• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Organoqel based on self-assembled 5- (4-nonylphenyl) -7-azaindoles. The present invention relates to a compound derived from 7-azaindole, to an organogel formed by these compounds that has an emission induced by aggregation (aie) in the blue region of the visible spectrum (450-495 nm) and a xerogel obtained by drying of said organogel. Given these properties, this organogel or xerogel can be applicable to optoelectronic devices or fluorescent sensors. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2583138A1
    申请号:ES201530187
    申请日:2015-02-17
    公开日:2016-09-19
    发明作者:Eva María GARCÍA FRUTOS
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

    5
    10
    fifteen
    twenty
    25
    30
    Organogel based on 5- (4-nonylphenyl) -7-self-assembled azaindoles
    DESCRIPTION
    The present invention relates to a compound derived from 7-azaindole, soluble in polar organic solvents which, when generating an organogel, has an aggregation-induced emission (IEA) in the blue region of the visible spectrum (450-495 nm). Given these properties, this organogel can be applicable to optoelectronic devices or fluorescent sensors.
    STATE OF THE TECHNIQUE
    In recent years, there has been immense interest in the self-assembly of low molecular weight organogelifiers (LMOG). Its unique supramolecular organization allows a wide variety of possible applications. A huge amount of different organogelifiers has been described, possessing various functional groups such as amides, hydroxyls, ureas, carboxylic acids, peptides, sugars, cholesterol, chiral / aquirals long aliphatic chains (Chem. Rev. 2014, 114, 1973-2129), etc. These groups help the formation of organogels by generating non-covalent interactions, such as stacking -n-n, hydrogen bonds, hydrophobic interactions, Van der Waals, etc.
    On the other hand, great scientific efforts have been made in the development of a variety of n-conjugated systems oriented to the preparation of organogels, since these aromatic remains allow to modulate their physical properties. Organogels with charge transfer mobility, electrical conductivity and luminescence properties have been described for different applications, such as optoelectronic devices, fluorescence sensors, cell image formation and logic states, among others. Among all these applications, those focused on photonics have been the most widely studied, because the organogelification processing entails significant changes in the fluorescent emission. Most aggregate compounds have a common characteristic known as a decrease in emission due to "quenching caused by aggregation" (ACQ), this effect being destructive for practical applications.
    5
    10
    fifteen
    twenty
    25
    observed the opposite effect, known as “aggregation-induced emission” (AIE) or “aggregation-induced enhanced emission” (AIEE). In this case, potentially luminescent materials are nothing or hardly emitting in very dilute solutions, but they become highly emitting in concentrated solutions. The reasons for this phenomenon are due to restrictions on intramolecular rotations (IMR), the formation of aggregates, a strengthened planarity, the suppression of intramolecular charge transfer with torsion (TICT) or the existence of intramolecular proton transfer in excited state ( ESIPT).
    A huge variety of IEA molecules have been developed, with a great structural diversity: luminogens with classic IEAs such as siloles, tetraphenylene (TPE) and cyanoestilbene or non-classical derivatives such as 1,3,4-oxadiazole derivatives, carbazoles and dendritic systems (Zhao, Z .; Lam, JWY; Tang, BZ Soft Mat-ter 2013, 9, 4564). Several luminogens with AIE have been described that provide emissions over the entire range of visible light. More specifically, those luminescent materials that emit blue light are of great interest, since they are necessary for high-quality full-color screens and white lighting. Thus, solid blue emitters have been developed, effectively constructed with IEA generating remains (Huang, J .; Yang, X .; Wang, J .; Zhong, C .; Wang, L .; Qin, J .; Li , ZJ Mater. Chem. 2012, 22, 2478).
    DESCRIPTION OF THE INVENTION
    In a first aspect, the present invention relates to a compound of formula (I):
    image 1
    5
    10
    fifteen
    twenty
    25
    30
    where Y is selected from CH2, NH, C (O), S, S (O), NHC (O), (O) CNH and R1, R2 and R3 are independently selected from H or C1-C4 alkyl.
