiently transferred to the metal components to afford CPPs with cyan, green,yellow, or red emission colors and Φ_(P)in the range of 5%–85%. The number of chiral anions is found to play a role in influencing the CPP magnitudes of these crystals. The dicationic Ru^(Ⅱ) and tricationic Ir^(Ⅲ) complexes show glumvalues in the 10^(-2)order, which are much larger with respect to those of monocationic Ir^(Ⅲ) complexes. Single crystal X-ray analysis is performed to obtain information on the chirality transfer of these materials. In addition, circularly polarized photonic signal waveguiding is demonstrated using the microcrystals of an Ir^(Ⅲ)complex. This work demonstrates an appealing strategy of constructing chiral micro/nano-architectures for potential applications in chiral nanophotonics.

Electropolymerized films of redox-active ruthenium complexes for multistate near-infrared electrochromism,ion sensing,and information storage

This paper summarizes our recent progress on the preparations and applications of electropolymerized thin films of redox-active ruthenium complexes.Thin films of vinyl-functionalized diruthenium or ruthenium-amine conjugated complexes are prepared by reductive electropolymerization.The resulting films are useful for multistate near-infrared electrochromism,ion sensing,and mimicking flip-flop and flip-flap-flop logic gates.The oxidative electropolymerization of diruthenium complexes with two distal triarylamine units affords electropolymers with an alternating diruthenium and tetraphenylbenzidine structural unit.The applications of the resulting films in multistate near-infrared electrochromism and resistive memory are discussed.

Near-infrared electrochromism of multilayer films of a cyclometalated diruthenium complex prepared by layer-by-layer deposition on metal oxide substrates

A cyclometalated diruthenium complex 2 bridged by 1,2,4,5-tetra(pyrid-2-yl)benzene with six carboxylic acid groups at two ends was synthesized.Monolayer and multilayer films FTO/TiO2/(2)n(Zr)(n=1,2)and FTO/SnO2:Sb/(2)n(Zr)(n=1-4)have been prepared via interfacial layer-by-layer coordination assembly of 2 with zirconium(IV)ions.All films show two consecutive redox couples in the potential range between 0 and+1.0 V vs.Ag/AgCl.These films exhibit reversible near-infrared electrochromism upon switching of redox potential.The response time of the films on SnO2:Sb is around a few seconds,while that on TiO2 is around a few tens of seconds.The film deposition cycles were found to have a great impact on the electrochromic performance.Among six films examined,the two-layered film on SnO2:Sb displays the best balanced performance with a contrast ratio of 56%at 1,150 nm and good cyclic stability(9%loss of contrast ratio after 1,000 continuous double-potential-switching cycles),which is superior to that of the previously reported electropolymerized films of a related diruthenium complex with the same bridging ligand.In addition,the X-ray photoelectron spectroscopy,scanning electron microscopy,and electron transfer mechanism of these films have been investigated.

Outgassing analysis of molecular glass photoresists under EUV irradiation

A device was designed and assembled to analyze the outgassing of molecular glass(MG)photoresists under extreme ultraviolet(EUV)exposure.The outgassing of the photoresists with different components and different concentrations of tert-butoxycarbonyl(t-Boc),photo-generated acid(PAG),and acid quencher was systematically investigated.Based on experiments,some solutions for reducing the outgassing of MG photoresists were proposed.

Cyclometalated Ruthenium Complexes of 1,2,3-Triazole-containing Ligands： Synthesis, Structural Studies, and Electronic Properties

Six bis-tridentate and two tris-bidentate cyclometalated ruthenium complexes with a 1,2,3-triazole-containing ligand have been prepared and characterized. Single-crystal X-ray analyses of complexes [（MeOptpy）Ru（Budtab）]-（PF6） and [（Mebip）Ru（Budtab）]（PF6） are presented, where MeOptpy is 4′-p-methoxyphenyl-2,2′：6′,2＂-terpyridine, Budtab is the 2-deprotonated form of 1,3-di（N-n-butyl-l,2,3-triazol-4-yl）benzene, and Mebip is bis（N-methyl-ben-zimidazolyl）pyridine. The electronic properties of these complexes are probed by spectroscopic and electrochemical analyses. Time-dependent density functional theory calculations have been performed to assist the assignment of the absorption spectra.

