CN114516965A - Intelligent photochromic material and preparation method and application thereof - Google Patents

Intelligent photochromic material and preparation method and application thereof Download PDF

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CN114516965A
CN114516965A CN202011312263.8A CN202011312263A CN114516965A CN 114516965 A CN114516965 A CN 114516965A CN 202011312263 A CN202011312263 A CN 202011312263A CN 114516965 A CN114516965 A CN 114516965A
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匡小飞
卢灿忠
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Xiamen Institute of Rare Earth Materials
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Abstract

The invention discloses aThe supermolecular complex is formed by assembling an electron acceptor and an electron donor, wherein the electron acceptor has an electron acceptor framework with a structure shown as a formula (I), and the electron acceptor and the electron donor realize charge transfer through an interaction path of lone pair electrons and a pi-plane, so that photochromic behavior is shown. The composite film formed by the supermolecular complex and the macromolecule shows colorless and transparent indoors, the color changes into brown and transparent outdoors, and the intelligent behavior is only controlled by the sunlight intensity and the oxygen in the air. The intelligent color-changing behavior shows broad application prospects in the fields of erasable paper, transparent glass windows, color-changing spectacle lenses, data storage, aging prevention, anti-counterfeiting and modern military.
Figure DDA0002790173150000011

Description

Intelligent photochromic material and preparation method and application thereof
Technical Field
The invention belongs to the field of photochromic materials, and particularly relates to an intelligent photochromic material and a preparation method and application thereof.
Background
With the progress of society, the quality requirements of people for life are higher and higher, and particularly, the requirements are reflected in the aspect of materials used in daily life, from traditional ceramics to metallurgy and later high polymer materials. In recent years, smart materials play an important role in our daily lives, such as smart phones, smart robots, and the like. The nature provides excellent blueprints for developing various novel materials, such as sunflower phototropism, cephalic and podomeric animals such as cyroma, squid, octopus and the like to disguise themselves by changing skin color, and gorgeous butterflies to change wing colorful color by air humidity. Therefore, the development of the bionic fully-intelligent material becomes a new research direction and a hot spot, wherein the material has the greatest characteristic of being capable of sensing the performance of the automatic adjusting material such as light, heat, humidity, temperature and the like in the nature, so that the fully-intelligent robot with sensing capability is assembled in an integrated mode. Among such materials, photochromic materials are a very important class of stimuli-responsive materials. At present, inorganic substances such as tungsten trioxide, titanium dioxide and silver halide are mainly coated by a high-temperature evaporation method in industry, so that not only is energy consumed, but also the coating is easy to fall off, and the application range is extremely limited. In recent years, organic photochromic materials have been developed, and four types of materials, such as azobenzene, fulgide, spiropyran, and diarylethene, have been mainly used. The common characteristic of the materials is that the photochromic performance can be controlled reversibly by controlling the wavelength of incident light, so that the materials are mainly used as molecular switches and widely applied to the fields of various molecular devices and the like. However, in natural systems, both the glazing and the sun protection spectacles we have produced are exposed directly to the sun, including part of the ultraviolet and most of the visible light, and thus the photochromic properties of these materials are lost. Therefore, a new organic system is searched, a bionic material which can not only fully automatically respond to sunlight, but also can adapt to the environment to realize self-regulation is developed, and the bionic material can show unique application in the fields of adaptive military camouflage, intelligent glasses, intelligent windows and the like under extreme conditions, and is a difficult problem in the fields of chemistry and materials science at present.
Disclosure of Invention
The invention provides a donor-acceptor charge transfer supramolecular complex, which is formed by assembling an electron acceptor and an electron donor, wherein the electron acceptor has an electron acceptor framework with a structure shown in a formula (I), and the electron acceptor and the electron donor realize charge transfer through an interaction path of lone pair electrons and a pi-plane, so that photochromic behavior is shown;
Figure BDA0002790173130000021
wherein R is1、R2Identical or different, independently of one another, from the group consisting of unsubstituted or optionally substituted by 1,2 or more halogen, C1-40Alkyl radical, C1-40Alkoxy-substituted the following groups: c6-20Aryl, 5-20 membered heteroaryl;
