Evaluation of Transient Absorption Spectra of N,N,N’,N’—Tetra—（p—methylphenyl）

Photoinduced electron transfer processes between fullerenes(C60/C70)and N,N,N’,N’-tetra-(p-methylphenyl-4,4’-diamino-1,1’-diphenyl ether(TPDAE)have been studied by nanosecond laser flash photolysis.Quantum yields and rate constants of electron trasfer from TPDAE to excited triplet state of fullerenes(C60/C70)in benzonitrile have been evaluated by observing the trasient absorption bands in the near-IR region where the excited triplet state.radical anion of fullerenes(C60/C70)and radical cations of TPDAE appear.     

Photophysical Properties and Photoinduced Electron Transfer between[60]Fullerene—containing Cyclic Sulphoxide [C60—C60H8SO]and Tetrathiafulvalene（TTF） by Laser Flash Photolysis

Photoinduced electron transfer(PET) processes between C60-C6H8SO and Tetrathiafulvalene(TTF) have been studied by nanosecond laser photolysis.Quantrm yiekds(φet) and rate constants of electron transfer(ket) from TTF to excited triplet state of[60] fullerene-containing cyclic sulphoxide in benzonitrile(BN) have been evaluated by observing the transient absorption bands in the NIR region.With the decay of excited triplet state of [60]fullerene-containing cyclic suplhoxide,the rise of radical anion of [60]fullerene-containing cyclic sulphoxinde is observed.     

Combined Transient Spectra and Semiempirical Calculation of [60]Fullerenes Attached with Piperidinodithiocarboxylate and 7-Chloro-phenazine

[60]Fullerenes attached with piperidinodithiocarboxylate dyad （1） and 7-chloro-1,2,3,4-tetrahydrophenazine （2） were efficiently synthesized through Diels-Atder cycloaddition with dienes. The physical properties of the triplet states of these compounds, in which strong electron acceptor moieties were covalently attached to C60 cores, were investigated by nanosecond laser flash photolysis. The excited triplet states in benzonitrite have been evaluated by observing the transient absorption bands in the near-IR region. The HOMO and LUMO were calculated by semiempirical methods AM1, which could predict the intramolecular photoinduced electron transfer in 1 and 2, and the nanosecond transient absorption spectra observed experimentally in solution were in excellent agreement with the calculated ones.     

Synthesis of Fullerene-end Functionalized Poly（methyl methacrylate） via Reverse Atom Transfer Radical Polymerization

The use of the reverse atom transfer radical polymerization （RATRP） to end-functionalize poly（methyl methacrylate） （PMMA） with fullerenes, e.g. C60 and C70 was described in this paper. The Cl-terrninated PMMA was prepared via RATRP with designed molecular weight and narrow molecular weight distributions, and then directly used to react with fullerenes to produce C60（C70） terminated PMMA polymers in the presence of CuBr/Cu/bipy or FeCl2/bipy catalysts. The resultant polymers exhibit good solubility in some common organic solvents, e.g. THF, CHCl3 and toluene, and were well structurally characterized by a variety of physical techniques.     

Characterization of transient species in laser photolysis of aromatic amino acids using acetone as photosensitizer

The photochemical processes of aromatic amino acids were investigated in aqueous solution using acetone as photosensitizer by KrF (248 nm) laser flash photolysis. Laser-induced transient species were characterized according to kinetic analysis and quenching experiments. The intermediates recorded were assigned to the excited triplet state of tryptophan, the radicals of tryptophan and tyrosine. The excited triplet state of tryptophan produced via a triplet-triplet excitation transfer and the radicals arising from electron transfer reaction has been identified. Neither electron transfer nor energy transfer between triplet acetone and phenylalanine can occur in photolysis of phenylalanine aqueous solution which contains acetone. Furthermore, triplet acetone-induced radical transformation: Trp/N-Tyr→Trp-Tyr/O was observed directly in photolysis of dipeptide (Trp-Tyr) aqueous solution containing acetone, and the transformation resulting from intramolecular electron transfer was suggested.     