Photofunction-Directed Coordination Molecular Engineering

Molecular engineering has emerged as a highly interdisciplinary field of study on function-directed molecular design,material synthesis,and property optimization,accompanied by a deep understanding of the structure-property relationship.In this review,our recent progress on the design and preparations of photofunctional metal complexes and related materials is summarized from the perspective of coordination molecular engineering.In particular,a series of cyclometalated diruthenium complexes with near-infrared(NIR)electrochromic property have been synthesized by engineering the bridging ligand structures.A group of ruthenium-amine conjugated complexes with multistage NIR electrochromism are obtained on the basis of a multicenter strategy.By engineering the ligand structures,a series of new ruthenium and platinum complexes are synthesized to show switchable luminescence in response to various stimuli.In addition,photoluminescent ruthenium,iridium,and platinum complexes are assembled to afford micro/nanocrystals with well-defined morphology and luminescent properties.

Regulation of Glucose Oxidase Activity through Interaction with Fullerene Derivatives

The 2-（hydroxymethyl）pyridine modified C60 （PY-C60） and methoxydiglycol modified C60 （MDG-C60） are synthesized using Bingel-Hirsch reaction and characterized by nuclear magnetic resonance （NMR） and mass spectra. PY-C60 and MDG-C60 can bind to glucose oxidase （GOx） and quench the fluorescence of tryptophan （Trp） residue in GOx through static mechanism. The conformation of GOx is disturbed after formation of complex with these fullerene derivatives. Kinetic analysis indicates that PY-C60 and MDG-C60 may affect the catalytic activity of GOx with a partial mixed-type inhibition mechanism. In the plasma glucose concentration range （3.6--5.2 mmol·L-1）, PY-C60 may significantly accelerate the catalytic velocity of GOx, however, MDG-C60 exerts almost no obvious change to the initial velocity of GOx, suggesting that elaborate design of molecular structure of fullerene derivative is very important for regulating the biological activity of fullerene-enzyme complex.

Controlled synthesis of multi-shelled transition metal oxide hollow structures through one-pot solution route

As one type of promising candidates for environmental and energy-related systems, multi-shelled transition metal oxide hollow structures （MS-TMOHSs） have drawn great scientific and technical interest in the past few years. This article highlights recent advances in one-pot solution synthesis of MS- TMOHSs. We begin it with an overview of synthetic strategies that have been exploited to achieve these peculiar structures. We then focus on one-pot solution approaches in the following four sections： i） soft templates directed growth; ii） Ostwald ripening; iii） controlled etching; and iv） gas bubble assisted growth. After giving a brief discussion on the unique properties and applications of these multi-shelled hollow structures, we conclude this review with the general challenges and the potential future directions of this excitin~ area of research.

Performances improvement of eosin Y sensitized solar cells by modifying TiO_2 electrode with silane-coupling reagent

Chemical fixing of xanthene dye (eosin Y) on the surface of TiO2 electrode was carried out by modifying the electrode with silane-coupling reagent to obtain stable dye-sensitized TiO2 electrode. Such silane modification can not only evidently enhance the stability of dye-sensitized TiO2 electrode but also im-prove the energy conversion efficiency of the assembled cells by increasing short-circuit photocurrent (JSC) and open-circuit photovoltage (VOC). It was found that the improvements of cell performances differ depending on the composition of the electrolyte. The optimum cell of the cell performance was achieved in the electrolyte with 0.5 mol/L TBAI/0.05 mol/L I2/EC:PC(3:1 w/w), yielding JSC of 4.69 mA·cm?2, VOC of 0.595 V, fill factor (FF) of 0.64 and η of 1.78%. Different spectroscopic techniques including UV-Vis spectra, fluorescence spectra, EIS and dark current measurements were employed to derive reasonable analysis and explanations.

