Assembly-enhanced triplet-triplet annihilation upconversion in the aggregation formed by Schiff-base Pt(II) complex grafting-permethyl-β-CD and 9, 10-diphenylanthracence dimer

Water-soluble triplet sensitizer with permethyl-β-cyclodextrin (PMCD) grafting on a Schiff-base Pt (II) complex (Pt-2),was synthesized to enhance the efficiency of triplet-triplet energy transfer through hostguest complexation.DPA dimer A-2 in which two DPA carboxylate were covalently linked with an alkyl chain showed an improved triplet-triplet annihilation through both intramolecular interaction and self-aggregation. Significantly improved TTA-UC emission was observed with Pt-2 and A-2 as the donor/acceptor pair.     

ELECTRON TRANSFER AND PHOTOCHEMICAL VALENCE ISOMERIZATION IN ANTHRACENE AND NORBORNADIENE SYSTEMS

To harvest the sun light and to promote the amount of energystored,a new binary compound which links a sensitizer(electron donor),anthracene,and substrate(electron acceptor),norbornadiene,in a non-conjugated manner without increase in molecular weight was synthesized.Theinter-and intramolecular photosensitized isomerization and the mechanismwere studied.     

Synthesis,crystal structure,and application of an acenaphtho[1,2-k] fluoranthene diimide derivative

Organic electron acceptor materials play an important role in organic electronics.Recently,many organic electron acceptors have been developed,in which aromatic fused-imides have proved to be a promising family of excellent electron acceptors.We report the first synthesis of a novel aromatic fused-imide,acenaphtho[1,2-k]fluoranthene diimide derivative(AFI),using lithium-halogen exchange and Diels-Alder reactions.The construction of a large conjugated plane and the introduction of electron-withdrawing imide groups endow AFI with a low lowest unoccupied molecular orbital(LUMO)level of 3.80 e V.AFI exhibits a regular molecular arrangement and strong - interactions in the single-crystal structure,which indicates its potential application in organic electronic devices.Solar cell devices that were fabricated using AFI as the electron acceptor and P3HT as the electron donor achieved an energy conversion efficiency of 0.33%.     

Triplet-triplet annihilation upconversion materials as electrophoretic inks

Luminescent materials that can be reversibly switched by electric field stimulation are attractive since the potential application for optoelectronic devices. Here we report a triplet-triplet annihilation upconversion(TTA-UC) system with electrophoretic response which is developed as the electrophoretic ink. The TTA-UC system consists of an ionic derivative of 9,10-diphenyl anthracene(DPA) as the annihilator and Pt(II)octaethylporphyrin(PtOEP) as the sensitizer. Upon applying an electric field, ...     

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.     

Effect of furan π-bridge on the photovoltaic performance of D-A copolymers based on bi(alkylthio-thienyl)benzodithiophene and fluorobenzotriazole

The medium band gap donor-acceptor(D-A) copolymer J61 based on bi(alkylthio-thienyl)benzodithiophene as donor unit and fluorobenzotriazole as acceptor unit and thiophene as π-bridge has demonstrated excellent photovoltaic performance as donor material in nonfullerene polymer solar cells(PSCs) with narrow bandgap n-type organic semiconductor ITIC as acceptor.For studying the effect of π-bridges on the photovoltaic performance of the D-A copolymers,here we synthesized a new D-A copolymer J61-F based on the same donor and acceptor units as J61 but with furan π-bridges instead of thiophene.J61-F possesses a deeper the highest occupied molecular orbital(HOMO) level at-5.45 eV in comparison with that(-5.32 eV) of J61.The non-fullerene PSCs based on J61-F:ITIC exhibited a maximum power conversion efficiency(PCE) of 8.24%with a higher open-circuit voltage(V_(oc)) of 0.95 V,which is benefitted from the lower-lying HOMO energy level of J61-F donor material.The results indicate that main chain engineering by changing π-bridges is another effective way to tune the electronic energy levels of the conjugated D-A copolymers for the application as donor materials in non-fullerene PSCs.     

Comparison of conventional and inverted structures in fullerene-free organic solar cells

A n-type small molecule DC-IDT2 F, with 4,4,9,9-tetrakis(4-hexylphenyl)-indaceno[1,2-b:5,6-b]dithiophene as a central building block, furan as π-bridges, and 1,1-dicyanomethylene-3-indanone as end acceptor groups,was synthesized and used as an electron acceptor in solution-processed organic solar cells(OSCs). DC-IDT2 F exhibited good thermal stability, broad and strong absorption in 500–850 nm, a narrow bandgap of 1.54 e V,LUMO of –3.88 eV, HOMO of –5.44 eV and an electron mobility of 6.5 × 10–4cm2/(V·s). DC-IDT2F-based OSCs with conventional and inverted structures exhibited power conversion efficiencies of 2.26 and 3.08%, respectively. The effect of vertical phase separation and morphology of the active layer on the device performance in the two structures was studied.     

