Tetraphenylethene-based hole transporting material for highly efficient and stable perovskite solar cells

2,2,7,7-Tetrakis-(N,N-di-p-methoxyphenylamine)-9,9-spirobifluorene(Spiro-OMeTAD)has been identified as the most widely used and effective hole transporting material(HTM)in perovskite solar cells(PSCs).However,the complicated multistep synthesis and low intrinsic hole mobility of Spiro-OMe TAD limit its commercialized application.Therefore,developing highly efficient HTMs with less synthetic steps becomes increasingly important.Moreover,understanding hot carriers transfer dynamics at the interface of perovskite layer and hole transport layer is crucial for further enhancing PSCs performance towards Shockley-Queisser limit,which still lacks full investigation to date.Herein,a new HTM based on tetraphenylethene(WP1)was successfully synthesized by a simple one-step reaction process.It was found that WP1-based HTM exhibits more matched energy level,higher hole mobility and conductivity than those of the control Spiro-OMe TAD.The femtosecond transient absorption results reveal that the transfer rate of hot holes in perovskite/WP1 sample is four times higher than that of perovskite/Spiro-OMeTAD,thereby helping enhance the device performance.Consequently,the efficiency of PSCs is enhanced to 24.04%(WP1)from 22.85%(Spiro-OMeTAD).Moreover,the un-encapsulated device prepared with WP1 exhibits better long-term stability,retaining 87%of its initial PCE value after storing for 72 days under air environment,while the reference device shows76%of its initial value.This work indicates that simple tetraphenylethene-based organic small molecule could be a very promising HTM candidate for highly efficient PSCs,and gives some significant insights for understanding intrinsic hot carriers transfer dynamics in device.

Recognition and chirality sensing of guanosine-containing nucleotides by an achiral tetraphenylethene-based octacationic cage in water

The development of molecular probes or systems with the ability of multiple orthogonal responses is an effective approach to precisely detect biomolecules with similar chemical structures.Herein,we report the synthesis of a water-soluble TPE-based octacationic cage(1)with the compressed TPE-containing bilayer,which endows it with good fluorescence properties and potential conformation chirality.As a result,1 exhibits molecular recognition for anionic nucleotides within its two“claw”-like cavities to form 1:2 host-guest complexes in water,companying with selective turn-off fluorescence and turn-on CD responses to G/GTP over other nucleotides.

An AEE-active Polymer Containing Tetraphenylethene and 9,10-Distyrylanthracene Moieties with Remarkable Mechanochromism

A polymer （poly（9,10）anthracenevinylene-alt-4,4＇-（9,9-bis（4-（4＇-（1,2,2＇-triphenyviny）phenoxy）butyl）-9H- fluorene-2,7-diyl） dibenzaldehyde）, P1） was successfully synthesized through the Wittig-Horner reaction by employing fluorene and 9,10-distyrylanthracene moieties as building blocks for backbone and tetraphenylethenes as pendant groups. Photophysical and thermal properties of the resulting polymeric emitter were fully characterized by ultraviolet-visible （UV- Vis） absorption and photoluminescence （PL） spectra, thermogravimetric analysis （TGA） and differential scanning calorimetry （DSC）. While P1 emits an orange-light centered at 567 nm in dilute tetrahydrofuran （THF） solution, the solid powder of the polymer exhibits strong yellow emission peaked at 541 nm. It is also found that the as-synthesized polymer shows unique property of aggregation-enhanced emission （AEE）. In addition, P1 possesses high thermal stability with a decomposition temperature （Td,5%） of 430 ℃ and high morphological stability with a glass transition temperature （Tg） of 171℃. Under the stimulus of mechanical force, the emission of P1 can be changed from yellow to red （△λmax = 61 rim）, showing a remarkable mechanochromism. The results from XRD analysis suggest that such mechanochromic phenomenonof PI is probably caused by the destruction of crystalline structure, which leads to the conformational planarization of the distyrylanthracene moieties forming by the polymerization and the increase of molecular conjugation of the backbone.