Photoinduced charge transfer in porphyrin-C_(60) oligomer

Photoinduced electron transfer (ET) between C60 and porphyrin (P) in a new polymer containing porphyrin, poly(p-phenyle nevinylene), and pendant fullerene units has been investigated by nanosecond transient absorption and phosphorescence spectroscopy. Compared to the physically doping material systems, binding porphyrin/C60 through chemical bonds in a polymer detains the formation of the triplet states of porphyrins and C60. The formation of intermediate charge transfer state (CSS) of P·+-C60·? was observed...     

CHROMATOGRAPHIC SEPARATION ON GRAPHITE OF FULLERENE-C_(60) AND-C_(70)

The mixture of fullerene—C_(60) and —C_(70) was successfully separated in larger amount by liquid chromatogra-phy on graphite column.The column was first eluted with a mixture of hexane and toluene,and then withtoluene.The eluates were monitored by UV/visible absorption spectroscopy.Graphite column shows high perfor-mance for separation.and much larger quantities of pure C_(60) can be easily obtained.The synthesis of fullerenes(C_(60) and C_(70))in macroscopic quantities has stimulated scientists to study on themethod for separating C_(60) and C_(70).Because of the poor solubility of fullerenes C_(60)/C_(70) in most organic solvents,theseparation of C_(60) and C_(70) proved to be a challenging task.Most attempts at the separation have used silica and alu-mina as the stationary phase and a mixture of hexane and benzene(or toluene)as the mobile phase.Fullerenes,however,have only limited solubility in hexane,these separations are usually only achieved by limit-ing the amount of sample to a few milligrams.The hexane-silica technique using phenylglycine based HPLCcolumns appears to offer good separation,but only for submilligram amounts. The use of graphite powder as the stationary phase in liquid chromatography is an advanced separation tech-nique for fullerenes C_(60)/C_(70).The technique is based on that the fullerene-C_(60) is different from C_(70) in the de-gree of electron delocalisation,and C_(60) is much less diamagnetic than C_(70).It is expected that the dissimilarity willcause the C_(60)/C_(70) molecules to exhibit different interactions with graphite,and can be separated from each other onthis basis.     

Transient species of fullerenes studied with pulse radiolysis and laser photolysis

The excited triplet of C60 or C70 is generated via either direct excitation by laser light or energy transfer from excited states of solvent to C60 and C70. The cation radical of C60 is produced either via hole transfer from cation radical of CCl4 to C60 or via electron transfer from excited triplet of C60 to CCl4. C60 and C70 could be added to trichloromethyl radical to produce adduct radicals with different mechanisms.     

High-efficiency quaternary polymer solar cells enabled with binary fullerene additives to reduce nonfullerene acceptor optical band gap and improve carriers transport

The polymer/small-molecule electron donor and nonfullerene organic electron acceptor are of structural similarity with both donor and acceptor molecules consisting of polycyclic fused-ring backbone and being decorated with alkyl-chains.In this study,we report that the introduction of binary fullerenes(C_(60)-/C_(70)-PCBM and C_(60)-/C_(70)-ICBA)into a nonfullerene binary system PBDB-T:ITIC reduces the polymer-nonfullerene acceptor intermixing,obtaining higher crystallinity with(100)crystal coherence length from 28 to 29–33 nm for the ITIC,and from 14 to 20–24 nm for the PBDB-T,and improved electron and hole mobilities both.Unprecedentedly,such a protocol reduces the ITIC optical band gap from 1.59 to 1.55 eV.As consequences,higher short-circuit current-density(17.8–18.4 vs.15.8 m A/cm~2),open-circuit voltage(0.92 vs.0.90 V)and fill-factor(0.72–0.73 vs.0.68)are simultaneously obtained,which ultimately afford higher efficient quaternary polymer solar cells with power conversion efficiencies(PCEs)up to 12.0%–12.8%comparing to the host binary device with 9.9%efficiency.For the polymer,ITIC,and ICBA/PCBM ternary blends,11%PCEs were recorded.The use of PCBM leads to larger red-shifting in thin film absorption and external quantum efficiency(EQE)response.Such effect is more pronounced when ICBA:PCBM mixture is used.These results indicate the size and shape of C_(60)and C_(70)as well as the substituent position of the second indene unit on C_(60)-/C_(70)-ICBA affect not only the blend morphology but also the electronic coupling in BHJ mixtures:the quaternary device performance increased in sequences of C_(70)-PCBM:C_(70)-ICBA→C_(70)-PCBM:C_(60)-ICBA→C_(60)-PCBM:C_(70)-ICBA→C_(60)-PCBM:C_(60)-ICBA.The resonant soft X-ray scattering(RSoXS)data indicated the most refined phase separation in the C_(60)-PCBM:C_(60)-ICBA based blend,corresponding to its best device function among the quaternary devices.These results indicate that the using of binary fullerenes as the acceptor additives allows for tuning nonfullerene blended film’s optical properties and filmmorphologies,shedding light on the designing high-performance multi-acceptor polymer solar cells.     

