Two extended hybrid conjugated systems based on a triphenylamine(TPA) core with two and three peripheral 1,4-dithiafulvenes(DTF) units coded WH-2 and WH-3 as hole-transporting materials(HTMs) applied in perovskite sol...Two extended hybrid conjugated systems based on a triphenylamine(TPA) core with two and three peripheral 1,4-dithiafulvenes(DTF) units coded WH-2 and WH-3 as hole-transporting materials(HTMs) applied in perovskite solar cells(PSCs) are synthesized by facile one-step reaction in good yield over 75%. DTF unit as electron donor can enhance the electron donating ability and the fusion of benzenic ring of TPA with DTF unit may lead to reinforced intermolecular interactions in the solid state. In addition,WH-2 and WH-3 exhibit a pyramid shape containing partial planarity and quasi three-dimensionality features, which is also conducive to enhancing the π-π stacking of molecules in the solid state. The above-mentioned structural characteristics make the two HTMs have good hole mobilities. As a result,WH-2 and WH-3 obtained the high intrinsic hole mobilities of 4.69 × 10^(-4)and 2.18 × 10^(-3)cm^(2)V^(-1)s^(-1)respectively. Finally, the power conversion efficiencies(PCEs) of PSCs with WH-2 and WH-3 as cost-effective dopant-free HTMs are 15.39% and 19.22% respectively and the PCE of PSC with WH-3 is on a par with that of PSC with Li-TFSI/t-BP doped Spiro-OMe TAD(19.67%).展开更多
An electron donor-π-bridge-electron acceptor(D-π-A) optical functional organic compound comprising a triphenylamine moiety as the electron donor and pyridine moiety as the electron acceptor was synthesized. The stru...An electron donor-π-bridge-electron acceptor(D-π-A) optical functional organic compound comprising a triphenylamine moiety as the electron donor and pyridine moiety as the electron acceptor was synthesized. The structure of the compound was solved by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21, with a = 9.753(5), b = 8.815(5), c = 25.554(5) ?, β = 96.315(5)°, V = 2184(2) ?~3, Z = 2, D_c = 1.136 g/m^3, F(000) = 792, Μr = 746.92, μ = 0.069 mm^(-1), the final R = 0.0658 and wR = 0.1730 for 6790 observed reflections with I > 2(I). Study of nonlinear optical properties shows that the compound exhibits excellent two-photon excited fluorescence with the two-photon absorption cross-section value of 116 GM. The structure-property relationship was researched in detail through X-ray crystallography and quantum chemical calculation. Result of living cell imaging experiment shows its potential in fluorescence microscopy bioimaging.展开更多
A starburst tripbenylamine cored N-vinyl carbazole (V-Cz) branched compound was designed and synthesized via optimized Heck reaction in a yield of 40-60%. Moderate yield came from decomposition of V-Cz and self-coup...A starburst tripbenylamine cored N-vinyl carbazole (V-Cz) branched compound was designed and synthesized via optimized Heck reaction in a yield of 40-60%. Moderate yield came from decomposition of V-Cz and self-coupling of triiodo-triphenylamine. TCz-TPA adopts a highly twisted propeller conformation by molecular mechanical optimization. It is readily soluble for its highly twisted conformation. Transparent and pinhole free films could be easily fabricated by spin-coating for its starburst structure. It emits blue-greenish light in CH2Cl2 peaked at 460 nm with a narrow full-width at half-maximum (FWHM) of 65 nm. As compared,展开更多
In the past decade,perovskite solar cells have become a promising candidate in the photovoltaic industry owing to their high power conversion efficiency that surpasses 25%.However,there are certain limitations that ha...In the past decade,perovskite solar cells have become a promising candidate in the photovoltaic industry owing to their high power conversion efficiency that surpasses 25%.However,there are certain limitations that have hindered the development and full-scale practical application of these cells,including the high cost and degradation of perovskite caused by the dopants.Hence,there is an urgent need to develop dopant-free hole transport materials(HTMs).In recent years,HTMs based on triphenylamine(TPA-HTMs)are receiving growing interest owing to their high hole mobility,excellent film formation,and suitable energy levels.The literature here covers work relevant to TPA-HTMs in the last five years.They have been classified according to different core types.The correlations between performance and structure are summarized,and the future development trend of TPA-HTMs is highlighted.展开更多
Here, a series of starburst triphenylamine(WD8) derivatives for dye-sensitized solar cells(DSSCs) applications have been designed. The frontier molecular orbitals(FMOs) property, absorption spectra, and charge transfe...Here, a series of starburst triphenylamine(WD8) derivatives for dye-sensitized solar cells(DSSCs) applications have been designed. The frontier molecular orbitals(FMOs) property, absorption spectra, and charge transfer rate property of WD8 and its derivatives were simulated. We also evaluated the FMOs energies and absorption spectra of WD8 and its derivatives with the TiO2 cluster. The simulation results show that the phenothiazine-triphenylamine and 2-cyanoacetic acid groups in the ortho-position will increase the HOMO energy, decrease the LUMO energy, and narrow the HOMO-LUMO gap of WD8. The charge injection from WD8 and its derivatives to TiO2 should be more favorable. The phenothiazine-triphenylamine and 2-cyanoacetic acid groups in the ortho-position will decrease the electron and hole injection barriers of WD8. The phenothiazinetriphenylamine and 2-cyanoacetic acid groups in the ortho-position will improve the absorption spectra properties of WD8. The absorption spectra of WD8 and its derivatives with the TiO2 cluster would have a red shift. The phenothiazine-triphenylamine and 2-cyanoacetic acid groups in the ortho-position will increase the charge transfer property of WD8.展开更多