Aggregation-induced emission or aggregation-caused quenching?Impact of covale nt bridge between tetraphenylethene and naphthalimide

Understanding the physical mechanisms governing aggregation-induced-emission(AIE)and aggrega-tion-caused-quenching plays a vital role in developing functional AIE materials.In this work,tetraphenylethene(TPE,a classical AiEgen)and naphthalimide(NI,a popular fluorophore with ACQ characteristics)were connected through non-conjugated linkages and conjugated linkages.We showed that the nonconjugated-linkage of TPE to NI fragments leads to substantial PET in molecular aggregates and ACQ.In con trast,the conjugated conn ection between TPE and NI moieties results in the AIE phenomenon by suppressing twisted intramolecular charge transfer.This work provides an important guideline for the rational design of AIE materials.

Aggregation-enhanced emission and efficient electroluminescence of conjugated polymers containing tetraphenylethene units

Tetraphenylethene (TPE) is a popular luminogen characterized by aggregation-induced emission and has been widely used to construct solid-state emissive materials. In this work, two thermally stable polymers (P1 and P2) consisting of TPE conjugated to the 2,7-positions of fluorene and carbazole, respectively, are synthesized and characterized. Both polymers are weakly fluorescent in solutions but show greatly enhanced emission as the aggregate formation, presenting an aggregation-enhanced emission feature. Two kinds of polymer light-emitting diodes are fabricated utilizing P1 and P2 as emitters (EML) (device I: ITO/PEDOT:PSS (45 nm)/PVK:EML (1:1 wt%, 55 nm)/TPBI (38 nm)/Ca:Ag; device II: ITO/PEDOT:PSS (45 nm)/ PVK:OXD-7:EML (3:1:3 wt%, 55 nm)/TPBI (38 nm)/Ca:Ag). The device II of P2 shows the best performances, affording a maximum luminance of 6500 cd/m 2 and a high peak efficiency of 2.11 cd/A.

Unsymmetrical photochromic bithienylethene-bridge tetraphenylethene molecular switches:Synthesis,aggregation-induced emission and information storage

Aggregation-induced emission(AIE) active photochromic molecules have attracted growing attention for their versatile applications.Here we designed and synthesized five newly unsymmetrical photochromic diarylethene(DAE) dyads(BTE1-5) by connecting tetraphenylethene(TPE) and aromatic substituent via bithienylethene(BTE) bridge.The chemical structures of those compounds were identified by ^1H NMR,^(13)C NMR and HRMS.The absorption and emission of these dyads were investigated by UV-vis and fluore scence spectroscopy,respectively.The results showed that all those compounds exhibited typically AIE or aggregation-induced emission enhancement(AIEE) characteristic.Particularly,when an aggregationcaused quenching(ACQ) fluorophore(triphenylamine) was grafted to the molecule,connecting with TPE via BTE-bridge,the ACQ phenomenon was dissipated and converted to an AIE luminophore,and those compounds exhibited photochromism upon irradiation with alternative UV and visible light.The solution or solid of those compounds showed distinctly fluorescence switching "ON" or "OFF" observation upon irradiation with alternative UV and visible light.It is interesting that BTE1 could be applied in recording and rewritable information storage,and the cyclization quantum yields could be affected by substituent significantly.

Effective enhancement of the emission efficiency of tetraphenylporphyrin in solid state by tetraphenylethene modification

Tetraphenylporphyrin(TPP) is a typical red-emitting luminogen showing evident aggregation caused quenching(ACQ) effect. To enhance its emission efficiency in solid state, four tetraphenylethene(TPE)units were attached to the four meso-positions of TPP core via ester group through a facile and efficient route. The derived compound(4(TPE-COO)-TPP) emits red fluorescence(peak at 655 nm) with a good quantum efficiency(F) of 7.5%, which is much higher than that of TPP(Φ～ 0.1%). In molecular aggregate formed in tetrahydrofuran(THF) and water mixtures, 4(TPE-COO)-TPP has a relative high F of 12%. The evidently subdued ACQ behavior can be ascribed to the propeller shape and bulky size of the TPE units,which prevent the close packing and strong p-p interaction of TPP cores. The loose molecular packing and weak interchromophore interactions were validated by different characterization methods including UV-visible absorption, steady state and transient fluorescence spectroscope, X-ray diffraction and scanning electronic microscope observations. It is noted that 4(TPE-COO)-TPP has an emission efficiency of 14.4% in dilute THF solution. This is due to the conjugation break between the TPP and TPE moieties, the rotational and vibrational motions of the phenyl groups cannot quench the fluorescence of 4(TPE-COO)-TPP.