    The term "alkyl" refers, in the present invention, to aliphatic, linear or branched chains, having 1 to 4 carbon atoms, for example, methyl, ethyl, n-propyl, / -propyl, n-butyl, tert-butyl, sec-butyl, etc. Preferably the alkyl group has 1 or 2 carbon atoms.The alkyl groups may be optionally substituted by one or more substituents such as halogen, hydroxyl, azide, carboxylic acid or a substituted or non-substituted group. substituted, selected from amino, amido, carboxylic ester, ether, thiol, acylamino or carboxamide.
    In a preferred embodiment, Y is CH2.
    In a more preferred embodiment, R1 is a C1-C4 alkyl and even more preferably methyl.
    In another more preferred embodiment, R2 is H.
    In another more preferred embodiment, R3 is H.
    In another preferred embodiment, the compound of formula (I) has the following formula:
    image2
    Another aspect of the invention relates to the use of a compound of formula (I) for the manufacture of fluorescent materials.
    Another aspect of the invention relates to an organogel comprising at least one compound of formula (I) as described above.
    5
    10
    fifteen
    twenty
    25
    30
    Another aspect of the invention relates to a xerogel characterized in that it is the organogel described above dried.
    In the present invention, gels are understood as viscoelastic structures formed by a cross-linked three-dimensional network and a solvent, which is the major component; the solid appearance of the gel is the result of occlusion and adhesion of the liquid on the surface of the three-dimensional solid matrix; The formation of this matrix is the result of the cross-linking of polymeric fibers formed from the union of the molecules by physical or chemical interactions. It is understood as organogels if the solvent used is of an organic nature. Xerogel is understood as a solid formed from a gel that has undergone a drying process.
    The compound of formula (I) is soluble in polar organic solvents such as chloroform or dichloromethane, giving rise to homogeneous solutions at room temperature. However, it precipitates in apolar solvents such as cyclohexane at room temperature. By heating these solutions in apolar solvents and subsequently cooling, the formation of gel-like materials is induced; During the sun-gel phase, an IEA phenomenon is induced that causes the organogel to emit fluorescence in the blue spectrum.
    The batochromic displacement and the blue light emission of the organogel of the invention is presumably due to the self-association of 7-azaindole due to the existence of H bonds forming dimer. Therefore, the emission band of 450-495 nm can be attributed to the number 7-azaindole.
    In a solid state, the xerogel formed from the organogel of the compound of formula (I) exhibits a blue emission, so it could be used as a blue emitter in the solid state. Because of this, the gel of the present invention is useful for obtaining an emitting material for different applications such as optoelectronic devices, fluorescent sensors, bioimage, organic light emitting diode etc.
    Another aspect of the invention relates to a material comprising the gel formed from a compound of formula (I) as described above.
    5
    10
    fifteen
    twenty
    25
    30
    Another aspect of the invention relates to a device comprising the material described above.
    Another aspect of the invention relates to the use of the material comprising the gel formed from a compound of formula (I) for the manufacture of optoelectronic devices, fluorescent sensors, etc.
    Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and characteristics of the invention will be derived partly from the description and partly from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    BRIEF DESCRIPTION OF THE FIGURES
    FIG. 1. a) Image of the organogel obtained from compound 1 (3.5% w / w) in cyclohexane at room temperature and the "inverted tube" procedure b) SEM images of a dried gel of 1 in cyclohexane .
    FIG. 2. Microphotograph of polarized light of the xerogel of 1 in cyclohexane at room temperature.
    FIG. 3. Standardized absorption of 1 in 10 "5 M cyclohexane and of the xerogel obtained from gel of 1 in cyclohexane.
    FIG. 4. Emission spectrum of 1 (Aexc = 306 nm) in cyclohexane (10-5 M).
    FIG. 5. Emission spectrum of 1 in cyclohexane at different concentrations of the compound.
    FIG. 6. Fluorescence spectrum with variation of the temperature of compound 1 in cyclohexane (Aex = 306 nm) at 10 "2 M at 60 ° C 0 ° C.
    5
    10
    fifteen
    twenty
    25
    30
    35
    FIG. 7. Emission spectra of 1 in cyclohexane, the corresponding organogel formed in cyclohexane (3.5% w / w) at 0 ° C and in xerogel film.
