• 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:
    Derivatives of 7,7'-diazaindigo and its uses. The present invention relates to new 7,7'-diazaindigo derivatives of formula I wherein the groups R1 to R6 have the meaning described in the description. The invention also relates to the use of these derivatives as components for the manufacture of organic electronic semiconductor devices. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2718418A1
    申请号:ES201731501
    申请日:2017-12-29
    公开日:2019-07-01
    发明作者:Frutos Eva Maria Garcia
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

    [0001]
    [0002] 7.7’-diaza¡nd¡qo derivatives and their uses
    [0003]
    [0004] The present invention relates to new 7,7'-diazandigo derivatives and their use as components for the manufacture of organic electronic semiconductor devices.
    [0005]
    [0006] BACKGROUND OF THE INVENTION
    [0007]
    [0008] For several years the development of semiconductor organic materials has grown exponentially as an interesting alternative to the inorganic materials used so far, such as silicon, for application in electronic devices such as transistors (OFETs), light emitting diodes (OLEDs) or solar cells (OSCs).
    [0009]
    [0010] In recent years, organic semiconductors have acquired great relevance for their application in different electronic devices.
    [0011]
    [0012] The objective of organic devices, both scientific and industrial, is to replace conventional silicon technology with new organic materials, with flexible mechanics, emitting nature, resistance, processability, low cost and one of its great advantages, molecular design. Organic electronics offer the possibility of modulating the properties of the compounds by chemical synthesis by adding substituents and can favor certain chemical, electronic, optical and mechanical characteristics.
    [0013]
    [0014] The organic materials used in the different electronic devices can be classified into high molecular weight materials (polymers / oligomers) and small molecules.
    [0015]
    [0016] Within the chemical units that can form small molecule materials there are units of type n (deficient of electrons) and of type p (rich in electrons).
    [0017] One of the groups of compounds of small n-type molecules recently investigated, are molecules with amide / imide functionality, as electron acceptor units for use in electronic devices since they have excellent stability and molecular design. Within this group, isoindigo molecules are being studied for use in this type of applications as an acceptor unit, due to their high planarity, crystallinity, modulation and easy obtaining of natural sources, first described in 2010. Without However, modifications in the core of the isoindigo structure have been poorly described in the literature, such as 7-azaisoindigo or 7,7'-diazaisoindigo (see for example Eva M. García Frutos et al, WO2017103318, WO2017005956 and J. Mater Chem. C, 2013,1, 3633-3645, J. Phys. Chem. C, 2017, 121 (48), 27071-27081) which have an almost-planar structure, improving the lifetime of fluorescence of the isoindigo platform that does not present emission and also increasing the possible mobility of cargo between platform and platform due to its high planarity.
    [0018]
    [0019] On the other hand, indigoid dyes represent an interesting class of semiconductor materials. Indigoids are among the few known chromophores of natural, blue color. Indigo and 6,6'-dibromoindigo (Tyria purple) have been exploited for thousands of years as valuable dyes. However, it has been found that vacuum evaporated indigo films show a high order with monocrystalline texture and exceptionally high dielectric constants (in the range of 5-6). These properties translate into high carrier mobility in indigo and Tyria purple, although there have been very few variations or modifications of the central unit to date.
    [0020]
    [0021] Therefore, it would be desirable to have other compounds alternative to the above that have improved properties for use as organic semiconductor devices.
    [0022]
    [0023] DESCRIPTION OF THE INVENTION
    [0024]
    [0025] In a first aspect, the present invention relates to a compound of formula I:
    [0026]
    [0027]
    [0028] where:
    [0029] each R1 and R2 independently represent H or halogen;
    [0030] each R3 and R4 independently represents H or C1-C25 alkyl where C1-C25 alkyl may be optionally substituted by one or more halogen, hydroxyl, azide, carboxylic acid, amino, amido, carboxylic ester, ether, thiol, acylamino or carboxamide groups; each R5 and R6 independently represents O, C (CN) 2, C (CN) (COOR7), or C (CN) (CONR7R8); Y
    [0031] each R7 and R8 independently represents H or C1-C4 alkyl,
    [0032] with the proviso that at least one R3 or R4 group is different from H.
    [0033]
    [0034] In another embodiment the invention relates to a compound of formula I wherein each R5 and R6 independently represents O.
    [0035]
    [0036] In another embodiment the invention relates to a compound of formula I wherein R5 and R6 represent O.
    [0037]
    [0038] In another embodiment the invention relates to a compound of formula I wherein each R7 and / or R8 represents H or CH3, and preferably H.
    [0039]
    [0040] In another embodiment the invention relates to a compound of formula I wherein each R3 and R4 independently represents H or C1-C25 alkyl, where C1-C25 alkyl may be optionally substituted by one or more halogen or hydroxyl groups.
    [0041]
    [0042] In another embodiment the invention relates to a compound of formula I wherein each R3 and R4 independently represents H or C1-C25 alkyl.