Blue luminescent compounds T1―T4 containing triphenylamine donors,bipyridine acceptors and olefinic linkers were synthesized and characterized by 1 H NMR,13 C NMR and high resolution mass spectrometry(HRMS).Four co...Blue luminescent compounds T1―T4 containing triphenylamine donors,bipyridine acceptors and olefinic linkers were synthesized and characterized by 1 H NMR,13 C NMR and high resolution mass spectrometry(HRMS).Four compounds T1―T4 exhibit excellent solubility in common solvents and good film forming properties.Quantum chemical calculations show that compounds T1―T4 have asymmetric linear structures and the proper highest occupied molecular orbital(HOMO) levels.The UV-Vis absorption and fluorescence emission spectra of the four compounds in dilute chloroform solutions and on the solid films were measured.It reveals that compounds T1―T4 exhibit similar spectral behavior,suggesting that these compounds can form amorphous state in solid films.The calculated absorption and emission spectra of compounds T1―T4 are in good agreement with experimentally determined ones.Compounds T1―T4 have absolute fluorescence quantum yield above 17% in dilute chloroform solutions.Four compounds possess high glass-transition temperature(T g) exceeding 97 ℃ and the maximum T g is 155.28 ℃ for compound T3.Cyclic voltammetry measurements show that these compounds have proper HOMO levels in a range of-5.01―-5.13 eV for hole injection.The properties of compounds T1―T4 indicate that these compounds are candidates for the application in organic light-emitting devices(OLEDs) as hole-transporting materials(HTMs).展开更多
The two-photon fluorescence properties and ultrafast responses of a hyperbranched polyyne (hb-DPP-J2) with triphenylamine as the central core, Diketo-Pyrrolo-Pyrrole as the connecting unit and electron acceptor are ...The two-photon fluorescence properties and ultrafast responses of a hyperbranched polyyne (hb-DPP-J2) with triphenylamine as the central core, Diketo-Pyrrolo-Pyrrole as the connecting unit and electron acceptor are studied. The polymer has a D-π-A-π-D conjugated structure along the extended polyyne w-bridge systems, and the effective condugated unit repeats itself in the whole hyperbranehed polymer chain. The polymer exhibits a large two-photon absorption cross section and high fluorescence quantum yields. The ultrafast dynamic results give a deep understanding of the excited energy transfer processes under excitation, and reveal a long relaxation lifetime of the intramolecular charge transfer (ICT) state.展开更多
A novel triphenylamine derivative of 4, 4'-bis-[2-[4-[N, N-bis-(4-methoxyphenyl-amino)]phenyl-1-yl]-vinyl-1-yl]-1, 1'-biphenyl (DMPAVBI) was synthesized. The chemical structure wasconfirmed by IR, H NMR spectr...A novel triphenylamine derivative of 4, 4'-bis-[2-[4-[N, N-bis-(4-methoxyphenyl-amino)]phenyl-1-yl]-vinyl-1-yl]-1, 1'-biphenyl (DMPAVBI) was synthesized. The chemical structure wasconfirmed by IR, H NMR spectroscopy and elemental analysis. Its properties were studied by 1UV-Vis spectroscopy, photoluminescence spectroscopy and cyclic voltammetry methods.展开更多
Four bipolar triphenylamine(TPA) charge transport materials were constructed by introducing imidazole and trifluoroacetyl groups into the TPA units, and characterized by the nuclear magnetic resonance spectrum(NMR) an...Four bipolar triphenylamine(TPA) charge transport materials were constructed by introducing imidazole and trifluoroacetyl groups into the TPA units, and characterized by the nuclear magnetic resonance spectrum(NMR) and mass spectrometry(MS). Among them, 4-(2-(1,3-trifluoroacetyl)imidazole)-phenyl-4,4?-di(4-methoxyphenyl)amine(2 Me OTPA-IOS, 1) was determined by X-ray single-crystal diffraction. The compound crystallizes in monoclinic system, space group P21/c with a = 24.338(5), b = 9.565(2), c = 11.456(2) ?, β = 99.427(3)°, Mr = 565.47, V = 2631.0(8) ?3,Z = 4,Dc = 1.428 g/cm3, μ = 0.125 mm–1, F(000) = 1160, the final R = 0.0559 and wR = 0.1265 for 5150 observed reflections with I > 2σ(I). The optimized configurations of the target compounds were obtained by quantum chemical calculation, and the bipolarity of transportable holes and electrons was predicted by the frontier molecular orbital(HOMO and LUMO), which was further confirmed by the time of flight(TOF) method. In addition, the introduction of the terminal flexible chain enhances the solubility, thermal stability(DSC and TGA) and film-forming property of all compounds, and the frontier orbital energy of the solid film of the compounds was also tested(UV-vis and PYS). Thus, these compounds have the bipolarity of transportable holes and electrons and show good solubility and thermal stability.展开更多
Triphenylamine(TPA)-based aggregation-induced emission luminogens(TPA-AIEgens),a type of photoactive material utilizing the typical TPA moiety,has recently attracted increasing attention for the diagnostics and treatm...Triphenylamine(TPA)-based aggregation-induced emission luminogens(TPA-AIEgens),a type of photoactive material utilizing the typical TPA moiety,has recently attracted increasing attention for the diagnostics and treatment of tumors due to their remarkable chemo-physical performance in optoelectronic research.TPA-AIEgens are distinguished from other photoactive agents by their strong fluorescence,good sensitivity,high signal-to-noise ratio,resistance to photobleaching,and lack of high concentration or aggregation-caused fluoresce quenching effects.In this review,we summarize the current advancements and the biomedical progress of TPA-AIEgens in tumor theranostics.First,the design principles of TPAAIEgens photoactive agents as well as the advanced targeting strategies for nuclei,cell membranes,cell organelle and tumors were introduced,respectively.Next,the applications of TPA-AIEgens in tumor diagnosis and therapeutic techniques were reviewed.Last,the challenges and prospects of TPA-AIEgens for cancer therapy were performed.The given landscape of the TPA-AIEgens hereby is meaningful for the further design and utilization of the novel photoactive material,which could be beneficial for the development of clinic applications.展开更多