A Star-Shaped Solvatofluorochromic Pyrene-Triarylamine Derivative as a Fluorescent Thermometer over a Wide Temperature Range

of main observation and conclusion A star-shaped compound 1 with a pyrene core and four triarylamine arms has been prepared and characterized.It exhibits intense intramolecular-charge-transfer(ICT)emissions with strong solvatofluorochromism.On the basis of the temperature-dependent emission color and wavelength changes,compound 1 behaves as a fluorescent thermometer between 200 and 400 Kwith a high theromosensitivity.In comparison,model compounds with one or two triarylamine arms show distinctly lower thermosensitivity.

Handedness-inverted polymorphic helical assembly and circularly polarized luminescence of chiral platinum complexes

Circularly polarized luminescence(CPL)materials have potential applications in three-dimensional(3D)displays,quantum encryption,and optical sensors.The development of single-component CPL materials with polymorphic assembly and handedness inversion remains a significant challenge.Herein,we present the access of such materials by controlling the underlying assembly pathway of well-designed chiral emitters.A pair of enantiomeric platinum complexes(R)-1 and(S)-1 decorated with a chiralα-methylbenzyl isocyanide ligand were prepared.By using the mixed-solvent(THF/n-hexane,THF=tetrahydrofuran)or high-concentration condition,these complexes were found to assemble via a cooperative or isodesmic pathway with significantly enhanced yellow or red emission,respectively.The aggregate samples obtained via these conditions show efficient CPL(dissymmery factor|glum|>0.02,emission quantum yieldΦ>20%).Interestingly,different assembly pathway leads to helical nanoribbons or nanofibers with opposite handedness from the complex with the same molecular chirality.This has been unambiguously and consistently manifested by circular dichroism and CPL spectral analysis and transmission electron,scanning electron,and atomic force microscope studies.This work demonstrates an appealing example of constructing polymorphic helical architectures with highly efficient CPL and inverted handedness thanks to the excellent assembly and emission of platinum complexes.

Design of quinoline-based fluorescent probe for the ratiometric detection of cadmium in aqueous media

A new fluorescent probe,DQCd2,based on 4-piperidinoquinoline has been synthesized as a fluorescent probe for Cd^2＋.It can ratiometrically respond to Cd^2＋ in PBS buffer by a remarkable emission intensity enhancement（88-fold） and wavelength shift（70 nm）.

Highly selective two-photon fluorescent probe for imaging of nitric oxide in living cells

A new two-photon fluorescent probe, ADNO, for nitric oxide （NO） based on intramolecular photoinduced electron transfer （PET） mechanism d/splays a rapid response to NO with a remarkable fluorescent enhancement in PBS buffer. The excellent chemoselectivity of ADNO for NO over other ROS/RNS （reactive oxygen species or nitrogen species） and common metal ions was observed. Moreover, ADNO has been successfully applied in fluorescence imaging of NO of living cells using both one-photon microscopy （OPM） and two-~hoton microscopy （TPM）,

Towards precise synthesis of functional polymers by iterative electropolymerization

The controllable synthesis of polymers and macromolecules with precise structures is one of the biggest challenges in polymer chemistry[1].Although polymers with welldefined architectures and compositions could now be prepared by various living polymerization techniques[1],it remains elusive to produce macromolecular materials with precise controls of monomer sequences and easy purification procedures.