    [0043]
    [0044] In another embodiment the invention relates to a compound of formula I wherein each R1 and R2 independently represent H, F, Cl or Br, and more preferably H.
    [0045] In another embodiment the invention relates to a compound of formula I wherein R3 represents C1-C16 alkyl, preferably C1-C12 alkyl, more preferably C3-C12 alkyl, more preferably C3-C9 alkyl, and more preferably C8 alkyl.
    [0046]
    [0047] In another embodiment the invention relates to a compound of formula I wherein R4 represents H.
    [0048]
    [0049] In another embodiment the invention relates to a compound of formula I wherein: each R1 and R2 independently represent H, F, Cl or Br, preferably H;
    [0050] R3 C1-C25 alkyl, where C1-C25 alkyl may be optionally substituted by one or more halogen, hydroxyl, azide, carboxylic acid, amino, amido, carboxylic ester, ether, thiol, acylamino or carboxamido groups;
    [0051] R4 represents H; Y
    [0052] R5 and R6 represent O.
    [0053]
    [0054] In another embodiment the invention relates to a compound of formula I wherein: each R1 and R2 independently represent H, F, Cl or Br, preferably H;
    [0055] R3 represents C1-C16 alkyl, preferably C1-C12 alkyl, more preferably C3-C12 alkyl, more preferably C3-C9 alkyl, and more preferably C8 alkyl; R4 represents H; Y
    [0056] where R5 and R6 represent O.
    [0057]
    [0058] In another embodiment the invention relates to a compound of formula I wherein the compound of formula I is the compound W-octyl-7,7'-diazaindigo, of formula 1:
    [0059]
    [0060]
    [0061]
    [0062]
    [0063] The term "C1-C25 alkyl" refers, in the present invention, to aliphatic chains, linear or branched, having 1 to 25 carbon atoms, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tere-butyl, sec-butyl, pentyl, dodecyl, etc. Preferably the alkyl group has 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 3 to 12 carbon atoms, more preferably 3 to 9 carbon atoms, and even more preferably 8 carbon atoms carbon.
    [0064]
    [0065] The term "halogen" refers, in the present invention, to a chlorine, bromine, fluorine or iodine atom, preferably it is bromine.
    [0066]
    [0067] The compounds of the present invention represented by formula I may include isomers, including optical isomers or enantiomers, depending on the presence of chiral centers. The individual isomers, enantiomers or diastereoisomers and mixtures thereof fall within the scope of the present invention. The individual enantiomers or diastereoisomers, as well as mixtures thereof, can be separated by conventional techniques. Preferably the isomers are trans (E) enantiomers.
    [0068]
    [0069] Another aspect of the invention relates to the use of a compound of formula I, described in the present invention, for the manufacture of organic semiconductor materials.
    [0070]
    [0071] Another aspect of the invention relates to a material comprising a compound of formula I as described in the present invention.
    [0072]
    [0073] Another aspect of the invention relates to a device comprising the material defined above.
    [0074]
    [0075] Another aspect of the present invention relates to the use of the device as defined above as an organic electronic semiconductor, and preferably as an organic photovoltaic cell.
    [0076]
    [0077] 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 features 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.
    [0078]
    [0079] BRIEF DESCRIPTION OF THE FIGURES
    [0080]
    [0081] FIG. 1. Shows the absorption spectrum of the compound of formula 1 in dichloromethane at a concentration of 1.5 x 10-5 M.
    [0082]
    [0083] FIG. 2. Shows the absorption spectrum of the compound of formula 2 in dichloromethane at a concentration of 2.9 x 10-5 M.
    [0084]
    [0085] EXAMPLES
    [0086]
    [0087] The invention will now be illustrated by tests carried out by the inventors, which demonstrates the effectiveness of the product of the invention.
    [0088]
    [0089] Example 1: Procedure for obtaining compound 1
    [0090] The synthesis of W-octyl-7,7'-diazaindigo (1, Scheme 1) has been carried out by alkylation of 7,7'-diazaindigo by 1-iodooctane in the presence of K2CO3 and DMF dried at 100 ° C for 2 h.
    [0091]
    [0092]
    [0093]
    [0094]
    [0095] Scheme 1
    [0096] A mixture of 7,7'-diazaindigo (36 mg, 0.15 mmol), 1-iodooctane (0.07 ml) and K2CO3 (42 mg, 0.31 mmol) in 4 ml of DMF was heated to 100 ° C for 2 hours The blue solution was dissolved in CH2Cl2, washed with water, and the organic phase was dried with anhydrous MgSO4. The solvent was evaporated and the residue was chromatographed on gel. silica (hexane: acetone, 3: 1) to give a blue solid (1) (20 mg, 37%):
    [0097]
    [0098] (E) -1-octyl- [2,2, -bipyrrolo [2,3-b] pyridinylidene] -3,3, (1H, 1, H) -dione (1): 1H NMR (300 MHz, CDCl3, ) 511.12 (s, 1H), 8.5 (dd, J = 1.7 Hz, J = 5.0 Hz, 1H), 8.41 (dd, J = 1.7 Hz, J = 5, 0 Hz, 1H), 8.03-7.99 (m, 2H), 7.00-6.95 (m, 2H), 4.70 (t, J = 7.6 Hz, 2H) 1.23 (m, 12H), 0.85 (t, J = 6.5 Hz, 3H); UV-vis (C ^ Cb, 25 ° C) AmaX (e) 317 (31066), 426 (703), 601 (10933); MALDI-TOF MS m / z 377 (M + H +); HRMS (MALDI-TOF) calculated for C22H24N4O2: 377.1972, found: 377.1967.