The photocatalytic oxidative coupling of thiols is one of the most popular methods to synthesize the disulfides.Triphenylamine and its derivatives(TPAs)are promising for the above reaction,but suffer from the easy pol...The photocatalytic oxidative coupling of thiols is one of the most popular methods to synthesize the disulfides.Triphenylamine and its derivatives(TPAs)are promising for the above reaction,but suffer from the easy polymerization and difficult separation.To overcome these obstacles while controlling the photogenerated electrons transfer directly to target substrates,herein,we constructed one TPA-based metal-organic framework(MOF),(Me_(2)NH_(2))[Sr(TCBPA)]·DMA·3H_(2)O(1),by direct self-assembly of tris(4′-carboxybiphenyl)amine(H_(3)TCBPA)and photoredox inert strontium ion(Sr^(2+)).DFT calculations revealed that the valence band maximum(VBM)and the conduction band minimum(CBM)are mainly located on TCBPA^(3-),successfully inhibiting the undesirable electron migration to metal nodes.Experimental results indicated that 1 displays superior performance than homogeneous H_(3)TCBPA,which may result from the abundant π…π and C—H…π interactions between the well-arranged TCBPA^(3-)and the build-in electric field between the anionic framework and the Me_(2)NH^(2+).This work highlights that immobilizing TPAs into MOFs is one promising approach to designing heterogeneous photocatalysts for the synthesis of disulfides by oxidative coupling of thiols.展开更多
The stable coordinated metallo-complexes based on 2,2′:6′,2″-terpyridine(tpy)and its derivatives have been widely researched for various wide-ranging applications in photoelectronics,catalysis,sensor,photoluminesce...The stable coordinated metallo-complexes based on 2,2′:6′,2″-terpyridine(tpy)and its derivatives have been widely researched for various wide-ranging applications in photoelectronics,catalysis,sensor,photoluminescence,and so on.However,the most reported studies ignored the comprehensive comparison between structures modified by different positions and photoluminescence.Herein,we design a series of metallo-complexes which were assembled with tpy substituted triphenylamine(TPA)at different positions and metal ions and explored their photophysical properties.In the solution state,MLE_(2)based on the 5,5″-positions modification showed the highest PLQYs and PL intensity.With the increase of solvent polarity,MLB2exhibit the largest redshift.In the solid state,from MLA_(2)to MLE_(2),the emission colours are gradually red-shifted from yellow to red.The findings in this work may pave a new way to design functional metallo-complexes,not just for PL properties.展开更多
Two triphenylamine-based star-type push-pull chromophores(T1, T2) were designed and synthesized.Triphenylamine serves as the central core and acts as an electron-donating group surrounded by electronwithdrawing pentaf...Two triphenylamine-based star-type push-pull chromophores(T1, T2) were designed and synthesized.Triphenylamine serves as the central core and acts as an electron-donating group surrounded by electronwithdrawing pentafluorobenzene or N,N-dimethyl substituted tetrafluorobenzene, which are connected by ethylene bridges. Single-crystal X-ray diffraction confirmed the structures and molecular arrangement of two chromophores. The systematic photophysical research of T1 and T2 absorption characteristics was carried out to gain a better understanding of how structure-property relationships affect the observed nonlinear optical absorption phenomenon. Complementary calculations based on density functional theory(DFT) further confirmed the experimental results. Both chromophores exhibited excellent two-photon absorption(TPA) properties in CH_(2)Cl_(2). Notably, T2 has more remarkable nonlinear optical absorption effects with the TPA cross-section up to 4.24 × 10~7GM. By adjusting the electronic structures of the chromophores through introducing pentafluorobenzene or N,N-dimethyl as functional groups with different electron-donating or withdrawing behaviors, the TPA performance of the small organic molecule could be greatly enhanced. These molecular structures with push-pull systems were excellent candidates for different two-photon applications.展开更多
Two new multibranched thiophene-based triarylamine derivatives with 1,3,5-triazine core are synthesized and characterized. Their one-and two-photon absorption properties and aggregation-induced emission effect have be...Two new multibranched thiophene-based triarylamine derivatives with 1,3,5-triazine core are synthesized and characterized. Their one-and two-photon absorption properties and aggregation-induced emission effect have been investigated. Both the STAPA-based compounds are AIE active. The two-photon absorption (2PA) cross sections measured by the open aperture Z-scan technique are determined to be 620 and 1610 GM for STAPA-a and STAPA-b in chloroform,respectively, which dramatically increase with the introduction of alkyl chains. The relationship between their structures and properties on one-and two-photon absorption and aggregation-induced emission is discussed, which allows us to examine the effect of introducing alkyl chains. In addition, solvent effects also show a significant influence on the 2PA cross section. The two compounds with excellent AIE and 2PA properties provide attractive alternatives for the biophotonic materials.展开更多
In this study,linear absorption,single-photon excited fluorescence,fluorescence quantum yields,fluorescence lifetime and two-photon excited fluorescence of a series of triphenylamine derivatives (L1,L2,L3 and L4) have...In this study,linear absorption,single-photon excited fluorescence,fluorescence quantum yields,fluorescence lifetime and two-photon excited fluorescence of a series of triphenylamine derivatives (L1,L2,L3 and L4) have been measured.L1 and L3 are D--A type dyes,while L2 and L4 are D--D--A type dyes (D=donor,A=acceptor).The investigated compounds consist of triphenylamine-bearing donor-substituted and/or systematically extended-conjugated length,which are designed to gain insight into the effect of the ethoxyl unit and-linkage length on the linear and nonlinear optical properties.The influence of solvent polarity on the photophysical properties was investigated.Employing time-dependent density functional theory (TD-DFT) calculations,the structure-property relationships are discussed.展开更多