Circularly polarized luminescence of coordination aggregates

The development and applications of materials with efficient circularly polarized luminescence(CPL)have become an interdisciplinary frontier research topic.We summarize herein the recent advance in the development and applications of CPLactive aggregates based on metal-ligand coordination materials(termed as“coordination aggregates”).The materials surveyed are classified as aggregates of smallmolecular metal complexes,which include monocomponent assemblies of Pt(II)complexes and other complexes and binary aggregates of metal complexes,and CPL-active metal-ligand coordination helicates,polymers,and frameworks.The efforts in improving the dissymmetry luminescence factors and quantum yields of these materials and the use of the aggregation strategy in enhancing the performance of isolated molecules are discussed.The recent applications of chiral metal complexes in circularly polarized organic light-emitting diodes(OLEDs)based on solution-or evaporation-processed procedures are surveyed.In addition,the uses of lanthanide complexes in CPL-contrast imaging and as CPL probes are highlighted.The common discussion on the mechanism of aggregation-enhanced CPLs and a perspective on future works of CPL-active coordination aggregates are finally given.

Influence of terminal substituents on the halide anion binding of foldamer-based receptors

Foldamers 1–4 incorporating different terminal substituents have been designed and synthesized for binding halide anions.~1H NMR titration experiments carried out in DMSO-d_6/CDCl_3（15/85, v/v）demonstrated that the short oligo （aryltriazole）s backbone 1 could not bind halide anions unless that amide H-bond donors were incorporated at the termini of the oligomer. Terminal substituents on oligo（aryltriazoleamide）s foldamers 2–4 display a considerable influence on the binding affinities of the foldamers for halide anions. Large steric hindrance of the terminal substituents was found to be unfavorable for binding halide anions, but aromatic π-π interactions between two terminal substituents are capable of stabilizing the conformation of foldamers thus giving rise to an enhancement in the binding strengths. However, the terminal substituents were found to hardly affect the binding selectivity in the studied cases.

Triarylamines with branched multi-pyridine groups： modulation of emission properties by structural variation, solvents,and tris(pentafluorophenyl)borane

Six triarylamine derivatives 1–6 with branched multi-pyridine substituents were prepared and characterized. These compounds are distinguished by the substituent on one of the phenyl group with NO2 for 1, CN for 2, Cl for 3, p-C6 H4 OMe for 4, OMe for 5,and NMe2 for 6, respectively. As revealed by single crystal X-ray analysis, these substituents play an important role in determining the configuration of the triarylamine framework and the crystal packing of 1–6. The emission properties of these compounds were examined in different solvents(toluene, CH2 Cl2, acetone, tetrahydrofuran(THF), and N,N-dimethylformamide(DMF)) and in solid states. Distinct dual emissions from the localized emissive state and the intramolecular charge transfer state were observed for compound 5 in CH2 Cl2. Compounds 1 and 6 show apparent aggregated enhanced emissions in acetone/H2 O.The emission properties of these compounds were further modulated by the addition of tris(pentafluorophenyl)borane. In addition, density functional theory(DFT) and time-dependent DFT(TDDFT) calculations have been performed on the ground and singlet excited states to complement the experimental findings.

Effect of TiO_2 nanotubes lateral spacing on photovoltaic properties of dye-sensitized solar cells

Vertically aligned Ti O2 nanotube arrays(*8 lm long, *110 nm wide) have been fabricated through anodic oxidation of Ti-metal sheet in fluoridecontaining electrolyte. By changing the volume ratio of ethylene glycol and diethylene glycol in the electrolyte,Ti O2 nanotube arrays with different tube-to-tube lateral spacing, i.e., closely packed, just separated, and fully separated, have been synthesized and applied as photoanodes for dye-sensitized solar cells(DSSCs). Photovoltaic efficiency of 2.99 %, 3.34 %, and 3.44 % has been obtained for DSSCs based on the closely packed, just separated, and fully separated Ti O2 nanotube arrays,respectively, illustrating the effect of tube-to-tube lateral spacing of Ti O2 nanotube arrays on the performances of DSSCs. It is suggested that fully separated Ti O2 nanotube arrays are beneficial to the conversion efficiency of DSSCs due to higher dye loading and faster electron transfer.