• <tr id="yyy80"></tr>
  • <sup id="yyy80"></sup>
  • <tfoot id="yyy80"><noscript id="yyy80"></noscript></tfoot>
  • 99热精品在线国产_美女午夜性视频免费_国产精品国产高清国产av_av欧美777_自拍偷自拍亚洲精品老妇_亚洲熟女精品中文字幕_www日本黄色视频网_国产精品野战在线观看 ?

    Synthesis, optical properties and self-organization of blue-emitting butterfly-shaped dithienobenzosiloles

    2022-09-15 03:11:10GaozhangGouZhaolingZhangTaoFanLeiFangMingxianLiuLiangchunLi
    Chinese Chemical Letters 2022年9期

    Gaozhang Gou, Zhaoling Zhang, Tao Fan, Lei Fang, Mingxian Liu, Liangchun Li

    Shanghai Key Lab of Chemical Assessment and Sustainability, School of Chemical Science and Engineering, Tongji University, Shanghai 200092, China

    ABSTRACT Ten novel butterfly-shaped dithienobenzosilole-based luminogens, which are peripherally installed with a variety of substituents including hydrogen, phenyl and substituted phenyl groups, have been readily prepared via an iodine-induced intramolecular electrophilic double-cyclisation reaction and subsequent deiodination or coupling reactions.The optical and electrochemical properties of these compounds were systematically investigated to clarify the relationships between their structures and properties, supported by theoretical calculations.These compounds exhibit deep-blue to sky-blue emissions and high photoluminescence quantum yields up to 0.84 in solution and solid states which are regulated by the functional blades and their steric hindrance on the α– and β–positions of thiophene rings.Their high thermal- and photo- stabilities have been revealed and mainly attributed to the dithienobenzosilole core.

    Keywords:Dithienobenzosilole Luminogen Double-cyclisation Blue-emitting Photo-stability

    Over the past two decades, fluorenes and polyfluorenes (PFs)derivatives have achieved great applications for the blue lightemitting diodes (OLEDs), tytically as the light-emitting active layers [1,2].However, for the future high-performanced displays, the most challenging topic remained is to realize highly stable bluecolor emission, since the typical blue-emitting fluorene derivatives have sufferred an unwanted low-energy green emission that has been attributed to the formation of carbonyl groups at the C?9 position under photo- and thermal-degradation [3].Hence,heteroatom-bridgedπ–conjugated molecules, especially siliconbridged biaryl frameworks, such as dithienosiloles and dibenzosiloles, have attracted enormous attention owing to their remarkable thermal stability and blue emissions utilised as functional organic building blocks [4–10].In particular, the dibenzosiloles have been demonstrated exhibiting high electron transport, thermal stability and excellent photoluminescence properties in virtue of the embedded metalloid Si atom and unique electronic interactions between theπ?orbital of the conjugated modules andσ?orbital of the exocytic silicon–carbon bonds which thereby lead to the low-lying lowest unoccupied molecular orbitals (LUMOs)[11–15].And thus the dibenzosiloles and their derivatives have been widely employed in organic optoelectronic materials, such as organic light-emitting devices (OLEDs), organic field-effect transistors (OFETs), nonlinear optic materials (NLOs), high-performance organic solar cells, fluorescence sensing and bio-imaging [16–22].Many facile and ingenious synthetic strategies to prepare dibenzosiloles have been spawned in recent years to further tailor them for novel structures and functionalities [18,23–30].

    On the other hand, thiophene-incorporatedπ–extended derivatives are also particularly intriguing because of their supereminent coplanarity, charge mobility and hole-transporting properties; they are among the most successful building blocks for synthesizing highly efficient photovoltaic materials [31–35].Recently,the benzothiophene derivatives have been proved as good holetransporting materials and the integrated thiophene groups have contributed greatly to the high charge-transportation and strong luminescence [36,37].It is desirable that the integration of thiophene moieties with dibenzosiloles could generate novel materials inheriting both of their characteristics such as high thermal stability, good charge mobility and glamorous photoluminescence.Although several facile strategies, especially electrophilic iodinecyclisation and intramolecular thiolate/acetylene cyclization, were reported for the syntheses of benzothiophene and dithienofluorene derivatives [38–42], the syntheses of Si–bridged benzothiophene have been barely reported because of the very limited synthetic strategy for silole compounds and their vulnerability of acidic or basic conditions.Our group has been retaining a keen interest in the design and syntheses of dibenzosilole derivatives with intriguing structures and luminescence properties [43,44].Taking advantage of the mild iodine-induced intramolecular electrophilic cyclisation (IIIEC) reactions the difurobenzosilole derivatives could be readily synthesized in excellent yields [45].And a series of rodlike dizenzosiloles functionalized by methylthio groups have been recently reported to potentially provide superior alternatives for traditional fluorescent dyes in biological analyses and bioimaging[44,46,47].Based on these works and fascinated by the fusedthiophene and dibenzosilole compounds, we have long sought to synthesize novel dithienobenzosiloles with the concern of intrinsically molecular electronic structure, fluorescence emission and photo-stability,etc.

    Herein, we report a straightforward strategy to synthesize a series of ladder-type dithienobenzosilolesπ–conjugated moduleviathe IIIEC reactions.Through the palladium-catalysed Sonogashira or Suzuki–Miyaura cross-coupling reactions versatile substituents with different bulkiness have been installed peripherally on the dithienobenzosilole core to form elegant butterflyshaped structures.Their molecular structures, intrinsic photophysical properties, thermal- and photo-stabilities as well as the molecular orbitals have been studied associated with theoretical calculations.