Five novel near-infrared electrochromic aromatic polyimides (PIs) with pendent benzimidazole group were synthesized from 4,4'-diamino-4"-(1-benzylbenzimidazol-2-yl)triphenylamine (named as DBBT) with five diff...Five novel near-infrared electrochromic aromatic polyimides (PIs) with pendent benzimidazole group were synthesized from 4,4'-diamino-4"-(1-benzylbenzimidazol-2-yl)triphenylamine (named as DBBT) with five different dianhydrides via two-step polymerization process, respectively. The maximum UV-Vis absorption bands of these PIs locate at about 335 nm for solid films due to the π-π* transitions. A reversible pair of distinct redox peaks, that were associated with a noticeable color change from original yellow to blue, was observed in the cyclic voltammetry (CV) test. A new absorption peak emerged at 847 nm in near-infrared (NIR) region with increasing voltage in UV-Vis-NIR spectrum, which indicates that PI can be used as NIR electrochromic material. These novel PIs have good electrochemical stability, appropriate energy levels for the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), in the range of-5.17 eV to -5.20 eV and -2.14 eV to -2.26 eV (versus the vacuum level) determined by cyclic voltammetry method. These values basically consisted with the results of quantum chemical calculation. These polyimides can be used as novel electrochromic and hole transportation materials.展开更多
Three novel donor-n-acceptor (D-π-A) metal-free organic dyes (TB, TS and TF) based on tri(triphenylamine)- substituted styrene as donor with various conjugated linkers (benzene, thiophene and furan) were synt...Three novel donor-n-acceptor (D-π-A) metal-free organic dyes (TB, TS and TF) based on tri(triphenylamine)- substituted styrene as donor with various conjugated linkers (benzene, thiophene and furan) were synthesized, characterized and used for the application of dye-sensitized solar cells (DSSCs). Under the same condition, The photo-to-electrical conversion efficiency of the DSSCs sensitized with TB, TS and TF reach 1.84%, 4.10% and 4.52%, respectively, which are lower than that sensitized with RI (5.02%) with one triphenylamine unit. The results suggest that these bulky donor-based sensitizers are unfavorable to DSSCs.展开更多
Organic small molecules (TPA-BT3T, TPA-PT3T, and TPA-DFBT3T) using triphenylamine as a donor unit, terthiophene as a bridge, and benzo-2,1,3-thiadiazole (BT), [1,2,5]thiadiazolo[3,4-e]pyridine (PT) or 5,6-difluo...Organic small molecules (TPA-BT3T, TPA-PT3T, and TPA-DFBT3T) using triphenylamine as a donor unit, terthiophene as a bridge, and benzo-2,1,3-thiadiazole (BT), [1,2,5]thiadiazolo[3,4-e]pyridine (PT) or 5,6-difluorobenzo[c][1,2,5]thiadiazole (DFBT) as an acceptor unit were designed and synthesized through Suzuki coupling reactions. These molecules exhibited good thermal stability with decomposition temperatures over 380℃ and broad absorption from 300 to 700 nm. Photovoltaic devices were fabricated with these small molecules as donors and PC71BM as an acceptor. The TPA-BT3T based devices exhibited a power conversion efficiency of 2.89%, higher than those of the TPA-PT3T- and TPA-DFBT3T-based devices (1.34% and 1.54% respectively). The effects of electron-withdrawing units on absorption, energy level, charge transport, morphology, and photovoltaic properties also were investigated.展开更多
In this work, a novel molecule pyridinylfluorene/triphenylamine hybrid (TPyFTPA) with bulky steric hindrance effects has been synthesized successfully by substituting 9-(pyridine-2-yl)-fluoren-9-yl with triphenyla...In this work, a novel molecule pyridinylfluorene/triphenylamine hybrid (TPyFTPA) with bulky steric hindrance effects has been synthesized successfully by substituting 9-(pyridine-2-yl)-fluoren-9-yl with triphenylamine (TPA) via Friedel-Crafts reaction, which possesses good thermal stability and triplet energy (ET) of 420 ℃ with 5% weight loss and 2.86 eV, respectively. Moreover, the bulky steric hindrance material shows high stable morphology by heating to 200 ℃ without finding melting phenomena and crystallization that is demonstrated by differential scanning calorimetry (DSC) curve. The bulky pyridinylfluorene end-capped TPA has been used as host material for blue phosphorescent organic light-emitting diodes (PhOLEDs) with maximum external quantum efficiencies (EQEs) of 2.7%, 3.7%, and 3.5%, at the doping ratios of 10%, 30%, and 40%, respectively. The performances of TPyFTPA-based blue PhOLEDs own wide concentration ranging from 10% to 40%, which indicates the bulky TPyFTPA might be a potential candidate for inexpensive products with simplifying process for the applications in full-color display and solid state lighting.展开更多
基金the Sichuan Science and Technology Program (2019YJ0162)the National Natural Science Foundation of China (21402023, 51773027)the National Key R@D Program of China (2017YFB0702802) for financial support。
文摘Two extended hybrid conjugated systems based on a triphenylamine(TPA) core with two and three peripheral 1,4-dithiafulvenes(DTF) units coded WH-2 and WH-3 as hole-transporting materials(HTMs) applied in perovskite solar cells(PSCs) are synthesized by facile one-step reaction in good yield over 75%. DTF unit as electron donor can enhance the electron donating ability and the fusion of benzenic ring of TPA with DTF unit may lead to reinforced intermolecular interactions in the solid state. In addition,WH-2 and WH-3 exhibit a pyramid shape containing partial planarity and quasi three-dimensionality features, which is also conducive to enhancing the π-π stacking of molecules in the solid state. The above-mentioned structural characteristics make the two HTMs have good hole mobilities. As a result,WH-2 and WH-3 obtained the high intrinsic hole mobilities of 4.69 × 10^(-4)and 2.18 × 10^(-3)cm^(2)V^(-1)s^(-1)respectively. Finally, the power conversion efficiencies(PCEs) of PSCs with WH-2 and WH-3 as cost-effective dopant-free HTMs are 15.39% and 19.22% respectively and the PCE of PSC with WH-3 is on a par with that of PSC with Li-TFSI/t-BP doped Spiro-OMe TAD(19.67%).