Laser photolysis of interaction of poly-guanylic acid (5'''') with anthraquinone-2-sulfonate

The electron transfer reaction between triplet anthraquinone-2-sulfonate and poly-guanylic acid (5') in CH3CN-H2O (97 : 3) has been investigated by 248 nm (KrF) laser flash photolysis. The transient absorption spectra and kinetics obtained from the interaction of triplet anthraquinone-2-sulfonate and poly[G] demonstrate that the primary ionic radical pair, radical cation of poly[G] and radical anion of anthraquinone-2-sulfonate have been detected simultaneously. The free energy changes in the process of the electron transfer were also calculated.     

Photoinduced Electron Transfer between N,N, Nr,N' ‐Tetra‐(p‐methylphenyl)‐4, 4‐diamino‐1, 1'‐diphenyl Ether (TPDAE) and Fullerenes (C60/C70) by Laser Flash Photolysis

The photoinduced electron‐transfer reaction of N, N, N', N'‐tetra‐(p‐methylphenyl)‐4,4'‐diamino‐1,1'‐diphenyl ether (TPDAE) and fullerenes (C₆₀/C₇₀) by nanosecond laser flash photolysis occurred in benzonitrile. Transient absorption spectral measurements were carried out during 532 nm laser flash photolysis of a mixture of the fullerenes (C₆₀/C₇₀) and TPDAE. The electron transfer from the TPDAE to excited triplet state of the fullerenes (C₆₀/C₇₀) quantum yields and rate constants of electron transfer from TPDAE to excited triplet state of fullerenes (C₆₀/C₇₀) in benzonitrile have been evaluated by observing the transient absorption bands in the near‐IR region where the excited triplet state, radical anion of fullerenes (C₆₀/C₇₀) and radical cations of TPDAE are expected to appear.     

Evaluation of Transient Absorption Spectra of N, N, N′, N′- Tetra - ( p -methylphenyl ) - 4, 4′- diamino - 1, 1′- diphenyl Ether ( TPDAE ) for Electron Transfer from TPDAE to Fullerenes ( C60 / C70 ) by Laser Flash Photolysis

Photoinduced electron transfer processes between fullerenes (C60 / C70) and N, N, N′, N′- tetra - ( p-methylphenyl ) - 4, 4′- diamino - 1, 1′- diphenyl ether ( TPDAE ) have been studied by nanosecond laser flash photolysis. Quantum yields and rate constants of electron transfer from TPDAE to excited triplet state of fullerenes (C60 / C70 ) in benzonitrile have been evaluated by observing the transient absorption bands in the near-IR region where the excited triplet state, radical anion of fullerenes ( C60 / C70 ) and radical cations of TPDAE appear.     