    Ten butterfly-shaped dithienobenzosilole compounds were synthesized in three steps by the same strategy from the 2,7-dibromo-9-silafluorene (1) (Scheme 1).First of all, rigid rodlike molecules(2a–2c) containing a dibenzosilole core, ethynylene linkages and versatile aryl terminal groups were synthesizedviathe Sonogashira cross-coupling based on our previously reported method[44].With 2a–2c in the hand, the preinstalled dimethylthio groups were exploited for annulation withortho-ethynylene to construct thiophene rings onto the dibenzosilole core.It is notable that the success of the reaction depends on the electron density of the triple bonds which is affected by the peripheral substituents;this result correlates with our previous report that electrondonating groups on the ethynylene terminal are demanded for this annulation reaction [45].And then, featuring the terminal electron-donating B, C or D groups, the IIIEC reactions of 2a–2c were successfully accomplished to afford the iodine-functionalized dithienobenzosilole 3a–3c in 88.5%–90.3% yields.The fluorescence of the double-cyclisation products 3a–3c was quenched because of the introduced iodine atoms.In addition, although intermediates 3a–3c show poor solubility in common solvents, they could be treated witht-BuLi at –78 °C, followed by quenching with methanol, affording the double-deiodination compounds 4a–4c in quantitative yield.Finally, key intermediates 3a–3c as specific building blocks were found to be readily functionalizedviacoupling reactions.The substituents with different steric bulkiness were peripherally installed onto theβ–position of the thiophene ringsviathe palladium-catalysed Suzuki–Miyaura reactions to give 5a–5f in good yields.Sonogashira cross-coupling reaction of 3b smoothly proceeded to afford 6a in 71.6% yield.The efficient coupling reactions suggest that the dithienobenzosiloles 3a–3c manifest high activity for developing superior photovoltaic and photoelectric polymers as novel building blocks.All these synthesized ladder-type dithienobenzosilole compounds were fully characterised by multinuclear (1H,13C and29Si) NMR, HRMS and IR spectroscopies.

    Scheme 1.Synthetic routes and chemical structures of the dithienobenzosilole derivatives.

    A plausible mechanism of this IIIEC reaction is shown in Fig.S1 (Supporting information).First, molecular iodine reacts with electron-rich alkynes and forms an iodine-ethynylene complex.Thereafter, the intermediate I, I′or I′′is generated by the iodinecyclisation and the intramolecular isomerisation [48,49].The terminal electron-donating groups such as methoxy and substituted amino groups play an indispensable role in the formation of intermediate I′, which facilitated by the intramolecular attack of ortho methylthio groups could form the five-membered ring intermediate I′′.Finally, the methyl groups will be removed by I?in the systemviathe SN2reaction to generate the target double-cyclisation product.

    To elucidate the molecular structures, suitable crystals of 3a,5a and 5d were grown from a mixed solution of ethanol and dichloromethane at room temperature for the X–ray diffraction analysis.The crystal structures of 3a, 5a and 5d are depicted in Fig.1 and Fig.S2 (Supporting information), and the detailed crystallographic data are summarised in Table S1 (Supporting information).The crystal packing diagrams of 3a, 5a and 5d are shown in Fig.S3 (Supporting information).Compounds 3a, 5a and 5d are crystallized in a triclinic lattice withP1space group.All the structures intuitively feature the dithienobenzosilole cores and reveal distorted tetrahedron coordination geometry around the Si atoms.The distances of the Si–C(Ar) bonds of 3a, 5a and 5d were comparable, that are, (1.874, 1.868), (1.869, 1.865) and (1.875, 1.876) ?A,respectively.The C(Ar)–Si–C(Ar) bond angles around the respective Si atom (91.83°, 91.10° and 91.53°) correlate well with the reported dimethylthio-modified rigid rod-like dibenzosiloles, suggesting that the post-annulation reactions have little effect on the parent dibenzosilole cores [44].

    Fig.1.Crystal ORTEP diagrams of 3a, 5a and 5d

    Fig.S2 shows the torsion angles between the dithienobenzosilole plane and phenyl rings on theα– orβ–positions of thiophene units which are greatly induced by the steric hindrance between the two neighbouring rings.The torsion angles of theα–positions are asymmetrically (57.36°, 39.77°), (60.58°, 74.91°)and (35.29°, 26.39°) for 3a, 5a and 5d, respectively; those of theβ–positions are (65.63°, 55.05°) and (54.03°, 80.65°) for 5a and 5d, respectively.These torsions largely influence the extent ofπ–conjugation, and thus exert great impact on the distribution ofπelectrons, photophysical properties.In addition, the steric substituents on thiophene rings and sp3–hybridised Si atom shall cause inefficient packing in the solid state [7].The crystal packing diagrams reveal that these compounds indeed exhibit ineffectiveπ–πstacking interactions.The distances between the layers are 4.12 and 6.55 ?A for 3a and 5a respectively, while compound 5d exhibits the largest packing distance accompanied by slight bending of the dithienobenzosilole core (Fig.S3).

    Figs.S4–S7 (Supporting information) show the absorption and fluorescence spectra of 4a–6a, and the data are collected in Table S2.The UV–vis absorption spectra inn-hexane and THF are shown in Figs.2a and c respectively, and the corresponding photophysical data are listed in Table 1.All the compounds exhibit absorption maxima at 331–406 nm with very large extinction coefficients (2.66–9.66 × 104L mol?1cm?1) and intense absorptions in the range of 296–402 nm (2.26–9.94 × 104L mol?1cm?1).The low-energy absorption bands, which are significantly split into two peaks, could be assinable to the 0→0 vibrational bands of the strong S0→S1transition due to the newly formed thiophene rings.Moreover, no discernible red/blue shift accompanied by distinct solvent polarity effect is observed, indicating that the absence of intramolecular charge transition (ICT) with proper electron-withdrawing characteristic of the dithienobenzosilole core(Figs.S4–S7).

    Fig.2.UV–vis absorption and emission spectra of 4a–6a in n-hexane (a, b) and tetrahydrofuran (THF) (c, d) measured at a concentration of 5 × 10?6 mol/L.Photographs of 4a–6a captured in n-hexane (e) and THF (f) under UV light (365 nm).

    Among these compounds, 4b, 5a, 5c and 5e with the peripheral substituents on theβ–positions of the thiophene rings from H,phenyl andp-methoxyphenyl to diphenylaminophenyl (DPAP) exhibit significant blue shifts from 390 nm to 331 nm inn-hexane solution.Similiarly, the same phenomenon was observed for the analogous compounds, 4c, 5b, 5d and 5f in which the same DPAP group is installed on theα–positions.With the same substituent on theβ–positions, varying the substituents on theα–positions from dimethoxyphenyl to DPAP results in a significant red-shift in the absorption maximum and broader absorption bands such as 5e versus 5f.Compared with analogue 4b, compound 6a shows a broad band and hypsochromic shift in the absorption.It was found that electron-donating orπ–conjugated substituents on theα–position of the thiophene rings could cause the red-shift in the absorption, while the introduction of the steric bulky substituents on theβ–positions resulted in a blue shift.Thus, the absorption spectra of this system can be jointly tailored by the substituents on theα– andβ–positions of the thiophene rings.