    [0099]
    [0100] Example 2: Photophysical studies
    [0101] Absorption spectrum of compound 1
    [0102] In FIG. 1 shows the absorption spectrum of the compound of formula 1 at a concentration of 1.5 x 10-5 M in dichloromethane. In the spectra three absorption bands are observed, centered at Amax = 317, 426 and 601 nm, the last one being wider than the other three and the second one with very low absorption. The extinction coefficients (£) for the absorption peaks in dichloromethane are £ = 31066, 703, 10933Lmol-1cm-1.
    [0103]
    [0104] In FIG. 2 the absorption spectrum of the 7,7'-diazaisoindigo derivative of formula 2 described in application WO2017005956A1 for a concentration of 2.9 x 10-5 M in dichloromethane is shown: In the spectra there are three absorption bands, centered at Amax = 282, 329 and 477 nm, the latter being wider than the other two. The extinction coefficients (£) for the absorption peaks in dichloromethane are £ = 30664, 12081 and 5020 Lmol-1cm-1.
    [0105]
    [0106] The absorption data of compounds 1 and 2 demonstrate that the variation in the position of the double bond affects the properties of the compounds, so that their absorption in UV is different, observing in the case of compound 1 a very blue color intense where in the absorption bands there is a batochromic shift towards red with respect to compound 2, which will lead to a change in the energy states of the molecule, this result is of interest in the use of these compounds as organic electronic semiconductors, such as organic photovoltaic cells.
    权利要求:
    Claims (16)
    [1]
    1. A compound of formula I:

    [2]
    2. The compound of formula I according to claim 1, wherein R5 and R6 represent O.
    [3]
    3. The compound of formula I according to any one of claims 1 or 2, wherein each R3 and R4 independently represents H or C1-C25 alkyl, wherein C1-C25 alkyl may be optionally substituted by one or more halogen or hydroxyl groups.
    [4]
    4. The compound of formula I according to claim 3, wherein each R3 and R4 independently represents H or C1-C25 alkyl.
    [5]
    5. The compound of formula I according to any one of claims 1 to 4, wherein each R1 and R2 independently represent H, F, Cl or Br.
    [6]
    6. The compound of formula I according to claim 5, wherein each R1 and R2 independently represent H.
    [7]
    7. The compound of formula I according to any one of claims 1 to 6, wherein R3 represents C1-C16 alkyl, and more preferably C1-C12 alkyl.
    [8]
    8. The compound of formula I according to claim 7, wherein R3 represents C3-C12 alkyl.
    [9]
    9. The compound of formula I according to claim 8, wherein R3 represents C3-C9 alkyl.
    [10]
    10. The compound of formula I according to any one of claims 1 to 9, wherein R4 represents H.
    [11]
    11. The compound of formula I according to claim 1, wherein the compound is N-octyl-7,7'-diazaindigo.
    [12]
    12. Use of a compound of formula I according to any of claims 1 to 11, for the manufacture of organic semiconductor materials.
    [13]
    13. A semiconductor material comprising a compound of formula I according to any one of claims 1 to 11.
    [14]
    14. A device comprising the material according to claim 13.
    [15]
    15. Use of the device according to claim 14 as an organic electronic semiconductor.
    [16]
    16. The use of the device according to claim 15 as organic photovoltaic cells.
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    同族专利:
    公开号 | 公开日
    ES2718418B2|2019-10-31|
    WO2019129911A1|2019-07-04|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2017005956A1|2015-07-06|2017-01-12|Consejo Superior De Investigaciones Científicas |Organogel based on molecules derived from 7,7'-diazaisoindigo|
    WO2017103318A1|2015-12-18|2017-06-22|Consejo Superior De Investigaciones Científicas |7,7'-diazaisoindigo derivative compounds and uses thereof|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201731501A|ES2718418B2|2017-12-29|2017-12-29|DERIVATIVES OF 7,7'-DIAZAINDIGO AND ITS USES|ES201731501A| ES2718418B2|2017-12-29|2017-12-29|DERIVATIVES OF 7,7'-DIAZAINDIGO AND ITS USES|
    PCT/ES2018/070833| WO2019129911A1|2017-12-29|2018-12-27|Derivatives of 7,7'-diazaindigo and uses thereof|
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