Aggregation behavior of amphiphilic D-π-A molecules bearing recognition group

Aggregation behavior of two amphiphilic D-π-A molecules bearing barbituric acid as both recogniton group and electron-drawing substituent , 5-(4-dodecyl oxybenzylidene)-(1H, 3H)-2,4,6-pyrimidine trione (PB12) and 5-(4-N,N-didodecyl aminobenzylidene)-(1H,3H)-2,4,6-pyrimidine trione (AB12) was studied by UV-visible, fluorescence, and surface voltaic spectroscopies (SPS). The experimental results indicate that PB12 tends to form J-aggregate and AB12 tends to form H-aggregate under increasing concentration. An intramolecular twisted charge transfer (TICT) emission around 500 nm is observed when J-aggregate is formed between PB12 molecules, and an excimer emission around 600 nm is observed when H-aggregate is formed between AB12 molecules.

Selective fluorination on donor and acceptor for management of efficiency and energy loss in non-fullerene organic photovoltaics

Although fluorination has been proved effective to modulate optoelectronic properties and film morphology,knowledge of managing power conversion efficiency(PCE)and energy loss(Eloss)of organic photovoltaics(OPVs)by selective fluorination on the donor and/or acceptor is lacking.Herein we designed and synthesized three 1,2,3-benzotriazole(BTA)-based linear polymers(PE45,PE46 and PE47)with different numbers of fluorine atom substitution on the conjugated phenyl side chain.Two classic non-fullerene acceptors(NFAs)Y5(without fluorination)and Y6(with fluorination)were utilized to manage the device efficiency and energy loss.The results revealed that increasing fluorine substitutions on polymer donor improved the OPV efficiencies when the fluorinated Y6 was used as the acceptor,whereas decreased the PCEs when the non-fluorinated Y5 was used as the acceptor.The energy loss declined with the growing fluorine substitutions on polymer donor,and Y5 systems gave the lower values in comparison with the corresponding Y6 cases.It turns out that PE47:Y6 achieved the highest PCE of 15.58%with an open-circuit voltage(VOC)of 0.84 V(Eloss=0.56 e V)due to the highest and balanced hole/electron mobilities,suppressed bimolecular recombination and fibril network morphology,which is the highest value in the BTA-based polymers.Furthermore,PE47:Y5 attained an ultralow non-radiative energy loss of 0.15 e V,which is one of the lowest values among the reported OPVs.Our work could not only give a direct path on how to manage the efficiency and energy loss by selective fluorination on donor and acceptor,but also show a deep understanding on charge generation,transport and collection induced by selective fluorination.

Tailoring Excited State Properties and Energy Levels Arrangement via Subtle Structural Design on D-π-A Materials

The donor-n-conjugated-acceptor （D-n-A） structure is an important design for the luminescent materials be- cause of its diversity in the selections of donor, n-bridge and acceptor groups. Herein, we demonstrate two examples of D-^-A structures capable to finely modulate the excited state properties and arrangement of energy levels, TPA-AN-BP and CZP-AN-BP, which possess the same acceptor and n-bridge but different donor. The investigation of their photophysical properties and DFT calculation revealed that the D-n-A structure with proper donor, n-bridge and acceptor can result in separation of frontier molecular orbitals on the corresponding donor and acceptor with an obvious overlap on the n-bridge, resulting in a hybridized local and charge-transfer （HLCT） excited state with high photoluminescent （PL） efficiencies. Meanwhile, their singlet and triplet states are arranged on corresponding moie- ties with large energy gap between T2 and T1, and a small energy gap between S1 and T2, which favor the reverse intersystem crossing （RISC） from high-lying triplet levels to singlet levels. As a result, the sky-blue emission non-doped OLED based on the TPA-AN-BP reached maximum external quantum efficiency （EQE） of 4.39% and a high exciton utilization efficiency （EUE） of 77%. This study demonstrates a new strategy to construct highly effi- cient OLED materials.

Cooperative Supramolecular Polymerization of Propeller-Shaped Triphenylamine Cyanostilbenes for Explosive Detection

Self-assembly ofπ-conjugated compounds into supramolecular polymers has received considerable attention because of their intrinsic scientific interests and technological applications.As compared toπ-conjugated rods,discotics,and macrocycles,propeller-shapedπ-conjugated molecules have been less exploited to form long-range-ordered supramolecular polymers.Herein a novel type of supramolecular polymers has been constructed on the basis of propeller-shaped triphenylamine cyanostilbenes.The designed compound adopts nucleation-elongation cooperative mechanism for the supramolecular polymerization process,because of the participation of three-fold hydrogen bonds between the neighbouring monomers.The supramolecular polymeric state displays amplified chirality and enhanced emission than those in the monomeric state.The resulting supramolecular polymers exhibit severe emission quenching upon addition of 2,6-dinitrotoluene,ascribed to photoinduced electron transfer from the triphenylamine cyanostilbenes to the explosive analyte.The current study proves the feasibility to supramolecular polymerize propeller-likeπ-conjugated molecules,serving as a promising type of explosive sensor owing to their guest encapsulation and signal amplification capabilities.