Triphenylamine(TPA)is the most promising donor fragment for the construction of long-wavelength thermally activated delayed fluorescence(TADF)emitters owing to its suitable dihedral angle that could enhance radiative ...Triphenylamine(TPA)is the most promising donor fragment for the construction of long-wavelength thermally activated delayed fluorescence(TADF)emitters owing to its suitable dihedral angle that could enhance radiative decay to compete with the serious non-radiative decay.However,the moderate electron-donating capacity of TPA seriously limits the selection of acceptor for constructing longwavelength TADF emitters with narrow bandgaps.To address this issue,in this work,the peripheral benzene of TPA was replaced with 1,4-benzodioxane and anisole to obtain two new electrondonating units N-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-N-phenyl-2,3-dihydrobenzo[b][1,4]dioxin-6-amine(TPADBO,−5.02 eV)and 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline(TPAMO,−5.00 eV),which possess much shallower highest occupied molecule orbital(HOMO)energy levels than the prototype TPA(−5.33 eV).Based on TPA and the modified TPA donor fragments,three TADF emitters were designed and synthesized,namely Py-TPA,Py-TPADBO and Py-TPAMO,with the same acceptor fragment 12-(2,6-diisopropylphenyl)pyrido[2′,3′:5,6]pyrazino[2,3-f][1,10]phenanthroline(Py).Among them,Py-TPAMO exhibits the highest photoluminescence quantum yield of 78.4%and the smallest singlet-triplet energy gap,which is because the introduction of anisole does not cause significant molecule deformation for the excited Py-TPAMO.And Py-TPAMO-based OLEDs successfully realize a maximum external quantum efficiency of 25.5%with the emission peak at 605 nm.This work provides a series of candidate of donor fragments for the development of efficient long-wavelength TADF emitters.展开更多
Triphenylamine(TPA)derivatives and their radical cation counterparts have successfully demonstrated a great potential for applications in a wide range of fields including organic redox catalysis,organic semiconductors...Triphenylamine(TPA)derivatives and their radical cation counterparts have successfully demonstrated a great potential for applications in a wide range of fields including organic redox catalysis,organic semiconductors,magnetic materials,etc.,mainly because of their excellent redox activity.The stability of TPA radical cation has significant effect on the properties of the TPA-based functional materials,especially in relation to their electronic properties.Considering the instability of parent TPA radical cation,many efforts have been devoted to the development of stable TPA radical cations and related materials.Among them,TPA radical cation-based macrocycles have attracted particular attention because their large delocalized structures can stabilize the TPA radicals,thus endow them with outstanding redox behaviors,multiple resonance structures,and wide application in various optoelectronic devices.In this review,we give a brief introduction of organic radicals and the documented stable TPA radicals.Subsequently,a number of TPA radical cation-based macrocycles are comprehensively surveyed.It is expected that this minireview will not only summarize the recent development of TPA radical cations and their macrocycles,but also shed new light on the prospect of the design of more sophisticated radical cation-based architectures and related materials.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
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
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
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
A series of triphe nylamine(TPA)derivatives with various substituent groups were prepared and showed different absorption and fluorescence characteristics due to the substituent effect.On account of the existence of p...A series of triphe nylamine(TPA)derivatives with various substituent groups were prepared and showed different absorption and fluorescence characteristics due to the substituent effect.On account of the existence of pyridine units,these TPA derivatives exhibited acid-induced tunable multicolor fluorescence emission including white light emission.In addition,acid-induced fluorescence regulation of these compounds has been also realized in the solid state,which enable them to be successfully constructed the stimuli-responsive fluorescent films and fluorescent inks for inkjet printing.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
Two novel organic hole-transporting materials have been synthesized by combination of triphenylamines（TPA） viaπ-conjugated bonds using Wittig reaction.The structures were characterized by NMR,FT-IR and HRMS.The opt...Two novel organic hole-transporting materials have been synthesized by combination of triphenylamines（TPA） viaπ-conjugated bonds using Wittig reaction.The structures were characterized by NMR,FT-IR and HRMS.The optical,electrochemical and thermal properties of the materials were studied in detail.The results show that these two compounds have blue emission,proper HOMO levels and high thermal stability.Furthermore,a quantum chemical calculation on electron distribution of the two compounds was performed, which suggests the current synthesized materials would be promising candidates for hole-transporting materials.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