Rationally pairing photoactive materials for high-performance polymer solar cells with efficiency of 16.53%

The emergence of non-fullerene acceptors(NFA) offers a promising opportunity to develop high-performance donor/acceptor pairs with high power conversion efficiency,as NFAs offer tunable energy levels,broad absorption and suitable aggregation property.In order to enhance light-harvesting capability of active layers,we choose a wide bandgap polymer PTQ10 as the donor to blend with a narrow bandgap NFAY6 as the acceptor.In comparison with PTQ10:IDIC blend,~130 nm red-shifted absorption spectrum is observed in the PTQ10:Y6 blend,which potentially enhance the short-circuit current density(Jsc) for the PSCs.In addition,the optimal PTQ10:Y6 blend shows higher photoluminescence quenching efficiency and more efficient charge separation,higher charge mobilities,as well as weaker bimolecular recombination over the PTQ10:IDIC blend,which leads to an outstanding power conversion efficiency(PCE) of 16.53%,with a notable Jsc of 26.65 mA cm^-2 and fill factor(FF) of 0.751.     

Rylene diimide and dithienocyanovinylene copolymers for polymer solar cells

Two polymers containing(E)-2,3-bis(thiophen-2-yl)acrylonitrile(CNTVT) as a donor unit, perylene diimide(PDI) or naphthalene diimide(NDI) as an acceptor unit, are synthesized by the Stille coupling copolymerization, and used as the electron acceptors in the solution-processed organic solar cells(OSCs). Both polymers exhibit broad absorption in the region of 300–850 nm. The LUMO energy levels of the resulted polymers are ca. –3.93 eV and the HOMO energy levels are –5.97 and –5.83 eV. In the binary blend OSCs with PTB7-Th as a donor, PDI polymer yields the power conversion efficiency(PCE) of up to 1.74%, while NDI polymer yields PCE of up to 3.80%.     

Synthesis of two-dimensional π-conjugated polymers pendent with benzothiadiazole and naphtho[1,2-c:5,6-c]bis[1,2,5]thiadiazole moieties for polymer solar cells

Four new 2D donor–acceptor conjugated polymers were designed and synthesized.These new polymers comprised fluorenealt-triphenylamine or carbazole-alt-triphenylamine as the backbones,and pendants with 2,1,3-benzothiadiazole(BT)or naphtho[1,2-c:5,6-c]bis[1,2,5]thiadiazole(NT)in a triphenylamine unit as the side groups.By changing the acceptor BT for a stronger electron-withdrawing unit of NT moiety in the side chain,the energy levels,absorption spectra,band gaps,and charge-transport abilities of the resultant polymers could be effectively tuned.Bulk heterojunction solar cells with these polymers as the electron donors and(6,6)-phenyl-C71-butyric acid methyl ester as the electron acceptor exhibited high open-circuit voltage(more than 0.8 e V).The power conversion efficiency can be improved from 1.37%to 3.52%by replacing the BT with an NT moiety,which indicates that introducing NT as the side-chain building block can be an effective strategy to construct efficient 2D conjugated polymers for PSCs.     

Effects of Self—coiling of Organic Molecules on Intramolecular Exciplex Formation and Fluoresscence Quenching in DX—H2O Solvent System

Effects of self-coiling of organic molecules on intramolecular exciplex formation of compound I,in which the carbazole chromophore and terephthalic acid methylester acceptor group are linked by one (CH2)10 chain,and the decrease of the fluorescence intensities of compounds Ⅱ，Ⅲ，and Ⅳ,in which the carbazole chromophore and 3,5-dinitrobenzoate are connected by one aliphatic chain of (CH2)10 (Ⅱ），（CH2）12（Ⅲ）,or (CH2)4(Ⅳ）,have been studied in the dioxane (DX)-H2O binary system.The results show that self-coiling of organic molecules in DX-H2O facilitates intramolecular exciplex formation of I and induces the decrease of fluorescence intensities of Ⅱ,bacause of the proximity effect brought about by selfcoiling of organic molecules under hydrophobic-lipophilic interaction(HLI) between the excited carbazole chromophore and the acceptor.Since the similar effects are observed even when the concentration of the probes are less than their CAgCs(critical aggregate concentrations )in the DX-H2O mixture with the same φ values,formation of the intermolecular exciplex has been excluded.The effects are found to be strongly depended on φ values,indication that they are mainly driven by HLI.The properties of the acceptors can also affect the intramolecular exciplex formation.With terephthalic acid methylester moiety as the acceptor,the carbazole chromophore exhibits the fluorescence spectra of the exciplex,while with 3,5-dinitrobenzoate moiety as the acceptor,only the fluorescence spectra of excited carbazolyl chromophore are observed.     