Evaluation of Transient Absorption Spectra of N, N, N, N- Tetra - ( p -methylphenyl ) - 4, 4- diamino - 1, 1- diphenyl Ether ( TPDAE ) for Electron Transfer from TPDAE to Fullerenes ( C_(60) / C_(70) ) by Laser Flash Photolysis

Fullerenes C60 and C70 have high electron affinity ( 2.6 - 2.8 ev ) and readily form anions on electronchemical reduction1, which were famous as electron acceptor in photo-excitation because of symmetrical shape, large size, and properties of its p - electron system2. After observation of molecular ferromagnetism3 in the tetrakis (dimethylamino ) ethylene salt of C60 as well as the occurrence of ultra-fast photoinduced electron transfer within the dimethyl aniline - C60 complex4, prompted us…     

One‐dimensional CuII coordination polymers containing C2h‐symmetric 1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylate linkers

Two new one‐dimensional Cu^II coordination polymers (CPs) containing the C_2h‐symmetric terphenyl‐based dicarboxylate linker 1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylate (3,3′‐TPDC), namely catena‐poly[[bis(dimethylamine‐κN)copper(II)]‐μ‐1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylato‐κ⁴O,O′:O′′:O′′′] monohydrate], {[Cu(C₂₀H₁₂O₄)(C₂H₇N)₂]·H₂O}_n, (I), and catena‐poly[[aquabis(dimethylamine‐κN)copper(II)]‐μ‐1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylato‐κ²O³:O^3′] monohydrate], {[Cu(C₂₀H₁₂O₄)(C₂H₇N)₂(H₂O)]·H₂O}_n, (II), were both obtained from two different methods of preparation: one reaction was performed in the presence of 1,4‐diazabicyclo[2.2.2]octane (DABCO) as a potential pillar ligand and the other was carried out in the absence of the DABCO pillar. Both reactions afforded crystals of different colours, i.e. violet plates for (I) and blue needles for (II), both of which were analysed by X‐ray crystallography. The 3,3′‐TPDC bridging ligands coordinate the Cu^II ions in asymmetric chelating modes in (I) and in monodenate binding modes in (II), forming one‐dimensional chains in each case. Both coordination polymers contain two coordinated dimethylamine ligands in mutually trans positions, and there is an additional aqua ligand in (II). The solvent water molecules are involved in hydrogen bonds between the one‐dimensional coordination polymer chains, forming a two‐dimensional network in (I) and a three‐dimensional network in (II).     

Synthesis and Crystal Structure of N,N＇-Dimethyldithio-arbamato-Copper（Ⅰ） Polymer {[Cu（Me2dtc）]2}n

Reactions of CuSCN with tetramethylthiuram disulfide in CH₃CN in the presence of styrene and N,N,N′,N″,N″‐pentamethyldiethylenetriamine gave rise to a new copper(I) complex ofN,N′‐dimethyldithiocabamate ([CU(S₂CNMe₂)]₂)_n. The title compound crystallized in the triclinic P‐1 space group with lattice parameters a=0.7610(4) nm, b=0.8911(4) nm, c=0.9268(5) nm, α=68.66(1)°, β=83.88(2)°, γ=79.31(2)°, V=0.5748(5) nm³, Z=2. The compound has a unique 1D chain structure composed of CuSCSCuSCS eight‐membered rings and a pair of CU? S bonds, the structure of which has been determined by singlecrystal X‐ray crystallography. The isolation of this compound may provide some helpful information for the cause of the induction periods of the reverse atom transfer radical polymerization.     

