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    • 专利摘要:
    Organogel based on molecules derived from 7,7'-diazaisoindigo. The present invention relates to a compound derived from 7,7'-diazaisoindigo, to an organogel formed by these compounds that presents an emission induced by aggregation (aie) in the red region of the visible spectrum (600-800 nm) and a xerogel obtained by drying 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:ES2600305A1
    申请号:ES201530966
    申请日:2015-07-06
    公开日:2017-02-08
    发明作者:Eva Maria GARCIA FRUTOS
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

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    Organogel based on molecules derived from 7.7’-diazaisoindiqo
    DESCRIPTION
    The present invention relates to a compound derived from 7,7'-diazaisolndigo soluble in polar organic solvents which, when generating an organogel, exhibits an aggregation-induced emission (IEA) in the red region of the visible spectrum (600-800 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 n-n stacks, 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 aggregates have a common characteristic known as a decrease in emission due to "quenching caused by aggregation" (ACQ), this effect being destructive to
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    Practical applications. The opposite effect has also been observed, 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 in intramolecular rotations (IMR), formation of aggregates, a strengthened planarity, 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 cyanoestylbeno derivatives or non-classical derivatives such as 1,3,4-oxadiazole derivatives, carbazoles and dendritic systems (Zhao, Z .; Lam, JWY; Tang, BZ Soft Mater. 2013, 9, 4564).
    Document ES201530187 describes a series of 7-azaisoindole derivatives capable of self-assembling to give rise to organogels and xerogels with important fluorescent properties.
    DESCRIPTION OF THE INVENTION
    In a first aspect, the present invention relates to a compound of formula
    (I):
    image 1
    N

    image2
    where Y is selected from CH2, O, NH, C (O), S, S (O), NHC (O), (O) CNH and R1, is a C1-C12 alkyl.
    The term "alkyl" refers, in the present invention, to aliphatic, linear or branched chains, having 1 to 12 carbon atoms, for example, methyl, ethyl, n-propyl, / -propyl, n-butyl , tert-butyl, sec-butyl, pentyl, dodecyl, etc. Preferably the alkyl group has 3 to 11 carbon atoms.The alkyl groups may be optionally substituted by one or more substituents such as halogen, hydroxyl, azide, acid carboxylic or a substituted or unsubstituted group, selected from amino, amido, carboxylic ester, ether, thiol, acylamino or carboxamido.
    In a preferred embodiment, Y is CH2.
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    In a more preferred embodiment, R1 is a C3-C11 alkyl and even more preferably heptyl.
    In another preferred embodiment, the compound of formula (I) has the following formula:
    C8H17
    image3
    Another aspect of the invention relates to the use of a compound of formula (I) for the manufacture of fluorescent materials.
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    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 sol to gel phase, an IEA phenomenon is induced that causes the organogel to emit fluorescence in the red spectrum. The bromochromic displacement and the red emission of the organogel of the invention is presumably due to the auto-association of 7,7’-diazaisolndigo.
    In a solid state, the xerogel formed from the organogel of the compound of formula (I) exhibits an emission in red, so it could be used as a solid emitting red emitter. 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.
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    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 (2.75% 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. Absorption 1 in cyclohexane 2 x 10 "5 M.
    FIG. 3. Emission spectrum of 1 (Aexc = 328 nm) in cyclohexane, the continuous line is (2x10-4 M), the broken line is the gel at 4.6x10 "2M in cyclohexane
    FIG. 4. Emission spectrum of the gel state and in the sun state of 1 at different temperatures in cyclohexane.
    FIG. 5. Optical microphotograph of the crystals obtained by hot acetone cooling.
    FIG. 6. Packaged crystallographic structure of compound 1 FIG. 7. 1H NMR spectrum spectrum of 1 in CDCl3.
    FIG. 8. 13C NMR spectrum spectrum of 1 in CDCl3.
    EXAMPLES
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    The invention will be illustrated below by tests that show the effectiveness of the product of the invention.
    Example 1: synthesis of compound (1)
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    The synthesis of N-dioctyl 7,7'-diazaisoindigo (1, Scheme 1) has been carried out by alkylating 7,7'-diazaisoindigo by means of 1-iodooctane in the presence of K2CO3 and DMF at 100 ° C for 16 h.