Aggregation-induced emission and self-assembly of functional tetraphenylethene-based tetracationic dicyclophanes for selective detection of ATP in water

Functional dicyclophanes with various substituents(e.g.,NO_(2),Br,OCH_(3)and OH)were synthesized via one-pot S_(N)2 reaction.Dicyclophanes can form nanospheres via the head-to-tail self-assembly between the cavities and the TPE units to exhibit aggregation-induced emission(AIE)in aqueous solution.These AIE-active nanospheres with cationic feature exhibited selective recognition with fluorescence response for anionic ATP via electrostatic interactions and hydrophobic effects in water.

Deciphering Benzene-Heterocycle Stacking Interaction Impact on the Electronic Structures and Photophysical Properties of Tetraphenylethene-Cored Foldamers

Conjugation,as an essential chemical term used to describe electron delocalization,can be roughly grouped into two categories,through-bond conjugation(TBC)and through-space conjugation(TSC).A hybrid conjugation system integrating both TBC and TSC is rarely studied and utilized,for lack of a well-established model and difficulty of structure modification and property tuning,despite its theoretical significance and potential applications.Herein,various foldamers with a tetraphenylethene(TPE)core are employed as hybrid conjugation models to investigate structure–property correlation by introducing heterocycles of furan/thiophene into theπ-stacking TSC component.For comparison,two kinds of TPE-cored foldamers with different stacking models,a benzene–heterocycle stacking model and a benzene–benzene stacking model,are designed.Combining experimental measurements and theoretical calculations,the impact of benzene–heterocycle interaction on the hybrid conjugation natures and photophysical properties has been studied systematically.The results reveal that the benzene–heterocycle stacking model can fabricate a hybrid conjugation nature with an improved TSC component to make a more dominant contribution to the electronic transition natures than the benzene–benzene stacking model,leading to the distinguishing photophysical behavior.This work provides valuable guidance for the design of new functional materials with hybrid conjugation systems.

Graphene Nanoribbons from Tetraphenylethene-Based Polymeric Precursor： Chemical Synthesis and Application in Thin-Film Field-Effect Transistor

Graphene nanoribbons （GNRs） with a non-zero bandgap are regarded as a promising candidate for the fabrica- tion of electronic devices. In this study, large-scale solution synthesis of narrow GNRs was firstly achieved by the intramolecular cyclodehydrogenation of kinked tetraphenylethene （TPE） polymer precursors prepared by A2B2-type Suzuki-Miyaura polymerization. After the cyclization reaction, the nanoribbons have a better conjugation than the twisted polymer precursor, resulting in obvious red shift in UV/vis absorption and photoluminescence （PL） spectra. The efficient formation of conjugated nanoribbons was also investigated by Raman, FTIR spectroscopy, and micro- scopic studies. Furthermore, such structurally well-defined GNRs have been successfully developed for top-gated field-effect transistor （FET） by directly solution processing. The AFM images show that the prepared-GNRs thin films form crystalline fibrillar intercalating networks, which can effectively facilitate the charge transport. These FET devices with ion-gel gate dielectrics exhibit low-voltage operation （〈5 V） with excellent mobility up to 0.41 cm2·V-1·s-1 and an on-off ratio of 3 × 104, thus opening up new opportunities for flexible GNRs-based electronic devices.

Direct observation of intramolecular coplanarity regulated polymorph emission of a tetraphenylethene derivative

Polymorphism makes it possible to clarify the relationship between emission property and crystal structure.However,based on the exact molecular conformation in tetraphenylethene polymorphisms,it is still challenging to evaluate the difference of intramolecular coplanarity without the support of calculation because of the complex combination of four different torsion angles between four peripheral benzenes and the central ethylene plane.Here,by using a di-formyl-functionalized tetraphenylethene derivative,two ideal polymorphisms with a consistent trend of the corresponding torsion angles have been obtained.For the first time,we explicitly demonstrated that intramolecular coplanarity is the underlying cause of the polymorphism-dependent emission of tetraphenylethene derivatives.