    The emission spectra inn-hexane and THF are shown in Figs.2b and d.Upon excitation at the absorption maxima, all the dithienobenzosilole compounds (4a–6a) exhibit intense emissions withλmaxof 398–458 nm corresponding to deep to sky blue emissions in solution, as well as 11%–84% quantum yields (QYs) in the air at an ambient temperature (Figs.2e, f, Figs.S8–S12 in Supporting information and Table 1).The emission spectra of 4a and 6a inn-hexane feature broad bands withλmax(lifetime, QY) of 421 nm (τ= 0.44 ns, 69%) and 441 nm (τ= 0.44 ns, 31%), respectively.Comparatively, in THF solution, a little bathochromic shift,improved lifetime and QY are obtained,i.e., 427 nm (τ= 0.52 ns,77%) for 4a and 448 nm (τ= 0.51 ns, 43%) for 6a.Moreover,the emission spectra of 4b, 5a, 5c and 5e inn-hexane manifest broad bands withλmax(lifetime, QY) of 402–428 nm (τ= 0.36–1.17 ns, 11%–79%) and 409–435 nm (τ= 0.48–1.00 ns, 9%–82%)in THF.In particular, in the same solvent (e.g., n-hexane), the QYs of 4b, 5a, 5c and 5e with the increase of steric hindrance on theβ–position of the thiophene rings significantly decrease from 0.75 for 4b to 0.11 for 5e.The emission spectra of 4c, 5b, 5d and 5f inn-hexane feature broad bands withλmax(lifetime, QY) of 434–458 nm (τ= 0.45–0.52 ns, 49%–78%) and 444–449 nm (τ= 0.52–0.62 ns, 58%–79%) in THF.For the compound series of 4c, 5b, 5d and 5f, the variation tendency of QY andλmaxis similar, that is, a certain decrease with some blue shift.

    To gain a deeper insight into the correlation between the photophysical property and molecular structure, the whole moleculardistortions are attempted to be evaluated by the sum of the torsion angles (S?) of the substituents on theα– andβ–positions of the thiophene rings.By analysis of the crystal structures, theS?of 5a is much larger than those of 3a and 5d.The other compounds without crystal structures are verified from the optimised structures by density-functional theory (DFT) calculations at the B3LYP/6–31+G(d, p) level (Fig.S13 in Supporting information).It was found that the QY (ΦF) in solution is particularly affected by intramolecular rotation especially from the steric hindrances on theα– andβ–positions.The extents of the intramolecular rotation interfered by the steric hindrance could result in sharp distinction between the radiation (kr) and non-radiation (knr) rate constants,thus greatly affecting the QY (Table 1).The largeS?values, which could estimate the degree of intramolecular rotation, will cause radiation-less relaxation and further affect QYs and spectra.In general, the installed electron-donating orπ–conjugated substituents on theα–positions of the thiophene rings lead to red-shift in spectra, whereas introduction of the substituents with steric bulkiness on theβ–positions result in blue-shift in spectra and decreased QY.This rule revealed here is of great significance in applying molecular engineering for the design and syntheses of dithienobenzosilole derivatives with adjustable absorption and emission, as well as improved QYs.

    Table 1 Selected photophysical data of 4a–6a in different solvents at 298 K (c = 5 × 10?6 mol/L).

    For this kind ofπ–conjugated molecules installed with aryl blades, their photophysical variations in various states are particularly interesting, since a phenomenon antithetic to the general aggregation-induced quenching (ACQ) has been reported and termed aggregation-induced emission (AIE) [50–53].It has been revealed that the main contributions to the AIE effect are the restricted intramolecular rotation and suppressedπ–πstacking by the twisted molecular conformation of AIEgens in the aggregation state.And thus the energy of the excited molecules will be overwhelmingly exhausted by the radiative channel leading to enhanced emission [54,55].The photophysical properties of 5a–6a were investigated by their fluorescence spectra in THF/H2O mixtures with different water fractions (fw) in a concentration of 10 μmol/L (Figs.S14–S17 in Supporting information).Compounds 5a–6a exhibited strong fluorescence in the THF solution but the emission intensity gradually decreased and the emission maxima are red-shifted withfwincreasing, which could be classified as a typical ACQ effect.This is because 5a–6a as a novel molecular system featuring largeπ–conjugated dithienobenzosilole core and plenty of peripheral blade groups are likely to have impededπ–πstacking but the intramolecular dynamics cannot be completely restricted in the aggregation state [56].

    Fig.3.(a) Normalized solid-state emission spectra of 4a–6a measured at room temperature.Inset: emission maximum.(b) Photographs of compounds 4a–6a powders under 365 nm irradiation.

    Fig.4.Energy level diagrams of the frontier orbitals of 4a–6a by DFT calculations.

    In view of that various applications of the organic emitting materials have been developed in their solid state, the solid-state photophysical properties of 4a–6a were studied systematically (Fig.3 and Table 1).Owing to the dithienobenzosilole core, the normalised solid-state emission maxima of 4a–6a cover a wide range from 436 nm to 498 nm.The emission maxima of all the compounds are red-shifted with respect to the corresponding emission maxima in solution, whereas the fluorescence QYs considerably decrease to 0.1%–11% due to the ACQ effect.Notably, the CIE color coordinates of these dithienobenzosiloles in solution are located at the blue (0.15, 0.06) or deep-blue (0.15, 0.10) light emission region, while the powders’CIE color coordinates fall in the blue (0.15,0.06) or green (0.3, 0.6) light emission region with good and stable color purity (Figs.S18–S20 in Supporting information).Therefore,abundant alternatives to the traditional blue-emitting materials are supplied for developing this kind of key materials with high stability and color purity.