基金supported by the Major Project of Natural Science Research in Universities of Anhui Province(KJ2018ZD037,KJ2018A0333)Key Project of Youth Talents in Universities of Anhui Province(gxyqZD2017067)+5 种基金National Natural Science Foundation of China(21401024)Natural Science Foundation of Anhui Province(1508085MB21)National Students Research Training Program(201810371028)Research Innovation Team of Fuyang Normal University(kytd201710)Horizontal Cooperation Project of Fuyang Municipal Government and Fuyang Normal University(XDHX2016011,XDHX2016004)Anhui University Research Innovation Platform Team Project(201549)
文摘An electron donor-π-bridge-electron acceptor(D-π-A) optical functional organic compound comprising a triphenylamine moiety as the electron donor and pyridine moiety as the electron acceptor was synthesized. The structure of the compound was solved by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21, with a = 9.753(5), b = 8.815(5), c = 25.554(5) ?, β = 96.315(5)°, V = 2184(2) ?~3, Z = 2, D_c = 1.136 g/m^3, F(000) = 792, Μr = 746.92, μ = 0.069 mm^(-1), the final R = 0.0658 and wR = 0.1730 for 6790 observed reflections with I > 2(I). Study of nonlinear optical properties shows that the compound exhibits excellent two-photon excited fluorescence with the two-photon absorption cross-section value of 116 GM. The structure-property relationship was researched in detail through X-ray crystallography and quantum chemical calculation. Result of living cell imaging experiment shows its potential in fluorescence microscopy bioimaging.
文摘A starburst tripbenylamine cored N-vinyl carbazole (V-Cz) branched compound was designed and synthesized via optimized Heck reaction in a yield of 40-60%. Moderate yield came from decomposition of V-Cz and self-coupling of triiodo-triphenylamine. TCz-TPA adopts a highly twisted propeller conformation by molecular mechanical optimization. It is readily soluble for its highly twisted conformation. Transparent and pinhole free films could be easily fabricated by spin-coating for its starburst structure. It emits blue-greenish light in CH2Cl2 peaked at 460 nm with a narrow full-width at half-maximum (FWHM) of 65 nm. As compared,
基金supported by the Fundamental Research Funds for the Central Universitiesthe National Key Research and Development Program of China(2020YFB0408002)。
文摘In the past decade,perovskite solar cells have become a promising candidate in the photovoltaic industry owing to their high power conversion efficiency that surpasses 25%.However,there are certain limitations that have hindered the development and full-scale practical application of these cells,including the high cost and degradation of perovskite caused by the dopants.Hence,there is an urgent need to develop dopant-free hole transport materials(HTMs).In recent years,HTMs based on triphenylamine(TPA-HTMs)are receiving growing interest owing to their high hole mobility,excellent film formation,and suitable energy levels.The literature here covers work relevant to TPA-HTMs in the last five years.They have been classified according to different core types.The correlations between performance and structure are summarized,and the future development trend of TPA-HTMs is highlighted.
基金supported by the Science and Technology Developmental Plan of Jilin Province(No.20170520145JH)
文摘Here, a series of starburst triphenylamine(WD8) derivatives for dye-sensitized solar cells(DSSCs) applications have been designed. The frontier molecular orbitals(FMOs) property, absorption spectra, and charge transfer rate property of WD8 and its derivatives were simulated. We also evaluated the FMOs energies and absorption spectra of WD8 and its derivatives with the TiO2 cluster. The simulation results show that the phenothiazine-triphenylamine and 2-cyanoacetic acid groups in the ortho-position will increase the HOMO energy, decrease the LUMO energy, and narrow the HOMO-LUMO gap of WD8. The charge injection from WD8 and its derivatives to TiO2 should be more favorable. The phenothiazine-triphenylamine and 2-cyanoacetic acid groups in the ortho-position will decrease the electron and hole injection barriers of WD8. The phenothiazinetriphenylamine and 2-cyanoacetic acid groups in the ortho-position will improve the absorption spectra properties of WD8. The absorption spectra of WD8 and its derivatives with the TiO2 cluster would have a red shift. The phenothiazine-triphenylamine and 2-cyanoacetic acid groups in the ortho-position will increase the charge transfer property of WD8.