Recent development of perylene diimide-based small molecular non-fullerene acceptors in organic solar cells

This review summarizes the recent progress of perylene diimide (PDI) derivatives used as the acceptor materials in non-fullerene organic solar cells. The resulting structure-property correlations and design strategies of this type of acceptors are discussed and commented, which will help to constructing high-performance PDI-based acceptor materials in the future. The problems at present and the effort direction are also pointed out in this review.     

Zinc-coordination Polymers Based on a Donor-acceptor Mix-ligand System: Syntheses,Crystal Structures and Photophysical Properties

By employing an electron-rich tricarboxytriphenyl amine as donor ligand and electron-deficient 2,4,6-tris(pyridin-4-yl)-1,3,5-triazine as acceptor ligand to assemble with Zn2+ions,three new coordination polymers were successfully synthesized and characterized systematically.Three compounds with different structures were obtained by regulating the reaction solvent,and the effect of the reaction solvent on the synthesis of crystals was explored.Furthermore,the photophysical properties of the compounds were investigated.     

Syntheses,Structures and Properties of Two 2D Coordination Polymers from 5-（Pyridin-2-yl-methyl）aminoisophthalate

Hydrothermal reactions of 5-(pyridin-2-yl-methyl)aminoisophthalic acid(H2paip) with Mn(OAc)2·4H2O and Cu(NO3)2·3H2O produced two 2D complexes, [Mn(paip)]n·nH2O(1) and [Cu(paip)(H2O)]n(2). In complex 1, paip serves as a μ4-bridge, and its two carboxylate groups in μ2,η2-bridging and chelating modes connect Mn(Ⅱ) into 1D chains, which are further extended into a 2D layer through coordination of two chelating nitrogen atoms. However, paip in complex 2 acts as a μ3-bridge to link Cu(Ⅱ) into a 2D layer, in which two carboxylate groups function in a monodentate mode, and hydrogen bonds between the coordinated water and carboxylate oxygen atoms further extend the 2D layers into a 3D supramolecular network. The frameworks of complexes 1 and 2 are stable up to 470 and 250 ℃, respectively. Magnetic measurement shows that complex 2 possesses a weak antiferromagnetic interaction.     

Pt/FeSnO(OH)_5: A Novel Supported Pt Catalyst for Catalytic Oxidation of Benzene

Pt/FeSnO(OH)_5 was synthesized as a novel catalyst for VOCs oxidation. Compared with Pt/γ-Al_2O_3 during catalytic oxidation of benzene, Pt/Fe Sn O(OH)5 showed better catalytic activity. After characterization of the catalysts by XRD, SEM, TEM, EDS, XPS, BET, TGA and DTA, we found most Pt could be reduced to metallic state when the hydroxyl catalyst was used as supporter, and the metallic Pt in Pt/Fe Sn O(OH)5 was more active than the oxidized Pt in Pt/γ-Al_2O_3 in catalytic oxidation of VOCs. Pt/FeSnO(OH)_5 shows both good catalytic activity and high stability, which may be a promising catalyst. This study may also be helpful for the design and fabrication of new catalysts.     

Unprecedented 1D Mixed-metal Polynuclear Cyclometalated Platinum Complexes： Synthesis, Structural Characterization and Spectroscopic Properties

The complexes [Pt2L2（μ-dppm）]（ClO4）2 （1） and {[Pt2L2（μ-dppm）Li（CH3CN）2]（ClO4）3}n （2）, where HL is 6-[4-（diethoxyphosphorylmethyl）phenyl]-2,2′-bipyridinyl and dppm is bis（diphenylphosphino）methane, have been synthesized and characterized. In complex 1 the platinum（Ⅱ） center adopts a distorted square planar coordination geometry. The polymer 2 exhibits a ＂stairstep＂ configuration with one-dimensional Pt（Ⅱ）N^N^CPO- Li（Ⅰ）-OPC^N^ NPt（Ⅱ） mixed-metal units which are linked through dppm. Both complexes have metal-metal interaction with Pt- Pt distances of 3.325（2） and 3.1432（9） A, respectively, and display strong metal-metal-to-ligand charge-transfer （MMLCT） triplet state emission. The density-functional-theory calculation was used to interpret the absorption spectra of the complexes.     