    The electrochemical measurements of the dithienobenzosilolebased luminogens were conductedviacyclic voltammetry (CV)in dichloromethane (DCM) solutions utilizingn-Bu4NPF6as the supporting electrolyte to evaluate the energy levels [57].The CV curves are shown in Fig.S21 (Supporting information) and the electrochemical data, calculated highest occupied molecular orbit (HOMO) and lowest unoccupied MO (LUMO) energy levels are summarised in Table S3 (Supporting information).The oxidation peaks of the dithienobenzosilole luminogens are calculated by the onset values to be 1.17–1.94 V.The HOMO energy levels are estimated from the oxidation potential according to equationEHOMO= ?(Eonset+ 4.74) eV, and then the LUMO energy levels(ELUMO=EHOMO+Eg) are determined by the optical bandgaps.Compounds 4a–6a exhibit the first irreversible oxidation onset peaks from 0.65 to 0.93 V, however the reduction waves are structureless and explicit, which could be attributed to the irreversible single-electron oxidation and reduction from theσ?(Si)–π?(C) interaction in the Si–bridged species [58].The corresponding electrochemical gaps fall in the range of 2.76–3.12 eV.The electrondonating ability andπ–conjugation degree of the substituents on theα–positions, as well as the steric hindrance of the substituents on theβ–positions significantly affect the bandgaps, as observed from the optical and electrochemical measurements.

    To gain insight into the geometric, frontier orbital (FO), electronic and spectroscopic properties of the dithienobenzosiloles,DFT and time-dependent DFT (TD–DFT) calculations were conducted with the Gaussian 09 package [59].The geometric structures were optimised, employing the B3LYP/6–31+G(d, p) basis set with single-point energy.The UV–vis spectra and MOs were calculated with the TD–DFT (SCRF(PCM/Bader)–B3LYP/6–31+G(d, p)) basis set.The results of electronic absorption spectroscopy are shown in Figs.S22 and S23 (Supporting information) and the data are summarized in Tables S4 and S5 (Supporting information), which are well consistent with the experimental data.The minimum deviation between the calculated and experimental values of the absorption maxima is only 0.54%, namely the vertical excitation to the first excited state primarily involving the HOMO to LUMO(π→π?) transition (>94%) with very high oscillator strength.The FO energy level diagrams of 4a–6a are shown in Fig.4.The contours of MOs (HOMO?1, HOMO, LUMO and LUMO+1), along with the electrostatic potential maps, are shown in Figs.S24 and S25(Supporting information).The calculated HOMO and LUMO levels are in the range from –5.41/–4.90 to –2.02/–1.62 eV.Therefore,the theoretical energy gaps (Eg) of 4a–6a are 3.50, 3.50, 3.16, 3.73,3.28, 3.69, 3.33, 3.41, 3.19 and 3.23 eV.According to Fig.S24 and S25, HOMO and LUMO of 4a, 4b, 4c, 5a, 5c and 6a are distributed in the dithienobenzosilole cores, indicating that the S0→S1transitions of these compounds exhibit a local excitation characteristic.In addition, HOMOs of 5b, 5d, 5e and 5f are dominated on the dithienobenzosilole core and the substituent on theα–positions of the thiophene rings, while the LUMO densities are mainly concentrated on the dithienobenzosilole moieties, indicating the latent occurrence of the intramolecular charge transfer process.The calculatedEgvalues are larger than the experimental values from CV and the UV–vis absorption spectra but the trends exhibit a good coincidence.

    The thermal properties of the dithienobenzosilole luminogens were verified by the fluorescence spectra of the 4a–6a powder samples annealed in the air for 15 h at 200 °C in comparison with their spectra of pristine samples.Fig.5 shows the normalised fluorescence spectra of the pristine and annealed 4a–6a.No new emission bands, in particular the unwanted low-energy green emissions as that of the fluorenes, were detected for the annealed samples; each annealed sample exhibited identical spectrum to that of the corresponding pristine material, suggesting that the butterflyshaped dithienobenzosiloles possess good thermal stability [60].In addition, thermogravimetric analysis (TGA) of the representative compounds 4c, 5b and 5f were conducted under nitrogen atmosphere.The decomposition temperatures (Td) estimated by 5%weight loss were 345, 470 and 498 °C respectively, also suggesting the high thermal stability of these butterfly-shaped dithienobenzosiloles (Fig.S26 in Supporting information).

    The structures of these butterfly-shaped dithienobenzosiloles are similar to those of diphenylindene (DPI) derivatives [61],which exhibits extremely poor photo-stability on account of the reversible photo-cyclisation (PC).Other derivatives including spirofunctionalized diphenylethenes [62], tetraphenylethene (TPE)derivatives [63], diarylethenes (DAEs) [64],etc.also display unsatisfactory photo-stability ascribed to a similar photochromism reactivity.The photostability of luminogens is of vital importance in consideration of various applications involving light radiation.To our delight, except for the outstanding thermal stability, the dibenzosilole derivatives also manifest compelling photo-stability.

    The photo-stability of 5a–5f were tested in an argon-saturated DCM solution (5.0 × 10?6mol/L) by tracking the variations of UV–vis and fluorescence spectra after UV exposure from a lamp at 365 nm (power density = 86.5 mW/cm2) under ambient temperature.The absorption and fluorescence spectra of 5a–5f after UV exposure and the plots of the relative emission intensity (F/F0) versus the relative absorbance intensity (Abs/Abs0) are shown in Fig.S27 and S28 (Supporting information).Compounds 5a–5f show good to excellent photo-stability after UV light irradiation for 60 or 90 min.About 80% and 60% of the fluorescence intensity is retained for 5a and 5c after the exposures for 60 and 90 min respectively, while negligible changes in the absorption and emission intensity are observed for the other compounds.These results indicate that introduction of the amino group DPAP could considerably improve the photo-stability of dithienobenzosilole-based luminogens.Additionally, the photo-stability of 5a–5f has been monitored by taking the1H NMR spectra (1.0 mg in 0.6 mL of C6D6or CDCl3) under 365 nm irradiation in argon atmosphere at ambient temperature.As shown by the time-dependent1H NMR spectra (Figs.S29–S34 in Supporting information), no discernible variation appears for all these compounds after UV light irradiation for 8 h.Representative compounds 4c, 5b, 5d and 5f even show persistent photo-stability under the UV irradiation in the air-saturated solution (Figs.S35 and S36 in Supporting information).Compared with our previously reported rigid rod-like dimethylthio-modified dibenzosiloles[44], the photo-stability, photo-oxidation stability and QYs of these butterfly-shaped dithienobenzosilole-based luminogens have been greatly improved, suggesting that annulationviathis IIIEC reaction is a straightforward strategy to not only modulate the photophysical properties but also enhance the photo-stability and photooxidation stability [65,66].