    FIG. 8. 1H NMR spectrum spectrum of 1 in cyclohexane-d12 at 58 mM.
    FIG. 9. 1H NMR spectrum spectrum of 1 in cyclohexane-d12 at 9 mM.
    FIG. 10. Packaged crystallographic structure of compound 1.
    FIG. 11. Intermolecular interactions between two 7-azaindole molecules.
    EXAMPLES
    The invention will be illustrated below by tests carried out by the inventor, which demonstrates the effectiveness of the product of the invention.
    Example 1: synthesis of compound (1)
    Commercially available 5-bromo-7-azaindole served as a starting material for the preparation of 5- (4-nonylphenyl) -7-azaindole (1), by Suzuki coupling with 4- (nonyl) phenyl boronic acid, in presence of Pd (PPh3) 4 and aqueous K2CO3 (2 M), using toluene as solvent.
    A mixture of 5-bromo-7-azaindole (100 mg, 0.51 mmol), Pd (PPh3) 4 (66 mg, 0.057 mmol), 4-nonylbenzenboronic acid (130 mg, 0.52 mmol) was degassed. Then 0.5 ml of aqueous 2M K2CO3 and 4 ml of toluene were added. The mixture was heated at 130 ° C for 24 hours under N2 atmosphere. The yellow suspension was dissolved in CH2Cl2, washed with water, and dried with anhydrous MgSO4. The solvent was evaporated and the residue was chromatographed on silica gel (hexane: acetone, 4: 1) to give a white solid (1) (75 mg, 46%):
    1H NMR (300 MHz, acetone-d6) 5 10.64 (s, 1H), 8.45 (s, 1H), 8.10 (s, 1H), 7.57-7.54 (m, 2H), 7.46-7.44 (dd, J = 3.5 , J = 2.4, 1H), 7.28-7.26 (m, 2H), 6.49-6.47 (dd, J = 3.5, J = 2.4, 1H), 2.62 (t, J = 7.5, 2H), 1.65-1.60 (m , 2H), 1.31-1.24 (m, 12H), 0.83 (t, J = 6.6, 3H); 13C NMR (50 MHz, Acetone-da) 5 148.9, 142.5, 142.5, 141.9, 137.6, 129.7,
    5
    10
    fifteen
    twenty
    25
    30
    127.4, 126.7, 126.5, 120.5, 100.9, 35.7, 32.2, 31.9, 29.6, 29.3, 22.9, 13.9; UV-vis (CH2Cl2, 25 ° C) Amax (£) 250 (125370); FAB MS m / z 321.2 (M + H) +; HRMS (FAB) calculated for C22H29N2: 321.2331, found: 321.2338.
    Example 2: synthesis and study of the properties of the organogel based on the compound (1)
    To obtain the organogel based on the compound (1), the powder of this compound (3.5% w / w) was dissolved in cyclohexane, used as a nonpolar solvent, with heating, forming non-fluid gel-like materials after cooling. . In addition, this organogel of 1 is opaque and white, in which the sol-gel interconversion cycle was tested by the "tube inversion" procedure (Figure 1a).
    To obtain a visual understanding of the aggregation, the morphology of the dried gel (xerogel) was examined microscopically by polarized optical microscopy (POM) (Figure 2) and field emission scanning electron microscopy (FE-SEM) (Figure 1b). The xerogel of 1, prepared by slow evaporation of cyclohexane in the gel state, was not homogenous, with long fibers within the films easily found, with a small birefringence between the cross polarizers (Figure 2). In the SEM analysis, the gel was transferred onto a silicon substrate and the solvent was evaporated again slowly to give a xerogel.
    The spectroscopic characterizations of 1 were studied both in solution and in solid state (Figure 3). The electronic absorption spectrum of 1 in cyclohexane showed an absorption band centered at 248 nm and a shoulder at 303 nm (10-5 M). The absorption band of the xerogel 1 in film on quartz slides showed two absorption bands at 264 and 309 nm, with a noticeably wider band absorption spectrum compared to the state in solution. The absorption spectrum of the xerogel's pinch state is more batocromically displaced from that in a state of dissolution, presumably due to the increased intermolecular interactions between neighboring molecules in the solid state.