Triphenylamine(TPA) derivatives have been widely used as useful building blocks for diverse functional materials because of their excellent redox activity. Most of the molecular structures of TPA-based organic functio...Triphenylamine(TPA) derivatives have been widely used as useful building blocks for diverse functional materials because of their excellent redox activity. Most of the molecular structures of TPA-based organic functional materials contain 4-anisyl groups, which on one hand could reduce their oxidation potential and on the other hand significantly delocalize the spin density of the resultant TPA radical cation species and enhance their stability. However, molecular-level investigation of the redox behavior of triphenylamines consisting of 4-anisyl group and the electronic structures of their radical cation species has not been reported in the literature. Herein, we design a series of triphenylamines consisting of one, two, or three 3,5-di–tert–butyl–4-anisyl groups and investigate their redox behaviors and corresponding radical cation species. We disclose that the resonance hybrid and steric protection could both contribute to the stability of triphenylamine radical cations. Moreover, further oxidation leads to an unexpected oxidative demethylation. The findings in this work may reveal new insights for the understanding of the unique redox properties of 4-anisyl substituted triphenylamines.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
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
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
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 TiO_(2) 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 TiO_(2) 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
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
Stimuli-responsive organic luminescent materials exhibit significant sensitivity to various external stimuli,among which their excellent photosensitivity is particularly prominent.This unique feature gives them great ...Stimuli-responsive organic luminescent materials exhibit significant sensitivity to various external stimuli,among which their excellent photosensitivity is particularly prominent.This unique feature gives them great potential for applications.Herein,five organic small molecule emitters based on triphenylamine derivatives have been synthesized via Suzuki-coupling reaction.These small molecules have excellent fluorescence properties with fluorescence quantum yields(Φ)all reaching over 90%.When irradiated with a 365 nm UV lamp,interesting photochromic phenomena occurred in their chloroform solutions.This phenomenon has been studied intensively by UV-vis absorption and fluorescence spectroscopy,EPR measurements,and density functional theory calculations,and finally,the triphenylamine group was used as a photoinitiation precursor and electron donor,and the photo-induced charge transfer complex(PCTC)initiated by the donor molecule was successfully constructed.展开更多
基金supported by the National Natural Science Foundation of China (Nos. 62222503, 52073040 and 52130304)the Sichuan Science and Technology Program (Nos. 2024NSFSC0012,2023NSFSC1973 and 2024NSFSC1446)+2 种基金the China Postdoctoral Science Foundation (Nos. 2023M740504 and GZC20230380)the Sichuan Provincial Human Resources and Social Security Department Programthe Collaborative Innovation Center of Suzhou Nano Science&Technology
文摘Triphenylamine(TPA)is the most promising donor fragment for the construction of long-wavelength thermally activated delayed fluorescence(TADF)emitters owing to its suitable dihedral angle that could enhance radiative decay to compete with the serious non-radiative decay.However,the moderate electron-donating capacity of TPA seriously limits the selection of acceptor for constructing longwavelength TADF emitters with narrow bandgaps.To address this issue,in this work,the peripheral benzene of TPA was replaced with 1,4-benzodioxane and anisole to obtain two new electrondonating units N-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-N-phenyl-2,3-dihydrobenzo[b][1,4]dioxin-6-amine(TPADBO,−5.02 eV)and 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline(TPAMO,−5.00 eV),which possess much shallower highest occupied molecule orbital(HOMO)energy levels than the prototype TPA(−5.33 eV).Based on TPA and the modified TPA donor fragments,three TADF emitters were designed and synthesized,namely Py-TPA,Py-TPADBO and Py-TPAMO,with the same acceptor fragment 12-(2,6-diisopropylphenyl)pyrido[2′,3′:5,6]pyrazino[2,3-f][1,10]phenanthroline(Py).Among them,Py-TPAMO exhibits the highest photoluminescence quantum yield of 78.4%and the smallest singlet-triplet energy gap,which is because the introduction of anisole does not cause significant molecule deformation for the excited Py-TPAMO.And Py-TPAMO-based OLEDs successfully realize a maximum external quantum efficiency of 25.5%with the emission peak at 605 nm.This work provides a series of candidate of donor fragments for the development of efficient long-wavelength TADF emitters.
基金the Innovation Program of Shanghai Municipal Education Commission(No.2019-01-07-00-05-E00012)Program for Changjiang Scholars and Innovative Research Team in University for financial support+2 种基金the financial supports sponsored by NSFC/China(Nos.22071061,52003081)Shanghai Sailing Program(No.19YF1412900)Microscale Magnetic Resonance Platform of ECNU.