    Fig.5.Fluorescence spectra of pristine and annealed 4a–6a in DCM.

    Fig.6.SEM images of self-assembled 4a in toluene (a, b) and 5f in n-hexane (c–e).

    Compounds 4a and 5f were selected as representatives for selforganization in verious solvents, such asn-hexane, toluene and DCM/n-hexane (1:1),viaslow evaporation method (Fig.6 and Figs.S37–S40 in Supporting information).In particular, both of them exhibit a strong tendency to self-organize into different morphologies from different solvents and were characterised by scanning electron microscopy (SEM).As shown in Fig.6, 4a and 5f are readily to self-organize into one-dimensional micro-sheets and sticks which possess great potential in the applications of electronic devices such as photonic crystal and OFETs.

    In summary, ten novel butterfly-shaped dithienobenzosilolebased luminogens were synthesizedviathe iodine-induced intramolecular electrophilic double-cyclisation reaction.The readily produced diiodide dithienobenzosilole can serve as a useful building block for constructing versatile optoelectronic materials through the practicable cross-coupling reactions.Their photophysical and electrochemical properties, as well as thermal stability and photo-stability, were particularly evaluated and further elucidated by DFT studies.These dithienobenzosilole-based luminogens exhibit deep-blue to sky-blue emissions with very high quantum yields up to 0.84 in solution.The quantum yields of this molecular system are regulated by the substituents on theα– andβ–positions of the thiophene rings displaying different extent of intramolecular rotation based on the steric hindrances.Bulky substituents on theβ–positions result in twisted structure and distinct blue-shift in the adsorption.More rotatable and dynamic groups installed on the periphery will exhaust the excited energy in non-radiative way, leading to decreased quantum yields.These dithienobenzosiloles exhibit high thermal stability up to 200 °C and outstanding photo-stability as well as photo-oxidation stability attributed to the dithienobenzosilole core.The introduction of diphenylaminophenyl groups could suppress photo-bleaching to improve the photo-stability.The facile strategy to synthesize dithienobenzosiloles and principles for molecular engineering unveiled in this work will provide valuable guidance for molecular design and synthesis of novel organic optoelectronic materials with prominent properties such as luminous efficacy and stability in practical applications.

    Declaration of competing interest

    The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

    Acknowledgments

    This work was financially supported by the National Natural Science Foundation of China (No.21501135), the Fundamental Research Funds for the Central Universities, and the Recruitment Program of Global Experts of China.

    Supplementary materials

    Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.cclet.2021.12.052.