    The fluorescence spectrum of 1 in cyclohexane solution (10-5 M) showed a single band, with a maximum at 349 nm (Aexc = 306 nm) (quantum efficiency 0.56 in
    5
    10
    fifteen
    twenty
    25
    30
    cyclohexane, using quinine sulfate (QS) in 0.1 N H2SO4 as reference (Figure 4). However, when the concentration of 1 in cyclohexane was increased to 10 mM, fluorescence was removed (Figure 5). Interestingly, when said 10 mM solution was brought to lower temperatures, gradually from 60 to 0 ° C, studying the intensity of fluorescence every 5 ° C, there was an increase in the fluorescent response gradually by 484 nm, as it goes forming the gel state (Figure 6). Therefore, it is conjectured that the process of gelation and formation of supramolecular organogels induced an aggregation-induced emission phenomenon (IEA). Said IEA behavior was found during the transition from sun to gel phase.
    On the other hand, the emission spectrum of the xerogel of 1, obtained from the gel state in cyclohexane, also exhibits a considerable batochromic displacement compared to the dilute solution in cyclohexane. The xerogel of 1 exposes two broad emission bands at 378 and 460 nm (Figure 7). The xerogel of 1 also emits a blue fluorescence in its films in a solid state. This data is remarkable considering that the majority of luminous materials are used as solid films for their practical applications. Therefore, the xerogel of 1 could be used for the construction of solid blue emitters.
    For a better understanding of the fluorescent and self-assembly properties, different concentration dependence experiments were performed on 1 H NMR, using cyclohexane-d12 as deuterated solvent (see Figures 8 and 9).
    The 1H NMR experiments show that the self-association of these organogelling agents does not occur by means of -n-n interactions, since no displacement of the aromatic signals was observed, demonstrating that if they exist, they are very weak -n-n interactions. However, it was found that the protons corresponding to pyrrolic NH show a huge down-field displacement (12.6-13.3 ppm) after increasing the concentration from 1 from 9 to 58 mM, indicating that the hydrogen bond has an influence remarkable helping the formation of the organogelificante 1.
    All these discoveries are supported by the resolution of the crystalline structure of 1 in cyclohexane (see Tables 1, 2, Figure 10). Colorless crystals of 1, suitable for single crystal X-ray analysis, were obtained from slow evaporation in cyclohexane. The X-ray analysis indicates that the species 1 5 crystallizes in the tricllnic space group P-1.
    Table 1. Data of crystal 1
     Chemical formula  C22H28N2
     Molecular weight  320.46
     Temperature  296 (2) K
     Wavelength  0.71073 A
     Crystal size  0.07 x 0.08 x 0.18 mm
     Crystal habit  Clear colorless prismatic
     Crystalline system  tricllnic
     Space group  P-1
     Unit cell dimensions  a = 8.7383 (10) A a = 85.653 (6) °
     b = 10,2006 (10) A 3 = 87,290 (6) °
     c = 10.7289 (12) A v = 78.985 (6) °
     Volume  935.49 (18) A3
     Z  2
     Density (calculated)  1,138 Mg / cm3
     Absorption coefficient  0.066 mm-1
     F (000)  348
    10
    Table 2. Structure 1 refinement data
     Theta range for collected data  1.90 to 25.44 °
     Hkl Index Ranges  -10 <= h <= 10, -12 <= k <= 12, - 12 <= l <= 12
     Reflections collected  14649
     Independent reflections  3444 [R (int) = 0.0291]
     Coverage of independent reflections  99.1%
     Absorption correction  multi-scan
     Transmission coefficient max. and min.  0.9954 and 0.9882
     Structure Resolution Technique  Direct methods
     Program for the resolution of the structure  SHELXS-97 (Sheldrick, 2008)
     Refinement Method  Full-matrix least-squares on F2
     Refinement program  SHELXL-97 (Sheldrick, 2008)
     Minimized function  I w (Fo2 - Fc2) 2
     Data / Restrictions / Parameters  3444/0/236
    5
    10
    fifteen
    twenty
    25
     Goodness of fit in F2  1,037
     Max wing  0.001
     Final R indices  2496 data; I> 2nd (I) R1 = 0.0782, wR2 = 0.2612
     Weighing scheme  w = 1 / [o2 (Fo2) + (0.1989P) 2 + 0.2937P] P = (Fo2 + 2Fc2) / 3
     Positive and negative peaks of greater magnitude  0.420 and -0.258 eA-3
     Greater deviation R.M.S  0.093 eA-3
    The monocrystalline structure of 1 revealed the planarity of the 7-azaindole nucleus and a fairly important intermolecular interaction between two adjacent ones, where the azaindole derivative offers a coordination site (N atom of the pyridyl moiety), as well as a donor binding unit of H (NH group of the 5-member ring). The intermolecular hydrogen bond N pyrrolic-H --- N pyridlnic, with a distance of 2,092 A, plays a significant role in the crystalline packing, effectively forming a dimer through N-H --- N by two hydrogen bonds. Although it cannot be assured that the same interactions are present in the gel, it is reasonable to assume that the fluorescence of the bromochromic displacement could be due to the formation of these aggregates bound by hydrogen, forming a self-assembled supramolecular gel.