Effect of pH on the charge‐assisted hydrogen‐bonded assembly of the anionic [Cu(oxalate)2]2− building unit and N,N′‐ditopic cations

By the solvothermal reaction under acidic conditions of Cu(NO₃)₂·3H₂O, Na₂C₂O₄ and the N,N′‐ditopic organic coligands 1‐(pyridin‐4‐yl)piperazine (ppz) and 1,2‐bis(pyridin‐4‐yl)ethane (bpa), two novel anionic copper(II) coordination compounds were obtained, namely the one‐dimensional coordination polymer catena‐poly[4‐(pyridin‐1‐ium‐4‐yl)piperazin‐1‐ium [[(oxalato‐κ²O¹,O²)copper(II)]‐μ‐oxalato‐κ³O¹,O²:O^1′]], {(C₉H₁₅N₃)[Cu(C₂O₄)₂)]}_n or {(H₂ppz)[Cu(C₂O₄)₂]}_n, (I), and the discrete ionic complex 4,4′‐(ethane‐1,2‐diyl)dipyridinium bis(oxalato‐κ²O¹,O²)copper(II), (C₁₂H₁₄N₂)[Cu(C₂O₄)₂] or (H₂bpa)[Cu(C₂O₄)₂], (II). The products were characterized by single‐crystal X‐ray diffraction, elemental analysis, powder X‐ray diffraction, thermogravimetric analyses and UV and IR spectroscopic techniques. The [Cu(C₂O₄)₂]²⁻ units for (I) and (II) are stabilized by H₂ppz²⁺ and H₂bpa²⁺ cations, respectively, via charge‐assisted hydrogen bonds. Also, a study of the pH‐controlled synthesis of this system shows that (I) was obtained at pH values of 2–4. When using bpa, a two‐dimensional square‐grid network of [Cu(C₂O₄)(bpa)]_n was obtained at a pH of 4. This indicates that the pH of the reaction also plays a key role in the structural assembly and coordination abilities of oxalate and N,N′‐ditopic coligands.     

Axially Dissymmetric Chiral (R)‐N,W‐Bis(2‐hydroxy‐3,5‐ditert‐butyl‐arylmethyl)‐1, 1′‐binaphthalene‐2,2′‐diamine as Chiral Ligands in the Reaction of Diethylzinc to Aldehydes†

Chiral ligand (A)‐N,N′‐Bis(2‐hydroxy‐3,5‐di‐tert‐butyl‐arylmethyl)‐1,1′‐binaphthalene‐2,2′‐diamine derived from the reduction of Schiff base (R)‐2,2′‐bis (3,5‐di‐tert‐butyl‐2‐hydroxybenzylideneamino)‐1, 1′‐binaphthyl with LiAlH₄, is fairly effective in the asymmetric addition reaction of diethylzinc to aldehydes by which good yields (46%‐94%) of the corresponding sec‐alcohols can be obtained in moderate ee (51%‐79%) with R configuration for a variety of aldehydes.     

New Chiral Ligand N—Toluenesulfony1—2,2‘—dimethoxy—6,6’—di—aminobiphenyl for Catalytic Asymmetric Transfer Hydrogenation of Ketones

A new chiral ligand N‐p‐toluenesulfonyl‐2,2′‐dimethoxy‐6,6′‐diaminobiphenyl (Ts‐DMBDPPA) was prepared from 2,2′‐dimethoxy‐6,6′‐diaminobiphenyl via N‐tosylation. Its Ru(II) complex was effective catalysts for catalytic asymmetric transfer hydrogenation of aromatic ketones (with ee's up to 69.3%).     

Solid Phase Extraction of Thallium(III) on Micro Crystalline Naphthalene Modified with N,N’-Bis(3-methylsalicylidene)- ortho-phenylenediamine and Determination by Spectrophotometry

A novel, simple, sensitive and effective method has been developed for preconcentration of thallium on N,N’-bis(3-methylsalicylidene)-ortho-phenylenediamine (MSOPD) adsorbent in a pH range 5.0—10.0, prior to its spectrophotometric determination, based on the oxidation of bromopyrogallol red at λ＝520 nm. This method makes it possible to quantitize thallium in a range of 3.6×10－9 to 2.0×10－5 mol/L, with a detection limit (S/N＝3) of 1.42×10－9 mol/L. This procedure has been successfully applied to determine the ultra trace levels of thallium in the environmental samples, free from the interference of some diverse ions. The precision, expressed as relative standard deviation of three measurements, is better than 2.9%.