基金Supported by the National High-Tech Research and Development Program of China(No.2008AA03A315)the Natural Science Foundation of Tianjin City,China(No.08JCZDJC16900)
文摘Blue luminescent compounds T1―T4 containing triphenylamine donors,bipyridine acceptors and olefinic linkers were synthesized and characterized by 1 H NMR,13 C NMR and high resolution mass spectrometry(HRMS).Four compounds T1―T4 exhibit excellent solubility in common solvents and good film forming properties.Quantum chemical calculations show that compounds T1―T4 have asymmetric linear structures and the proper highest occupied molecular orbital(HOMO) levels.The UV-Vis absorption and fluorescence emission spectra of the four compounds in dilute chloroform solutions and on the solid films were measured.It reveals that compounds T1―T4 exhibit similar spectral behavior,suggesting that these compounds can form amorphous state in solid films.The calculated absorption and emission spectra of compounds T1―T4 are in good agreement with experimentally determined ones.Compounds T1―T4 have absolute fluorescence quantum yield above 17% in dilute chloroform solutions.Four compounds possess high glass-transition temperature(T g) exceeding 97 ℃ and the maximum T g is 155.28 ℃ for compound T3.Cyclic voltammetry measurements show that these compounds have proper HOMO levels in a range of-5.01―-5.13 eV for hole injection.The properties of compounds T1―T4 indicate that these compounds are candidates for the application in organic light-emitting devices(OLEDs) as hole-transporting materials(HTMs).
基金Supported by the National Natural Science Foundation of China under Grant Nos 11404048,61205154 and 11375034the Fundamental Research Funds for the Central Universities under Grant Nos 3132015233,3132013104,3132014337,3132015144 and3132015152+1 种基金the State Key Laboratory of Fine Chemicals(KF1409)the Program for Liaoning Excellent Talents in University under Grant No LJQ2014051
文摘The two-photon fluorescence properties and ultrafast responses of a hyperbranched polyyne (hb-DPP-J2) with triphenylamine as the central core, Diketo-Pyrrolo-Pyrrole as the connecting unit and electron acceptor are studied. The polymer has a D-π-A-π-D conjugated structure along the extended polyyne w-bridge systems, and the effective condugated unit repeats itself in the whole hyperbranehed polymer chain. The polymer exhibits a large two-photon absorption cross section and high fluorescence quantum yields. The ultrafast dynamic results give a deep understanding of the excited energy transfer processes under excitation, and reveal a long relaxation lifetime of the intramolecular charge transfer (ICT) state.
基金This work was supported by the National Natural Science Foundation of China No.50225312by Zhejiang Natural Science Foundation(No.ZC0101)the work was also partly supported by the Research Fund for the Doctoral Program of Higher Education(20020335016).
文摘A novel triphenylamine derivative of 4, 4'-bis-[2-[4-[N, N-bis-(4-methoxyphenyl-amino)]phenyl-1-yl]-vinyl-1-yl]-1, 1'-biphenyl (DMPAVBI) was synthesized. The chemical structure wasconfirmed by IR, H NMR spectroscopy and elemental analysis. Its properties were studied by 1UV-Vis spectroscopy, photoluminescence spectroscopy and cyclic voltammetry methods.
基金This project was supported by the Scientific Research Development Program of Shandong Provincial High School(J18KA082)the Under-graduate Training Program for Innovation and Entrepreneurship of Shandong Provincial High School(201710446042,2018A043)the Experimental Technology Research Program of Qufu Normal University(SJ201709)
文摘Four bipolar triphenylamine(TPA) charge transport materials were constructed by introducing imidazole and trifluoroacetyl groups into the TPA units, and characterized by the nuclear magnetic resonance spectrum(NMR) and mass spectrometry(MS). Among them, 4-(2-(1,3-trifluoroacetyl)imidazole)-phenyl-4,4?-di(4-methoxyphenyl)amine(2 Me OTPA-IOS, 1) was determined by X-ray single-crystal diffraction. The compound crystallizes in monoclinic system, space group P21/c with a = 24.338(5), b = 9.565(2), c = 11.456(2) ?, β = 99.427(3)°, Mr = 565.47, V = 2631.0(8) ?3,Z = 4,Dc = 1.428 g/cm3, μ = 0.125 mm–1, F(000) = 1160, the final R = 0.0559 and wR = 0.1265 for 5150 observed reflections with I > 2σ(I). The optimized configurations of the target compounds were obtained by quantum chemical calculation, and the bipolarity of transportable holes and electrons was predicted by the frontier molecular orbital(HOMO and LUMO), which was further confirmed by the time of flight(TOF) method. In addition, the introduction of the terminal flexible chain enhances the solubility, thermal stability(DSC and TGA) and film-forming property of all compounds, and the frontier orbital energy of the solid film of the compounds was also tested(UV-vis and PYS). Thus, these compounds have the bipolarity of transportable holes and electrons and show good solubility and thermal stability.