    The bulky phenyl spacers are rotated 35.3 ° with respect to the 7- azaindole ring. Intramolecular rotation is restricted by the interaction of the long phenylalkyl chains of another azaindole (see Figure 11). Therefore, as mentioned above, the presence of long alkyl chains has been considered essential to stabilize the assemblies of 1. The inhibition of intramolecular rotation helps the stability of the molecule and the formation of the gel state.
    In summary, new low molecular weight organic gelling agents with IEA capacity have been found. Self-assembly of the 5- (4-nonylphenyl) -7-azaindole (1) molecule in cyclohexane provides a soft supramolecular material. The compound 1 in concentrated solution at room temperature is not luminescent, but when the organogel is formed by reducing said temperature, it emits a strong emission of blue fluorescence with a batochromic shift with respect to the diluted solution, showing a typical AIE characteristic. The bromochromic displacement and the blue light emission of the organogel at 484 nm are presumably due to the
    self-association of 7-azaindole platforms by H bonds, providing dimeros. The monocrystalline X-ray analysis demonstrates the cooperation between two azaindole units through the intermolecular hydrogen bond, forming an effective dimer.
    5
    权利要求:
    Claims (12)
    [1]
    5
    10
    fifteen
    twenty
    1. Compound of formula (I):
    image 1
    [2]
    2. Compound according to claim 1, wherein Y is CH2.
    [3]
    3. Compound according to the preceding claim, wherein R1 is a C1-C4 alkyl.
    [4]
    4. Compound according to the preceding claim, wherein R1 is methyl.
    [5]
    5. Compound according to any of the preceding claims, wherein R2 is H.
    [6]
    6. Compound according to any of the preceding claims, wherein R3 is H.
    [7]
    7. Compound according to any of the preceding claims having the following formula:
    image2
    10
    [8]
    8. Use of a compound of formula (I) for the manufacture of fluorescent materials.
    [9]
    9. Organogel comprising at least one compound of formula (I) according to any one of claims 1 to 7, characterized in that it emits fluorescence at a wavelength between 450 and 495 nm.
    [10]
    10. Xerogel characterized in that it is the organogel according to claim 9 desiccated.
    [11]
    11. Device comprising the xerogel according to claim 10.
    [12]
    12. Use of the xerogel according to claim 10 for the manufacture of optoelectronic devices, fluorescent sensors, bioimage, organic light emitting diode.