High-performance all-polymer solar cells enabled by a novel low bandgap non-fully conjugated polymer acceptor

The non-fully conjugated polymer as a new class of acceptor materials has shown some advantages over its small molecular counterpart when used in photoactive layers for all-polymer solar cells(all-PSCs), despite a low power conversion efficiency(PCE)caused by its narrow absorption spectra. Herein, a novel non-fully conjugated polymer acceptor PFY-2 TS with a low bandgap of~1.40 eV was developed, via polymerizing a large π-fused small molecule acceptor(SMA) building block(namely YBO) with a nonconjugated thioalkyl linkage. Compared with its precursor YBO, PFY-2 TS retains a similar low bandgap but a higher LUMO level.Moreover, compared with the structural analog of YBO-based fully conjugated polymer acceptor PFY-DTC, PFY-2 TS shows a similar absorption spectrum and electron mobility, but significantly different molecular crystallinity and aggregation properties,which results in optimal blend morphology with a polymer donor PBDB-T and physical processes of the device in all-PSCs. As a result, PFY-2 TS-based all-PSCs achieved a PCE of 12.31% with a small energy loss of 0.56 eV enabled by the reduced non-radiative energy loss(0.24 eV), which is better than that of 11.08% for the PFY-DTC-based ones. Our work clearly demonstrated that non-fully conjugated polymers as a new class of acceptor materials are very promising for the development of high-performance all-PSCs.     

Preparation and Intramolecular Electron Transfer of A Covalently Linked Zinc Porphyrin-Methyl Viologen (MV2+) Complex

Porphyrins and methyl viologen(MV~(2+)) are widely used as a photosensitizer and an electron acceptor respectively in photoinduced electron transfer systems. Literatures covered numerous examples of photochemical studies of porphyrins covalently linked to various electron acceptor units, such as viologen, which functioned as both a photosensitizer and an electron acceptor in the same molecule. However, the length of the linked chain between porphyrin and viologen is very important. To improve the rate of photoin-     

Synergistic effect of fluorination on both donor and acceptor materials for high performance non-fullerene polymer solar cells with 13.5% efficiency

A high performance polymer solar cells(PSCs) based on polymer donor PM6 containing fluorinated thienyl benzodithiophene unit and n-type organic semiconductor acceptor IT-4 F containing fluorinated end-groups were developed. In addition to complementary absorption spectra(300–830 nm) with IT-4 F, the PM6 also has a deep HOMO(the highest occupied molecular) level(-5.50 e V), which will lower the open-circuit voltage(V_(oc)) sacrifice and reduce the E_(loss) of the IT-4 F-based PSCs. Moreover, the strong crystallinity of PM6 is beneficial to form favorable blend morphology and hence to suppress recombination. As a result, in comparison with the PSCs based on a non-fluorinated D/A pair of PBDB-T:ITIC with a medium PCE of 11.2%, the PM6:IT-4 Fbased PSCs yielded an impressive PCE of 13.5% due to the synergistic effect of fluorination on both donor and acceptor, which is among the highest values recorded in the literatures for PSCs to date. Furthermore, a PCE of 12.2% was remained with the active layer thickness of up to 285 nm and a high PCE of 11.4% was also obtained with a large device area of 1 cm~2. In addition, the devices also showed good storage, thermal and illumination stabilities with respect to the efficiency. These results indicate that fluorination is an effective strategy to improve the photovoltaic performance of materials, as well as the both fluorinated donor and acceptor pair-PM6:IT-4 F is an ideal candidate for the large scale roll-to-roll production of efficient PSCs in the future.     

Preparation, Characterization of Hydrotalcites and the Catalytic Properties in Synthesis of o-Phenylphenol over Pt／CHT

Mg/Al mixed oxides with molar ratios of 2-6 of Mg to Al used as supports for platinum catalysts were obtained by the thermal decomposition method. The effect of the composition of the mixed oxides on the physicochemical properties was studied by TPD, nitrogen sorption, XRD and TG-DTA characterization methods. The synthesis of o-phenylphenol (OPP) from a dimer (obtained from cyclohexanone condensation) was investigated over Pt/CHT catalysts and compared with those over Pt/MgO and Pt/Al2O3 catalysts. These catalysts show a high activity and selectivity for OPP, with a conversion reaching 93.8% and a selectivity reaching 87.9% in some experiments. For Pt/CHTx catalysts, the calcined hydrotalcites exhibited strong base sites, which were necessary to catalyze the synthesis of OPP.