文摘Triphenylamine(TPA)derivatives and their radical cation counterparts have successfully demonstrated a great potential for applications in a wide range of fields including organic redox catalysis,organic semiconductors,magnetic materials,etc.,mainly because of their excellent redox activity.The stability of TPA radical cation has significant effect on the properties of the TPA-based functional materials,especially in relation to their electronic properties.Considering the instability of parent TPA radical cation,many efforts have been devoted to the development of stable TPA radical cations and related materials.Among them,TPA radical cation-based macrocycles have attracted particular attention because their large delocalized structures can stabilize the TPA radicals,thus endow them with outstanding redox behaviors,multiple resonance structures,and wide application in various optoelectronic devices.In this review,we give a brief introduction of organic radicals and the documented stable TPA radicals.Subsequently,a number of TPA radical cation-based macrocycles are comprehensively surveyed.It is expected that this minireview will not only summarize the recent development of TPA radical cations and their macrocycles,but also shed new light on the prospect of the design of more sophisticated radical cation-based architectures and related materials.
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.
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 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 State Key Laboratory of Fine Chemicals(No.KF1801)。
文摘A series of triphe nylamine(TPA)derivatives with various substituent groups were prepared and showed different absorption and fluorescence characteristics due to the substituent effect.On account of the existence of pyridine units,these TPA derivatives exhibited acid-induced tunable multicolor fluorescence emission including white light emission.In addition,acid-induced fluorescence regulation of these compounds has been also realized in the solid state,which enable them to be successfully constructed the stimuli-responsive fluorescent films and fluorescent inks for inkjet printing.
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.
基金the National Natural Science Foundation ofChina(No21176180)Research Fund for the Doctoral Program of Higher Education of China(No20100032110021) for the financial support
文摘Two novel organic hole-transporting materials have been synthesized by combination of triphenylamines（TPA） viaπ-conjugated bonds using Wittig reaction.The structures were characterized by NMR,FT-IR and HRMS.The optical,electrochemical and thermal properties of the materials were studied in detail.The results show that these two compounds have blue emission,proper HOMO levels and high thermal stability.Furthermore,a quantum chemical calculation on electron distribution of the two compounds was performed, which suggests the current synthesized materials would be promising candidates for hole-transporting materials.
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financially supported by the National Natural Science Foundation of China (Nos. 22071061 and 52003081)Shanghai Sailing Pro-gram (No. 19YF1412900)Microscale Magnetic Resonance Platform of ECNU。
文摘Triphenylamine(TPA) derivatives have been widely used as useful building blocks for diverse functional materials because of their excellent redox activity. Most of the molecular structures of TPA-based organic functional materials contain 4-anisyl groups, which on one hand could reduce their oxidation potential and on the other hand significantly delocalize the spin density of the resultant TPA radical cation species and enhance their stability. However, molecular-level investigation of the redox behavior of triphenylamines consisting of 4-anisyl group and the electronic structures of their radical cation species has not been reported in the literature. Herein, we design a series of triphenylamines consisting of one, two, or three 3,5-di–tert–butyl–4-anisyl groups and investigate their redox behaviors and corresponding radical cation species. We disclose that the resonance hybrid and steric protection could both contribute to the stability of triphenylamine radical cations. Moreover, further oxidation leads to an unexpected oxidative demethylation. The findings in this work may reveal new insights for the understanding of the unique redox properties of 4-anisyl substituted triphenylamines.
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 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 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 TiO_(2) 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 TiO_(2) 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 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supported by the National Natural Science FoundationofChina(NSFC)(Nos.22165027,22471222,22461040)Gansu Province College Industry Support Plan Project(No.2022CYZC-18)+1 种基金Gansu Province Science Foundation for Youths(23JRRA690)Northwest Normal University Young Scholars Research Capacity Improvement Program(NWNU-LKQN2023-05).
文摘Stimuli-responsive organic luminescent materials exhibit significant sensitivity to various external stimuli,among which their excellent photosensitivity is particularly prominent.This unique feature gives them great potential for applications.Herein,five organic small molecule emitters based on triphenylamine derivatives have been synthesized via Suzuki-coupling reaction.These small molecules have excellent fluorescence properties with fluorescence quantum yields(Φ)all reaching over 90%.When irradiated with a 365 nm UV lamp,interesting photochromic phenomena occurred in their chloroform solutions.This phenomenon has been studied intensively by UV-vis absorption and fluorescence spectroscopy,EPR measurements,and density functional theory calculations,and finally,the triphenylamine group was used as a photoinitiation precursor and electron donor,and the photo-induced charge transfer complex(PCTC)initiated by the donor molecule was successfully constructed.