    类似技术:
    公开号 | 公开日 | 专利标题
    Wakamiya et al.2013|Benzene-fused BODIPY and fully-fused BODIPY dimer: impacts of the ring-fusing at the b bond in the BODIPY skeleton
    Liu et al.2018|Synthesis and remarkable mechano-and thermo-hypsochromic luminescence of a new type of DPP-based derivative
    Wang et al.2017|Introductory lecture: recent research progress on aggregation-induced emission
    Kamino et al.2013|A red-emissive aminobenzopyrano-xanthene dye: elucidation of fluorescence emission mechanisms in solution and in the aggregate state
    Huang et al.2014|A novel pyrene-containing fluorescent organogel derived from a quinoline-based fluorescent porbe: synthesis, sensing properties, and its aggregation behavior
    Zhu et al.2016|Novel perylene liquid crystals: investigation of the influence of bay-substituents on mesomorphism and photophysical property
    Ying et al.2017|Unusual mechanohypsochromic luminescence and unique bidirectional thermofluorochromism of long-alkylated simple DPP dyes
    Pang et al.2016|Tunable multicolor emissions in a monocomponent gel system by varying the solvent, temperature and fluoride anion
    Wang et al.2019|Multi-stimuli responsive supramolecular gels based on a D–π–A structural cyanostilbene derivative with aggregation induced emission properties
    JP2016534190A|2016-11-04|Light collection array
    Rananaware et al.2015|Solvophobic control aggregation-induced emission of tetraphenylethene-substituted naphthalene diimide via intramolecular charge transfer
    ES2583138B1|2017-06-23|ORGANOGEL BASED ON 5- | -7-SELF-ASSEMBLED AZAINDOLS
    ES2600305B1|2017-11-24|ORGANOGEL BASED ON MOLECULES DERIVED FROM 7,7&#39;-DIAZAISOINDIGO
    ES2625021B1|2018-05-03|DERIVATIVE COMPOUNDS 7,7`-DIAZAISOINDIGO AND ITS USES
    Liu et al.2017|Construction and function of a highly efficient supramolecular luminescent system
    Wu et al.2020|Solid-state photochromism and acidochromism multifunctional materials constructed by tetraphenylethene and spiropyran
    Yang et al.2011|Synthesis, X-ray crystal structure and optical properties of novel 2, 5-diaryl-1, 3, 4-oxadiazole derivatives containing substituted pyrazolo [1, 5-a] pyridine units
    Wu et al.2021|A chiral single-component sol–gel platform with highly integrated optical properties
    Liu et al.2017|Sensitive mechanofluorochromism based on conversion of paired and unpaired enantiomer packing modes
    Dai et al.2019|A stabilized lamellar liquid crystalline phase with aggregation-induced emission features based on pyrrolopyrrole derivatives
    Gao et al.2019|Red-emitting dyes based on phenothiazine-modified 2-hydroxychalcone analogues: mechanofluorochromism and gelation-induced emission enhancement
    Camerel et al.2011|Liquid-crystalline functional carbazole and naphthalene platforms
    Chen et al.2021|A pyridinium salt with crystalline phase transformation under water vapor and reversible mechanochromic luminescent properties
    Huang et al.2020|Synthesis, self-assembly and nonlinear optical activity of selenium-annulated perylene diimide
    Hu et al.2019|Multi-stimuli responsive properties switch by intra-and inter-molecular charge transfer constructed from triphenylamine derivative
    同族专利:
    公开号 | 公开日
    ES2583138B1|2017-06-23|
    WO2016132006A1|2016-08-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN102464978B|2010-11-17|2014-06-11|海洋王照明科技股份有限公司|Conductive cavity-type blue electroluminescent material and preparation method and application thereof|ES2600305B1|2015-07-06|2017-11-24|Consejo Superior De Investigaciones Científicas |ORGANOGEL BASED ON MOLECULES DERIVED FROM 7,7'-DIAZAISOINDIGO|
    法律状态:
    2017-06-23| FG2A| Definitive protection|Ref document number: 2583138 Country of ref document: ES Kind code of ref document: B1 Effective date: 20170623 |
    2017-11-30| FA2A| Application withdrawn|Effective date: 20171124 |
    优先权:
    申请号 | 申请日 | 专利标题
    ES201530187A|ES2583138B1|2015-02-17|2015-02-17|ORGANOGEL BASED ON 5--7-SELF-ASSEMBLED AZAINDOLS|ES201530187A| ES2583138B1|2015-02-17|2015-02-17|ORGANOGEL BASED ON 5--7-SELF-ASSEMBLED AZAINDOLS|
    PCT/ES2016/070094| WO2016132006A1|2015-02-17|2016-02-17|Organogel based on self-assembled 5--7-azaindoles|
    [返回顶部]