    亚洲成人国产一区在线观看| 别揉我奶头~嗯~啊~动态视频| 在线视频色国产色| 咕卡用的链子| 精品熟女少妇八av免费久了| 19禁男女啪啪无遮挡网站| 三上悠亚av全集在线观看| 国产成人精品久久二区二区免费| 两人在一起打扑克的视频| 老司机影院毛片| tube8黄色片| 女性被躁到高潮视频| av一本久久久久| 欧美成狂野欧美在线观看| 热99久久久久精品小说推荐| 精品一区二区三区视频在线观看免费 | 久久亚洲精品不卡| 国产精品欧美亚洲77777| 亚洲五月婷婷丁香| 国产日韩欧美亚洲二区| 亚洲第一欧美日韩一区二区三区| 在线永久观看黄色视频| 91大片在线观看| 一边摸一边抽搐一进一小说 | 黄片大片在线免费观看| 中文字幕人妻丝袜一区二区| 欧美+亚洲+日韩+国产| 在线十欧美十亚洲十日本专区| 久久ye,这里只有精品| 女警被强在线播放| 久久久久国内视频| 黄网站色视频无遮挡免费观看| 日日爽夜夜爽网站| 校园春色视频在线观看| 香蕉国产在线看| videosex国产| 亚洲色图综合在线观看| 国产一卡二卡三卡精品| 国产99白浆流出| 在线国产一区二区在线| 男女午夜视频在线观看| 99久久99久久久精品蜜桃| 国产高清videossex| 母亲3免费完整高清在线观看| 亚洲成人免费av在线播放| 国产1区2区3区精品| 国产黄色免费在线视频| 日韩精品免费视频一区二区三区| 夫妻午夜视频| 十八禁人妻一区二区| 欧美激情高清一区二区三区| 嫩草影视91久久| 国产成人免费无遮挡视频| 老司机午夜十八禁免费视频| 国产精品久久久久久人妻精品电影| 亚洲精品美女久久久久99蜜臀| 在线观看一区二区三区激情| 欧美国产精品va在线观看不卡| 亚洲色图综合在线观看| 久久这里只有精品19| 人成视频在线观看免费观看| 亚洲精品美女久久av网站| 一区二区日韩欧美中文字幕| 久久人人97超碰香蕉20202| 欧美国产精品va在线观看不卡| 人人妻人人添人人爽欧美一区卜| 色94色欧美一区二区| 国产欧美日韩一区二区三区在线| 下体分泌物呈黄色| 欧美日本中文国产一区发布| 美女视频免费永久观看网站| www.熟女人妻精品国产| 视频在线观看一区二区三区| 午夜福利免费观看在线| 精品一品国产午夜福利视频| 亚洲精品中文字幕在线视频| 国产免费男女视频| 91老司机精品| 在线av久久热| 午夜精品在线福利| 久久中文字幕一级| 一二三四社区在线视频社区8| 精品视频人人做人人爽| 老司机亚洲免费影院| 国产人伦9x9x在线观看| 多毛熟女@视频| 51午夜福利影视在线观看| 久久精品国产a三级三级三级| 精品久久蜜臀av无| 亚洲av第一区精品v没综合| 黄片小视频在线播放| 国产xxxxx性猛交| 伊人久久大香线蕉亚洲五| 女同久久另类99精品国产91| 又黄又粗又硬又大视频| 中文字幕av电影在线播放| 亚洲精品国产色婷婷电影| 99热网站在线观看| 久久午夜亚洲精品久久| 亚洲av欧美aⅴ国产| 黄色视频,在线免费观看| 十八禁网站免费在线| avwww免费| 亚洲成人手机| 久久久久国产一级毛片高清牌| 女人被狂操c到高潮| 免费女性裸体啪啪无遮挡网站| 亚洲国产精品sss在线观看 | 久久精品成人免费网站| 俄罗斯特黄特色一大片| 91成年电影在线观看| 日本黄色日本黄色录像| 欧美老熟妇乱子伦牲交| 老司机靠b影院| 久久狼人影院| 国产99白浆流出| 国产亚洲av高清不卡| 亚洲一区中文字幕在线| 欧美最黄视频在线播放免费 | 午夜免费成人在线视频| 国产精品亚洲一级av第二区| www日本在线高清视频| 久久精品亚洲精品国产色婷小说| 色综合婷婷激情| 欧美最黄视频在线播放免费 | 天天躁狠狠躁夜夜躁狠狠躁| 一边摸一边做爽爽视频免费| 97人妻天天添夜夜摸| 两性午夜刺激爽爽歪歪视频在线观看 | 成年版毛片免费区| av不卡在线播放| 精品国产国语对白av| 精品欧美一区二区三区在线| 亚洲人成伊人成综合网2020| 日本vs欧美在线观看视频| 亚洲avbb在线观看| 99riav亚洲国产免费| 中文字幕另类日韩欧美亚洲嫩草| 国产一卡二卡三卡精品| 1024香蕉在线观看| 久久久精品区二区三区| 欧美日韩瑟瑟在线播放| 韩国av一区二区三区四区| 91大片在线观看| 在线av久久热| 精品久久蜜臀av无| 中文字幕色久视频| 欧美成人免费av一区二区三区 | 国产精品久久电影中文字幕 | 国产成+人综合+亚洲专区| 亚洲av成人一区二区三| 久久 成人 亚洲| 天天躁日日躁夜夜躁夜夜| 99久久国产精品久久久| 国产精品偷伦视频观看了| 大香蕉久久成人网| 欧美精品人与动牲交sv欧美| 人人妻人人爽人人添夜夜欢视频| 丰满的人妻完整版| 日韩欧美一区视频在线观看| 精品人妻在线不人妻| 在线观看免费视频网站a站| 国产蜜桃级精品一区二区三区 | 久久这里只有精品19| av有码第一页| 一个人免费在线观看的高清视频| 国产成人精品无人区| 精品久久久久久久毛片微露脸| 亚洲视频免费观看视频| 80岁老熟妇乱子伦牲交| 亚洲第一av免费看| 精品久久久久久,| 老熟妇仑乱视频hdxx| 老熟妇仑乱视频hdxx| 十八禁高潮呻吟视频| 亚洲精品中文字幕在线视频| 亚洲五月色婷婷综合| 在线观看www视频免费| 12—13女人毛片做爰片一| 国产99白浆流出| 精品电影一区二区在线| 国产成人欧美| 三上悠亚av全集在线观看| 国产高清视频在线播放一区| 精品电影一区二区在线| 久久久久久久国产电影| 精品亚洲成国产av| 国产一区在线观看成人免费| 午夜福利欧美成人| 黄色女人牲交| 亚洲精品美女久久久久99蜜臀| 久久久久精品人妻al黑| 91成年电影在线观看| 男女之事视频高清在线观看| 国产成人精品无人区| 免费人成视频x8x8入口观看| 精品一品国产午夜福利视频| 一a级毛片在线观看| 国产精品免费一区二区三区在线 | 女性生殖器流出的白浆| 在线永久观看黄色视频| 男人舔女人的私密视频| 十八禁高潮呻吟视频| 纯流量卡能插随身wifi吗| 丝袜在线中文字幕| 