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    H
    image4
    1-lodooctane
    K2CO3 DMF 100 ° C
    Hi7C8
    image5
    Scheme 1
    A mixture of 7,7'-diazaisoindigo (25 mg, 0.09 mmol), 1-iodooctane (0.04 ml, 0.21 20 mmol) and K2CO3 (39.2 mg, 0.28 mmol) in 2 ml DMF was heated at 100 ° C for 16 hours. The red solution 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, 5: 1) to give a red solid (1) (30 mg, 65%):
    25 (E) -1,1'-dioctyl- [3,3'-bipyrrolo [2,3-fc] pyridinylidene] -2,2 '(1H, 1'H) -dione (1): 1H
    NMR (200 MHz, CDCl3) 59.46 (d, J = 8Hz, 2H), 8.24 (d, J = 8Hz, 2H), 7.02 (dd, J = 8Hz, 2H), 3.90 (t, J = 7.5Hz, 4H ), 1.76 (m, 4H), 1.24 (m, 20H), 0.87 (t, J = 6.5Hz, 6H); 13C NMR (50 MHz, CDC ^) 5 167.6, 157.7, 150.2, 137.5, 132.3, 118.4, 116.1, 39.4, 31.8, 29.2, 29.2, 27.8, 27.0, 22.6, 14.1; UV-vis (CH3Cl2, 25 ° C) ^ max (s) 283
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    (30690), 327 (12034), 477 (5069); MALDI-TOF MS m / z 489 (M +); HRMS (MALDI-TOF) calculated for C30H40N4O2: 489.3224, found: 489.3240.
    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 (2.75% 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 red in color, 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 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 homogeneous, with long fibers within the films easily found therein (Figure 1b). 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. The electronic absorption spectrum of 1 in cyclohexane showed three absorption bands at 280, 327, 470 nm (10-5 M) (Figure 2). The absorption band of the xerogel 1 in film on quartz slides showed three absorption bands at 287,329 and 507 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 solution of cyclohexane (2x10-4 M) showed two bands, with a maximum at 392 and 618 nm (Aexc = 328 nm). However, compound 1 at 4.6x10-2 M in cyclohexane forms an organogel, which emits in the
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    region of the red with a batocromic displacement with respect to the diluted solution, which shows a typical AIE characteristic. (Figure 3). However, when this organogel in cyclohexane warms up, it is observed how the emission that it had in the gel state is eliminated, observing that in the sun state it is almost not fluorescent (Figure 4). The transition from the gel-sun state is between 40-45 ° C.
    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 an emission band at about 610 nm (Aexc = 470 nm) approximately. The xerogel of 1 also emits a fluorescence in the red zone 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 fluorescent sensors.
    For a better understanding of the fluorescent properties and the interactions, different experiments of dependence of the concentration on 1 H NMR were carried out, using cyclohexane-d12 as deuterated solvent, where it is demonstrated that the formation of the organogelifiers occurs through very interactions weak nn type, since a slight displacement of the aromatic signals was observed.
    X-ray diffraction (DRX) has great potential to elucidate the molecular structure of the organogels and can provide information on the assembly of the molecules in the gel phase. The XRD of the cyclohexane xerogel (2.75% by weight), has four reflections, three of them in the low angle region at 18.01, 9.00 and 6.00, with a laminar packing ratio corresponding to the planes (001), (002), and (003).
    On the other hand, the crystalline structure of 1 in acetone / dichloromethane was resolved (Table 1, Table 2, Figures 4, 5 and 6). Reddish crystals of 1, suitable, were obtained
    for monocrystalline X-ray analysis, from slow evaporation in acetone / dichloromethane. X-ray analysis indicates that species 1 crystallizes in the monochromic spatial group P21 / c
    Table 1. Data of crystal 1
     Chemical formula  C30H40N4O2
     Molecular weight  488.66
     Temperature  296 (2) K
     Wavelength  0.71073 A
     Crystal size  0.04 x 0.18 x 0.24 mm
     Crystal habit  Clear red plate
     Crystalline system  monoclmic
     Space group  P2i / c
     a = 18.7376 (11) A  a = 90 °
     b = 4.8671 (3) A  3 = 106,762 (2) °
     Unit cell dimensions  a = 18.7376 (11) A a = 90 °
     b = 4.8671 (3) A 3 = 106.762 (2) °
     c = 15.8639 (8) A y = 90 °
     Volume  1385.28 (14) A3
     Z  2
     Density (calculated)  1,172 Mg / cm3
     Absorption coefficient  0.074 mm-1
     F (000)  528
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    Table 2. Structure 1 refinement data
     Theta range for collected data  2.27 at 25.35 °
     Hkl Index Ranges  -22 <= h <= 17, -5 <= k <= 5, -18 <= l <= 18
     Reflections collected  14003
     Independent reflections  2493 [R (int) = 0.0506]
     Coverage of independent reflections  98.7%
     Absorption correction  multi-scan