基金funded by the Hainan Provincial Joint Project of Sanya Yazhou Bay Science and Technology City(No.820LH027)the Hainan Provincial Natural Science Foundation of China(No.823RC472)+4 种基金the Open Project Program of Wuhan National Laboratory for Optoelectronics(No.2021WNLOKF008)the Hainan University Scientific Research Foundation(No.KYQD(ZR)19107)Natural Science Research Talent Project of Hainan Medical University(No.JBGS202101)Hainan Province Clinical Medical Center(2021)Project for Functional Materials and Molecular Imaging Science Innovation Group of Hainan Medical University。
文摘Triphenylamine(TPA)-based aggregation-induced emission luminogens(TPA-AIEgens),a type of photoactive material utilizing the typical TPA moiety,has recently attracted increasing attention for the diagnostics and treatment of tumors due to their remarkable chemo-physical performance in optoelectronic research.TPA-AIEgens are distinguished from other photoactive agents by their strong fluorescence,good sensitivity,high signal-to-noise ratio,resistance to photobleaching,and lack of high concentration or aggregation-caused fluoresce quenching effects.In this review,we summarize the current advancements and the biomedical progress of TPA-AIEgens in tumor theranostics.First,the design principles of TPAAIEgens photoactive agents as well as the advanced targeting strategies for nuclei,cell membranes,cell organelle and tumors were introduced,respectively.Next,the applications of TPA-AIEgens in tumor diagnosis and therapeutic techniques were reviewed.Last,the challenges and prospects of TPA-AIEgens for cancer therapy were performed.The given landscape of the TPA-AIEgens hereby is meaningful for the further design and utilization of the novel photoactive material,which could be beneficial for the development of clinic applications.
基金supported by NSFC(22101160)the"1331"Project of Shanxi ProvinceResearch Project Supported by Shanxi Scholarship Council of China(2020-088).
文摘The photocatalytic oxidative coupling of thiols is one of the most popular methods to synthesize the disulfides.Triphenylamine and its derivatives(TPAs)are promising for the above reaction,but suffer from the easy polymerization and difficult separation.To overcome these obstacles while controlling the photogenerated electrons transfer directly to target substrates,herein,we constructed one TPA-based metal-organic framework(MOF),(Me_(2)NH_(2))[Sr(TCBPA)]·DMA·3H_(2)O(1),by direct self-assembly of tris(4′-carboxybiphenyl)amine(H_(3)TCBPA)and photoredox inert strontium ion(Sr^(2+)).DFT calculations revealed that the valence band maximum(VBM)and the conduction band minimum(CBM)are mainly located on TCBPA^(3-),successfully inhibiting the undesirable electron migration to metal nodes.Experimental results indicated that 1 displays superior performance than homogeneous H_(3)TCBPA,which may result from the abundant π…π and C—H…π interactions between the well-arranged TCBPA^(3-)and the build-in electric field between the anionic framework and the Me_(2)NH^(2+).This work highlights that immobilizing TPAs into MOFs is one promising approach to designing heterogeneous photocatalysts for the synthesis of disulfides by oxidative coupling of thiols.
基金financially supported by the National Natural Science Foundation of China(Nos.22271116 and 22071079 for M.W)Jilin Provincial Science and Technology Department(No.20230101027JC for M.W.)the fellowship of China Postdoctoral Science Foundation(No.2021M701383 for J.S)。
文摘The stable coordinated metallo-complexes based on 2,2′:6′,2″-terpyridine(tpy)and its derivatives have been widely researched for various wide-ranging applications in photoelectronics,catalysis,sensor,photoluminescence,and so on.However,the most reported studies ignored the comprehensive comparison between structures modified by different positions and photoluminescence.Herein,we design a series of metallo-complexes which were assembled with tpy substituted triphenylamine(TPA)at different positions and metal ions and explored their photophysical properties.In the solution state,MLE_(2)based on the 5,5″-positions modification showed the highest PLQYs and PL intensity.With the increase of solvent polarity,MLB2exhibit the largest redshift.In the solid state,from MLA_(2)to MLE_(2),the emission colours are gradually red-shifted from yellow to red.The findings in this work may pave a new way to design functional metallo-complexes,not just for PL properties.
基金supported by the National Natural Science Foundation of China (Nos. 51972185, 12174211, 11874232 and 31202117)the Natural Science Foundation of Shandong Province (No. ZR2020ZD38)。
文摘Two triphenylamine-based star-type push-pull chromophores(T1, T2) were designed and synthesized.Triphenylamine serves as the central core and acts as an electron-donating group surrounded by electronwithdrawing pentafluorobenzene or N,N-dimethyl substituted tetrafluorobenzene, which are connected by ethylene bridges. Single-crystal X-ray diffraction confirmed the structures and molecular arrangement of two chromophores. The systematic photophysical research of T1 and T2 absorption characteristics was carried out to gain a better understanding of how structure-property relationships affect the observed nonlinear optical absorption phenomenon. Complementary calculations based on density functional theory(DFT) further confirmed the experimental results. Both chromophores exhibited excellent two-photon absorption(TPA) properties in CH_(2)Cl_(2). Notably, T2 has more remarkable nonlinear optical absorption effects with the TPA cross-section up to 4.24 × 10~7GM. By adjusting the electronic structures of the chromophores through introducing pentafluorobenzene or N,N-dimethyl as functional groups with different electron-donating or withdrawing behaviors, the TPA performance of the small organic molecule could be greatly enhanced. These molecular structures with push-pull systems were excellent candidates for different two-photon applications.
基金the National Natural Foundation of China (2116110444, 21172073)National Basic Research Program of China (973 program, 2013CB733700, 2013CB834701)the Fundamental Research Funds for the Central Universities (WJ0913001)
文摘Two new multibranched thiophene-based triarylamine derivatives with 1,3,5-triazine core are synthesized and characterized. Their one-and two-photon absorption properties and aggregation-induced emission effect have been investigated. Both the STAPA-based compounds are AIE active. The two-photon absorption (2PA) cross sections measured by the open aperture Z-scan technique are determined to be 620 and 1610 GM for STAPA-a and STAPA-b in chloroform,respectively, which dramatically increase with the introduction of alkyl chains. The relationship between their structures and properties on one-and two-photon absorption and aggregation-induced emission is discussed, which allows us to examine the effect of introducing alkyl chains. In addition, solvent effects also show a significant influence on the 2PA cross section. The two compounds with excellent AIE and 2PA properties provide attractive alternatives for the biophotonic materials.