精品人妻1区二区| 亚洲欧美色中文字幕在线| 国产一区在线观看成人免费| 国产欧美日韩一区二区三| 美女高潮喷水抽搐中文字幕| 亚洲av日韩精品久久久久久密| 黑丝袜美女国产一区| 久久久久久久精品吃奶| 国产精华一区二区三区| 国产aⅴ精品一区二区三区波| 国产成人av激情在线播放| 国产精品欧美亚洲77777| 精品久久久久久久久久免费视频 | 成人亚洲精品一区在线观看| 亚洲七黄色美女视频| 国产精品久久久久久人妻精品电影| 黄片大片在线免费观看| 99久久国产精品久久久| 自拍欧美九色日韩亚洲蝌蚪91| 国内久久婷婷六月综合欲色啪| 亚洲一区高清亚洲精品| 色综合欧美亚洲国产小说| 中文字幕av电影在线播放| 下体分泌物呈黄色| 日韩制服丝袜自拍偷拍| 美女视频免费永久观看网站| 午夜视频精品福利| 色在线成人网| 国产三级黄色录像| 久久精品国产亚洲av高清一级| 高清黄色对白视频在线免费看| 在线观看午夜福利视频| 日韩大码丰满熟妇| 别揉我奶头~嗯~啊~动态视频| 欧美亚洲 丝袜 人妻 在线| 久久精品91无色码中文字幕| 亚洲熟女精品中文字幕| 老司机午夜福利在线观看视频| 亚洲成国产人片在线观看| 午夜久久久在线观看| 日日爽夜夜爽网站| 欧美国产精品va在线观看不卡| 欧美日韩精品网址| 一边摸一边抽搐一进一出视频| 757午夜福利合集在线观看| 国产高清视频在线播放一区| 在线观看一区二区三区激情| 每晚都被弄得嗷嗷叫到高潮| 久久久精品区二区三区| 亚洲午夜精品一区,二区,三区| av免费在线观看网站| 老熟女久久久| 啦啦啦免费观看视频1| a级片在线免费高清观看视频| 久久精品人人爽人人爽视色| 欧美精品人与动牲交sv欧美| 国产欧美日韩综合在线一区二区| 91麻豆av在线| 国产1区2区3区精品| 在线十欧美十亚洲十日本专区| 婷婷成人精品国产| 国产成人系列免费观看| 亚洲av美国av| 中文字幕人妻丝袜制服| 成年人黄色毛片网站| 大码成人一级视频| 精品少妇久久久久久888优播| 黄色a级毛片大全视频| 精品国产国语对白av| 欧美不卡视频在线免费观看 | 国产精品九九99| 亚洲熟妇中文字幕五十中出 | 国产又色又爽无遮挡免费看| www.999成人在线观看| 久久99一区二区三区| 欧美色视频一区免费| 国产精品免费大片| 国产成人精品久久二区二区免费| 女同久久另类99精品国产91| 亚洲美女黄片视频| 精品人妻熟女毛片av久久网站| 亚洲国产精品一区二区三区在线| 日韩有码中文字幕| 午夜成年电影在线免费观看| 午夜91福利影院| 天堂俺去俺来也www色官网| 丁香欧美五月| 亚洲精品粉嫩美女一区| 一级,二级,三级黄色视频| 亚洲欧美激情综合另类| 欧美久久黑人一区二区| 美女国产高潮福利片在线看| 大型黄色视频在线免费观看| 18禁国产床啪视频网站| 丝袜美腿诱惑在线| 香蕉丝袜av| 一边摸一边做爽爽视频免费| 99久久人妻综合| 亚洲av电影在线进入| 桃红色精品国产亚洲av| 日本一区二区免费在线视频| 久久影院123| 在线十欧美十亚洲十日本专区| 日韩欧美国产一区二区入口| a级片在线免费高清观看视频| 国产成人精品无人区| 国产亚洲欧美98| 一区二区三区国产精品乱码| 麻豆乱淫一区二区| 国产免费av片在线观看野外av| 丰满的人妻完整版| 亚洲欧美一区二区三区黑人| 麻豆国产av国片精品| 免费av中文字幕在线| 久久精品国产综合久久久| 天堂俺去俺来也www色官网| 精品人妻1区二区| 国产一卡二卡三卡精品| 满18在线观看网站| 日本wwww免费看| 亚洲情色 制服丝袜| 亚洲午夜理论影院| 天堂俺去俺来也www色官网| 欧美精品高潮呻吟av久久| 欧美激情极品国产一区二区三区| 一级片免费观看大全| 99热网站在线观看| 亚洲色图综合在线观看| 一级黄色大片毛片| av天堂在线播放| 一二三四社区在线视频社区8| 亚洲黑人精品在线| 亚洲人成伊人成综合网2020| 国产成人av激情在线播放| 国产精品一区二区精品视频观看| 免费看a级黄色片| 日韩欧美三级三区| 精品福利永久在线观看| 自拍欧美九色日韩亚洲蝌蚪91| 欧美日韩国产mv在线观看视频| 亚洲国产欧美日韩在线播放| 欧美黑人精品巨大| 午夜亚洲福利在线播放| 久久久精品国产亚洲av高清涩受| 欧美最黄视频在线播放免费 | 99精国产麻豆久久婷婷| 日韩大码丰满熟妇| 久久精品国产99精品国产亚洲性色 | 人成视频在线观看免费观看| 嫁个100分男人电影在线观看| 免费av中文字幕在线| 热99国产精品久久久久久7| 人人妻,人人澡人人爽秒播| 岛国毛片在线播放| 成人手机av| 男女高潮啪啪啪动态图| 国产精品国产高清国产av | 久99久视频精品免费| 最近最新中文字幕大全电影3 | 欧美丝袜亚洲另类 | 19禁男女啪啪无遮挡网站| 香蕉国产在线看| 午夜免费鲁丝| 午夜视频精品福利| 亚洲成av片中文字幕在线观看| 大香蕉久久成人网| 国产精品 欧美亚洲| 啦啦啦在线免费观看视频4| 999久久久国产精品视频| av有码第一页| 精品国产一区二区久久| 久久人妻av系列| 色婷婷久久久亚洲欧美| 国产xxxxx性猛交| 亚洲av电影在线进入| 如日韩欧美国产精品一区二区三区| 黄色a级毛片大全视频| 久热爱精品视频在线9| 国产真人三级小视频在线观看| 久久人妻熟女aⅴ| 777米奇影视久久| 激情在线观看视频在线高清 | 大型av网站在线播放| 亚洲免费av在线视频| 亚洲中文日韩欧美视频| ponron亚洲| 国产三级黄色录像| 午夜老司机福利片| 啦啦啦在线免费观看视频4| 国产一区二区三区视频了| 亚洲av美国av| 久久精品亚洲av国产电影网| av天堂久久9| 亚洲成人免费电影在线观看| 国产不卡av网站在线观看| 亚洲人成电影观看| 久久午夜综合久久蜜桃| 亚洲专区国产一区二区| 久久亚洲精品不卡| av超薄肉色丝袜交足视频| 多毛熟女@视频| 老熟妇乱子伦视频在线观看| 欧美av亚洲av综合av国产av| 国产亚洲精品久久久久5区| 成年女人毛片免费观看观看9 | 亚洲在线自拍视频| 两性午夜刺激爽爽歪歪视频在线观看 | 一进一出抽搐gif免费好疼 | 韩国精品一区二区三区| 欧美激情极品国产一区二区三区| 超色免费av| 国产高清国产精品国产三级| 丰满饥渴人妻一区二区三| 久久精品国产清高在天天线| 最新的欧美精品一区二区| 国产人伦9x9x在线观看| 日韩中文字幕欧美一区二区| 十八禁网站免费在线| 久久九九热精品免费| 精品国产国语对白av| 午夜福利乱码中文字幕| 国产精品久久久久久人妻精品电影| 首页视频小说图片口味搜索| 咕卡用的链子| 天天影视国产精品| 国产精品久久视频播放| 91大片在线观看| 一边摸一边做爽爽视频免费| 亚洲,欧美精品.