Blue fluorophores comprised of tetraphenylethene and imidazole： aggregation-induced emission and electroluminescence

By melting tetraphenylethene （TPE） and 1,2,4,5-tetraphenyl-lH-imidazole （TPI） units together through different linking positions, three new fluorophores are synthesized, and their optical, electronic and electro- luminescence （EL） properties are fully studied. Owing to the presence of TPE unit（s）, these fluorophores are weak emitters in solutions, but are induced to emit strongly in the aggregated state, presenting typical aggregation-induced emission characteristics. The experimental and computational results reveal that different connection patterns between TPE and TPI could impact the molecular conjugation greatly, leading to varied emission wavelength, fluorescence quantum yield and EL performance in organic light emitting diodes （OLEDs）. The fluorophore built by attaching TPE unit to the 1-position of imidazole ring shows bluest fluorescence, and its EL device emits at deep blue region （445 nm; CIE= （0.16, 0.15））. And the device based on the fluorophore by linking TPE to the 2- position of imidazole ring shows EL at 467 nm （CIE= （0.17, 0.22）） with good efficiencies of 3.17 cd.A ^-1, and 1.77%.

Tetraphenylethene based zinc complexes as fluorescent chemosensors for pyrophosphate sensing

We described a serious of zinc complexes that exhibit characteristic fluorescence responses toward pyrophosphate （PPi） and adenosine triphosphate （ATP） in aqueous media. These novel probes exploited tetraphenylethene （TPE） as fluorophore and macrocycle-polyamine （including 1,4,7,10-tetraazacyclo- dodecane and 1,4,7-triazacyclononane） Zn（ll） complexes as binding group. These ＂OFF-ON＂ type probes exhibited promising selectivity and sensitivity to PPi and ATP via a restriction ofintramolecular rotation （RIR） mechanism. The detection limit for PPi was found within nmol/L range.

Preparation and self-assembly of amphiphilic polymer with aggregation-induced emission characteristics

An amphiphilic polymer bearing tetraphenylethene (TPE) moiety was synthesized by convenient reactions. The polymer exhibits unique aggregation-induced emission (AIE) characteristics and can self-assemble to size-tunable particles in DMF/water mixtures. The polymer nanoparticles can be used for cell imaging, which provides a potential stable fluorescent tool to monitor the distribution of drugs and bioconjugates in living cells.

An AIEE polyelectrolyte as a light-up fluorescent probe for heparin sensing in full detection range

Polyelectrolyte PTPEPyH, containing tetraphenylethene (TPE) and pyridinium, was synthesized. Its optical properties were investigated with spectroscopies and the results showed that there were two emission-enhanced stages in the interaction between positive-charged PTPEPyH and negative-charged biomacromolecule heparin. The mechanism was very different due to the reduced non-radiative energy loss and the change of surroundings. The polyelectrolyte PTPEPyH, compared with ChS and HA, also showed high selectivity for heparin in the buffer solution and could be used as a potential bio-probe for heparin quantification in the clinical full range.

Construction of deep-blue AIE luminogens with TPE and oxadiazole units

In this paper, two AIE-active luminogens (Oxa-pTPE and Oxa-mTPE) constructed from tetraphenylethene and oxadiazole units were successfully synthesized and their thermal, optical and electronic properties were investigated. By linking TPE to the oxadiazole core through meta-or para-position, the intramolecular conjugation is effectively controlled. Thanks to the intelligent molecular design and specific AIE feature, when fabricated as emissive layers in non-doped OLEDs, they exhibit blue or deep-blue emission with CIE coordinates of (0.17, 0.23) and (0.15, 0.12), and good efficiencies with ηC, max and ηP, max up to 1.52 cd A-1 and 0.84 Im W-1 , shedding some light on the construction of deep-blue AIE fluorophores.