基金supported by the National Natural Science Foundation of China (NSFC,21071001,51142011,21101001)Education Department of Anhui Province (KJ2010A030)the "211" Project of Anhui University
文摘In this study,linear absorption,single-photon excited fluorescence,fluorescence quantum yields,fluorescence lifetime and two-photon excited fluorescence of a series of triphenylamine derivatives (L1,L2,L3 and L4) have been measured.L1 and L3 are D--A type dyes,while L2 and L4 are D--D--A type dyes (D=donor,A=acceptor).The investigated compounds consist of triphenylamine-bearing donor-substituted and/or systematically extended-conjugated length,which are designed to gain insight into the effect of the ethoxyl unit and-linkage length on the linear and nonlinear optical properties.The influence of solvent polarity on the photophysical properties was investigated.Employing time-dependent density functional theory (TD-DFT) calculations,the structure-property relationships are discussed.
基金financially supported by the National Natural Science Foundation of China(Nos.51373049,51372055,21372067,21206034,51303045 and 51473046)Doctoral Fund of Ministry of Education of China(Nos.20132301120004 and 20132301110001)Reserve Talented Person of Harbin(No.2015RAXXJ015)
文摘Five novel near-infrared electrochromic aromatic polyimides (PIs) with pendent benzimidazole group were synthesized from 4,4'-diamino-4"-(1-benzylbenzimidazol-2-yl)triphenylamine (named as DBBT) with five different dianhydrides via two-step polymerization process, respectively. The maximum UV-Vis absorption bands of these PIs locate at about 335 nm for solid films due to the π-π* transitions. A reversible pair of distinct redox peaks, that were associated with a noticeable color change from original yellow to blue, was observed in the cyclic voltammetry (CV) test. A new absorption peak emerged at 847 nm in near-infrared (NIR) region with increasing voltage in UV-Vis-NIR spectrum, which indicates that PI can be used as NIR electrochromic material. These novel PIs have good electrochemical stability, appropriate energy levels for the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), in the range of-5.17 eV to -5.20 eV and -2.14 eV to -2.26 eV (versus the vacuum level) determined by cyclic voltammetry method. These values basically consisted with the results of quantum chemical calculation. These polyimides can be used as novel electrochromic and hole transportation materials.
文摘Three novel donor-n-acceptor (D-π-A) metal-free organic dyes (TB, TS and TF) based on tri(triphenylamine)- substituted styrene as donor with various conjugated linkers (benzene, thiophene and furan) were synthesized, characterized and used for the application of dye-sensitized solar cells (DSSCs). Under the same condition, The photo-to-electrical conversion efficiency of the DSSCs sensitized with TB, TS and TF reach 1.84%, 4.10% and 4.52%, respectively, which are lower than that sensitized with RI (5.02%) with one triphenylamine unit. The results suggest that these bulky donor-based sensitizers are unfavorable to DSSCs.
基金supported by the National Natural Science Foundation of China(21025418,51261130582)the National Basic Research Program of China(2011CB808401)the Chinese Academy of Sciences
文摘Organic small molecules (TPA-BT3T, TPA-PT3T, and TPA-DFBT3T) using triphenylamine as a donor unit, terthiophene as a bridge, and benzo-2,1,3-thiadiazole (BT), [1,2,5]thiadiazolo[3,4-e]pyridine (PT) or 5,6-difluorobenzo[c][1,2,5]thiadiazole (DFBT) as an acceptor unit were designed and synthesized through Suzuki coupling reactions. These molecules exhibited good thermal stability with decomposition temperatures over 380℃ and broad absorption from 300 to 700 nm. Photovoltaic devices were fabricated with these small molecules as donors and PC71BM as an acceptor. The TPA-BT3T based devices exhibited a power conversion efficiency of 2.89%, higher than those of the TPA-PT3T- and TPA-DFBT3T-based devices (1.34% and 1.54% respectively). The effects of electron-withdrawing units on absorption, energy level, charge transport, morphology, and photovoltaic properties also were investigated.
文摘In this work, a novel molecule pyridinylfluorene/triphenylamine hybrid (TPyFTPA) with bulky steric hindrance effects has been synthesized successfully by substituting 9-(pyridine-2-yl)-fluoren-9-yl with triphenylamine (TPA) via Friedel-Crafts reaction, which possesses good thermal stability and triplet energy (ET) of 420 ℃ with 5% weight loss and 2.86 eV, respectively. Moreover, the bulky steric hindrance material shows high stable morphology by heating to 200 ℃ without finding melting phenomena and crystallization that is demonstrated by differential scanning calorimetry (DSC) curve. The bulky pyridinylfluorene end-capped TPA has been used as host material for blue phosphorescent organic light-emitting diodes (PhOLEDs) with maximum external quantum efficiencies (EQEs) of 2.7%, 3.7%, and 3.5%, at the doping ratios of 10%, 30%, and 40%, respectively. The performances of TPyFTPA-based blue PhOLEDs own wide concentration ranging from 10% to 40%, which indicates the bulky TPyFTPA might be a potential candidate for inexpensive products with simplifying process for the applications in full-color display and solid state lighting.