| 国产熟女午夜一区二区三区| 真人做人爱边吃奶动态| 女人高潮潮喷娇喘18禁视频| 久久中文字幕人妻熟女| 18禁裸乳无遮挡动漫免费视频| 757午夜福利合集在线观看| avwww免费| 中文欧美无线码| 国产1区2区3区精品| 在线观看一区二区三区激情| x7x7x7水蜜桃| 少妇的丰满在线观看| 久久久久国产精品人妻aⅴ院 | 日韩有码中文字幕| 亚洲专区字幕在线| 国产高清激情床上av| 波多野结衣一区麻豆| 国产成人精品久久二区二区免费| 国产真人三级小视频在线观看| 中国美女看黄片| 精品少妇久久久久久888优播| 大型黄色视频在线免费观看| 黄频高清免费视频| av天堂久久9| 成人国产一区最新在线观看| 51午夜福利影视在线观看| 伦理电影免费视频| 纯流量卡能插随身wifi吗| 少妇裸体淫交视频免费看高清 | 欧美不卡视频在线免费观看 | 高潮久久久久久久久久久不卡| av线在线观看网站| 啪啪无遮挡十八禁网站| 亚洲欧美日韩高清在线视频| 99久久人妻综合| 精品福利永久在线观看| 人妻丰满熟妇av一区二区三区 | 黄色视频不卡| 亚洲一区高清亚洲精品| 一二三四在线观看免费中文在| 久久香蕉国产精品| 欧美一级毛片孕妇| 999久久久精品免费观看国产| 亚洲欧美一区二区三区黑人| 黄片播放在线免费| 国产在线一区二区三区精| 中亚洲国语对白在线视频| 亚洲av片天天在线观看| 一区福利在线观看| 精品国产一区二区久久| 欧美日韩av久久| 99在线人妻在线中文字幕 | 少妇粗大呻吟视频| 51午夜福利影视在线观看| 欧美久久黑人一区二区| 91成人精品电影| 男人的好看免费观看在线视频 | 露出奶头的视频| 成人18禁在线播放| 99久久人妻综合| 久久精品91无色码中文字幕| 王馨瑶露胸无遮挡在线观看| 他把我摸到了高潮在线观看| 亚洲人成伊人成综合网2020| 一级黄色大片毛片| 免费观看人在逋| 精品久久久久久久久久免费视频 | 99久久99久久久精品蜜桃| 他把我摸到了高潮在线观看| 老司机午夜十八禁免费视频| 久久久精品区二区三区| 免费观看人在逋| xxxhd国产人妻xxx| 国产淫语在线视频| 亚洲人成伊人成综合网2020| 一边摸一边做爽爽视频免费| 99国产综合亚洲精品| 黄片播放在线免费| 一区二区日韩欧美中文字幕| 极品人妻少妇av视频| 超碰97精品在线观看| 欧美在线一区亚洲| 久久国产亚洲av麻豆专区| 国产不卡av网站在线观看| 亚洲精品乱久久久久久| 欧美成人午夜精品| а√天堂www在线а√下载 | 俄罗斯特黄特色一大片| 熟女少妇亚洲综合色aaa.| 老司机靠b影院| 中亚洲国语对白在线视频| 好看av亚洲va欧美ⅴa在| a级片在线免费高清观看视频| 久久久国产成人精品二区 | 亚洲欧美精品综合一区二区三区| 国产精品自产拍在线观看55亚洲 | 久久亚洲精品不卡| 夜夜夜夜夜久久久久| 美女视频免费永久观看网站| 久久久久久久久久久久大奶| av电影中文网址| 在线天堂中文资源库| 高清在线国产一区| 亚洲第一av免费看| 国产成人一区二区三区免费视频网站| 麻豆乱淫一区二区| 国产成人精品无人区| 午夜91福利影院| 亚洲九九香蕉| 成人永久免费在线观看视频| 99精国产麻豆久久婷婷| 国产成人精品久久二区二区免费| 亚洲第一青青草原| 美女扒开内裤让男人捅视频| 国产深夜福利视频在线观看| 两性夫妻黄色片| 少妇 在线观看| 亚洲国产精品一区二区三区在线| 精品高清国产在线一区| 99热只有精品国产| 欧美精品av麻豆av| 国产又色又爽无遮挡免费看| 亚洲成a人片在线一区二区| 12—13女人毛片做爰片一| 日韩大码丰满熟妇| 国产精品99久久99久久久不卡| 少妇裸体淫交视频免费看高清 | 国产野战对白在线观看| 日韩一卡2卡3卡4卡2021年| 老熟妇仑乱视频hdxx| 在线观看免费日韩欧美大片| 国产精品98久久久久久宅男小说| 亚洲av日韩在线播放| 久久精品亚洲精品国产色婷小说| 日韩熟女老妇一区二区性免费视频| 亚洲 欧美一区二区三区| 男女床上黄色一级片免费看| 久久ye,这里只有精品| 宅男免费午夜| 中文字幕最新亚洲高清| av视频免费观看在线观看| 欧美另类亚洲清纯唯美| 国产又爽黄色视频| 欧美黄色淫秽网站| 亚洲av成人不卡在线观看播放网| 女警被强在线播放| 天天躁夜夜躁狠狠躁躁| 操出白浆在线播放| 伊人久久大香线蕉亚洲五| 在线观看免费午夜福利视频| 亚洲精品中文字幕在线视频| 久久性视频一级片| 侵犯人妻中文字幕一二三四区| 满18在线观看网站| 欧美国产精品va在线观看不卡| 黑丝袜美女国产一区| 看片在线看免费视频| 欧美日本中文国产一区发布| 我的亚洲天堂| 欧美黑人欧美精品刺激| 9色porny在线观看| 黄片小视频在线播放| 国产日韩一区二区三区精品不卡| 两个人免费观看高清视频| svipshipincom国产片| 精品国产一区二区三区四区第35| 久久久久国产一级毛片高清牌| 涩涩av久久男人的天堂| 免费不卡黄色视频| 免费黄频网站在线观看国产| 操美女的视频在线观看| av中文乱码字幕在线| 日本撒尿小便嘘嘘汇集6| 亚洲美女黄片视频| 18禁裸乳无遮挡动漫免费视频| 国产野战对白在线观看| 久久久久久亚洲精品国产蜜桃av| 十八禁高潮呻吟视频| 亚洲成国产人片在线观看| 亚洲国产毛片av蜜桃av| 女人精品久久久久毛片|