Bioactivated in vivo assembly(BIVA)peptide-tetraphenylethylene(TPE)probe with controllable assembled nanostructure for cell imaging

The emergence of fluorescent light-up molecular probe,which can specifically turn on their fluorescent in the presence of stimulation factors,has open up a new opportunity to advance biosensing and bioimaging.In this work,we designed and synthesized a peptide-AIE conjugate probe for cell imaging with controlled in situ assembled nanostructures.The modular designed probe is consisted of a selfassembled peptide-tetraphenylethene(TPE)motif,a fibroblast activation protein alpha(FAP-α)responsive motif,a hydrophilic motif and a targeting motif.The probe exhibits typically turn-on fluorescence property specifically triggered by FAP-α,which is a significant overexpressed membrane protein on pancreatic tumor cells.Interestingly,the peptide modified the TPE dramatically impacts the assembled nanostructure,which can be modulated by peptide sequences.As a result,the peptide FF(PhePhe)modification of TPE as the self-assembled motif provides a suitable balance of the probe with lightup property and nanofiber assembled structure in situ.Finally,our probe could effectively detect the FAP-αon tumor cells with high specificity.Meantime,the nanofibers in situ assembled on the surface of CAFs enhanced the probe accumulation and prolonged the retention for cell imaging.We envision that this study may inspire new insights into the design of nanostructure controlled AIE light-up bio-probe.

Synthesis of Fluorene-Bridged Arylene Vinylene Fluorophores： Effects of End-Capping Groups on the Optical Properties, Aggregation Induced Emission

We have synthesized a series of fluorene-based fluorophores, in which a central fluorene core has been modified with different peripheral arylene vinylene substituents that are able to activate aggregation-induced emission （AIE） characteristics. 9,9-Dioctylfluorene doubly end-capped at the 2,7-positions with triphenylethene groups, such as 4-（2,2-diphenylvinyl）phenyl （F1-（2,2）-HTPE） and 4-（1,2-dipbenylvinyl）phenyl （F1-（1,2）-HTPE） were synthesized and compared to the tetraphenylethene analogue （F1-TPE）. Both FI-（2,2）-HTPE and F1-（1,2）-HTPE glow with a deep blue fluorescence in THF solution with emission maxima （λem） of 426 and 403 nm, respectively. The λem slightly red-shifts in the solid-state to 458 nm for F 1-（2,2）-HTPE and 437 nm for F 1-（1,2）-HTPE. The fluorescence quantum yields （ΦF） of F1-（2,2）-HTPE （ΦF=35.1%） and FI-（1,2）-HTPE （ΦF=26.2%） were found to be higher in solution compared to the near quenching of F 1-TPE （ΦF = 0.1%）. Consequently, this results in weaker AIE-stability of F1-（2,2）-HTPE （αAIE= 1.5） and F1-（1,2）-HTPE （αAIE=1.9） compared to F1-TPE （αAIE=125）, suggesting that four phenyl groups are necessary for efficient AIE-activity of these fluorene bridged arylene vinylene type materials In addition, decreasing the steric hindrance around the arylene vinylene moiety by removal of a phenyl ring is an- other method to decrease the AIE characteristics, in a similar manner to the commonly known ＂phenyl-locking＂. Non-polar triphenylethenes are poorer AlE materials than their tetraphenylethene analogues. Replacing the hydro- gen atom of F1-（2,2）-HTPE with a cyano group affords fluorene end-capped with 2,3,3-triphenylacrylonitrile （F1-TPAN）, which boosts the AIE-effect to αAIE=90.5 and red-shifts the solid-state emission （λem=528 nm） with near quenching in THF solution （ΦF= 0.12%）. X-ray crystallographic analysis of F1-TPAN indicates that the intro- duction of cyano groups can not only diminish the intramolecular steric hindrance in comparison of F1-TPE, but also improve the molecular cohesion ability via multiple C--H...N interactions.

AIE Ligand Constructed Zn(Ⅱ)Complex with Reversible Photo-induced Color and Emission Changes

Fluoran salicylaldehyde hydrazone metal complex(FSHMC)is a kind of recently reported photo-responsive system,which has the advantages of simple synthesis,multiple colors as well as distinct color change before and after UV light irradiation.However,the emission property of FSHMC is relatively unitary.In solid state,especially,only fluorescence quench is induced after UV light irradiation,which limits their applications.In this work,a typical aggregation-induced emission(AIE)moiety of tetraphenylethene(TPE)was introduced to the design of FSHMC.The obtained FSHMC,2-Zn,exhibited reversible color and fluorescence changes upon UV light irradiation.Due to the AIE feature of compound 2,2-Zn exhibited different emission changes upon UV light irradiation in THF and in solid matrix,because of the fluorescence resonance energy transfer(FRET)process from TPE moiety to rhodamine B moiety.