     Transmission coefficient max. and min.  0.9970 and 0.9824
     Structure resolution technique  Direct methods
     Program for the resolution of the structure  SHELXS-97 (Sheldrick, 2008)
     Refinement Method  Matrix method of square millimeters on F2
     Refinement program  SHELXL-97 (Sheldrick, 2008)
     Minimized function  I w (Fo2 - Fc2) 2
     Data / Restrictions / Parameters  2493/0/165
     Goodness of fit in F2  1,056
     Max wing  0.001
     Final R indices  1569 data; I> 2nd (I) R1 = 0.0564, wR2 = 0.1270 All data R1 = 0.1045, wR2 = 0.1618
     Weighing scheme  w = 1 / [o2 (Fo2) + (0.0925P) 2 + 0.0000P] where P = (Fo2 + 2Fc2) / 3
     Positive and negative peaks of greater magnitude  0.392 and -0.337 eA-3
     Greater deviation R.M.S  0.147 eA-3
    The monocrystalline structure of 1 revealed the planarity of the nucleus and a fairly important intermolecular interaction between adjacent platforms. The crystals of compound 1 formed crystals in the form of very thin fibers. Compound 1 crystallizes in the spatial group P21 / c monocllnica. Only one half of the molecule in the asymmetric unit, with an investment center that is located in the center. The central ring is completely flat, the coupling of the molecules in the crystal is achieved through n-n interactions that give rise to columns of 10 stairs parallel to the direction b, where the adjacent molecules are located at 3,335 A distance, with a slip angle of 43.28 °. The slip angle is calculated as the angle between the long axis of a molecule, and the line of centers of adjacent molecules in the column. The packing of the columns in the glass showed that the neighboring columns lean in the same direction of the angle, while the nuclei of molecules in columns
    Adjacent in the c direction show an almost perpendicular angle 86.52 °.
    权利要求:
    Claims (8)
    [1]
    1. Compound of formula (I):
    image 1
    5 o
    where Y is selected from CH2, O, NH, C (O), S, S (O), NHC (O), (O) CNH and R1, is a C1-C12 alkyl.
    10 2. Compound according to claim 1, wherein Y is CH2.
    [3]
    3. Compound according to the preceding claim, wherein R1 is a C3-C11 alkyl.
    [4]
    4. Compound according to the preceding claim, wherein R1 is heptyl
    [5]
    5. Compound according to any of the preceding claims having the following formula:
    C8H17
    image2
    [6]
    6. Use of a compound of formula (I) for the manufacture of fluorescent materials.
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    [7]
    7. Organogel comprising at least one compound of formula (I) according to any one of claims 1 to 5, characterized in that it emits fluorescence at a wavelength between 600 and 800 nm.
    10 8. Xerogel characterized in that it is the organogel according to claim 7
    dried.
    [9]
    9. Device comprising the xerogel according to claim 8.
    15 10. Use of the xerogel according to claim 8 for the manufacture of devices
    Optoelectronics
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    [11]
    11. Use of the xerogel according to claim 8 for the manufacture of fluorescent sensors.
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    同族专利:
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    WO2017005956A1|2017-01-12|
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    引用文献:
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    ES2583138B1|2015-02-17|2017-06-23|Consejo Superior De Investigaciones Científicas |ORGANOGEL BASED ON 5- -7-SELF-ASSEMBLED AZAINDOLS|
    ES2625021B1|2015-12-18|2018-05-03|Consejo Superior De Investigaciones Científicas |DERIVATIVE COMPOUNDS 7,7`-DIAZAISOINDIGO AND ITS USES|ES2718418B2|2017-12-29|2019-10-31|Consejo Superior Investigacion|DERIVATIVES OF 7,7'-DIAZAINDIGO AND ITS USES|
    CN110828670B|2019-11-28|2021-03-30|华南理工大学|Multiplication type organic photoelectric detector based on AIE material and preparation method|
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    ES201530966A|ES2600305B1|2015-07-06|2015-07-06|ORGANOGEL BASED ON MOLECULES DERIVED FROM 7,7'-DIAZAISOINDIGO|ES201530966A| ES2600305B1|2015-07-06|2015-07-06|ORGANOGEL BASED ON MOLECULES DERIVED FROM 7,7'-DIAZAISOINDIGO|
    JP2018500728A| JP2018527313A|2015-07-06|2016-07-06|Organogels based on molecules derived from 7,7'-diazaisoindigo|
    EP16820892.4A| EP3330268A4|2015-07-06|2016-07-06|Organogel based on molecules derived from 7,7'-diazaisoindigo|
    KR1020187003544A| KR20180037963A|2015-07-06|2016-07-06|A molecular-based organogel derived from 7,7 ' -diazaisobindigo|
    PCT/ES2016/070504| WO2017005956A1|2015-07-06|2016-07-06|Organogel based on molecules derived from 7,7'-diazaisoindigo|
    US15/741,441| US20190233410A1|2015-07-06|2016-07-06|Organogel based on molecules derived from 7,7'-diazaisoindigo|
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