Figure BDA0002790173130000022
selected from unsubstituted or optionally substituted by 1,2 or more RaSubstituted of the following groups:
Figure BDA0002790173130000023
Figure BDA0002790173130000024
is a linking site;
each RaIdentical or different, independently of one another, from H, halogen, C1-40Alkyl radical, C3-40Cycloalkyl radical, C1-40Alkoxy, and optionally halogen, C1-40Alkyl radical, C3-40Cycloalkyl radical, C1-40Alkoxy radicalSubstituted or unsubstituted C6-20Aryl, 5-20 membered heteroaryl, C6-20Aryloxy, 5-20 membered heteroaryloxy;
the electron donor is an electron-rich organic molecule, and for example, may be an organic solvent molecule containing a lone pair of electrons, preferably one, two or more of dimethylacetamide (DMAc), Dimethylformamide (DMF), Diethylformamide (DEF), N-dimethylpropionamide, N-dimethylallylamine, N-diethylchloroformamide, N-diethylacrylamide, N-diethylbenzamide, N-methylpyrrolidone (NMP), Dimethylsulfoxide (DMSO), and Tetrahydrofuran (THF).
According to an embodiment of the invention, R1、R2Identical or different, independently of one another, from C6-10Aryl, 5-14 membered heteroaryl; such as pyridyl, phenyl, imidazolyl, triazole, tetrazole, acridinyl, and the like.
According to an embodiment of the invention, each R isaSame or different, independently from each other selected from H, C1-8Alkyl radical, C6-10Aryl, 5-10 membered heteroaryl; for example, each RaSame, are all H, methyl, ethyl, phenyl, mercapto, amino or
Figure BDA0002790173130000031
According to an embodiment of the present invention, the electron acceptor is selected from any one of the compounds represented by formulae (I-1) to (I-3):
Figure BDA0002790173130000032
R1、R2、Rahave the meaning as described above.
Illustratively, the electron acceptor is selected from at least one of the following compounds:
Figure BDA0002790173130000041
according to an exemplary embodiment of the invention, the donor-acceptor charge transfer supramolecular complexes are assembled from an electron acceptor and an electron donor;
the electron acceptor is selected from a compound with a structure shown in a formula (I-1) or a compound with a structure shown in a formula (I-2), and is preferably a compound 4-pyNDI or 9-arnDI;
the electron donor is selected from organic solvent molecules containing a lone pair of electrons, preferably DMF or DMAc;
the electron acceptor and the electron donor realize charge transfer through an interaction path of lone pair electrons and a pi-plane, thereby showing photochromic behavior.
According to embodiments of the present invention, the supramolecular complex may be a co-crystal formed by an electron acceptor and an organic solvent molecule, or a conjugated structure formed by the electron acceptor itself.
According to an exemplary embodiment of the invention, the supramolecular complex formed by charge transfer assembly of the compound 4-pyNDI and DMAc molecules, denoted as 4-pyNDI-DMAc, the unit cell parameters of the 4-pyNDI-DMAc crystal include:
Figure BDA0002790173130000051
α＝96.808(2)°,β＝90.660(2)°,γ＝91.724(2)°,
Figure BDA0002790173130000052
the space group is P-1.
According to an exemplary embodiment of the present invention, the unit cell parameters of a supramolecular complex formed by charge transfer assembly of the compound 4-pyNDI and DMF molecules, denoted as 4-pyNDI-DMF, 4-pyNDI-DMF crystal, include:
Figure BDA0002790173130000053
α＝90.110(16)°,β＝97.024(11)°,γ＝90.086(11)°,
Figure BDA0002790173130000054
the space group is P-1.
The invention also provides a preparation method of the supramolecular complexThe preparation method comprises the following steps: reacting compound 1 with R1-NH2And/or R2-NH2Mixing the materials in a first organic solvent, refluxing, standing and crystallizing to obtain the supramolecular complex;
wherein, the compound 1 is
Figure BDA0002790173130000055
Figure BDA0002790173130000056
R1、R2Having the definitions as described above.
Preferably, the first and second electrodes are formed of a metal,
Figure BDA0002790173130000057
selected from unsubstituted or optionally substituted by 1,2 or more RaSubstituted of the following groups:
Figure BDA0002790173130000058
the R isaHaving the definitions as described above.
According to an embodiment of the invention, the first organic solvent is an electron-rich organic molecule or an acetic acid molecule, for example an organic solvent or an acetic acid molecule containing a lone pair of electrons, preferably the organic solvent containing a lone pair of electrons is dimethylacetamide (DMAc), Dimethylformamide (DMF), Diethylformamide (DEF), N-dimethylpropionamide, N-dimethylallylamine, N-diethylchloroformamide, N-diethylacrylamide, N-diethylbenzamide, N-methylpyrrolidone (NMP), Dimethylsulfoxide (DMSO) or Tetrahydrofuran (THF).
According to a preferred embodiment of the invention, when RaWhen H, the first organic solvent is an electron-rich organic molecule; when R isaAnd (c) when the above optional other substituent is present, the first organic solvent is an acetic acid molecule.
According to an embodiment of the invention, compounds 1 and R1-NH2And/or R2-NH2The molar ratio of (A) to (B) may be 1 (1-10),e.g., 1 (1-4), illustratively 1: 2.
According to an embodiment of the invention, R1-NH2And R2-NH2Examples of the same include at least one of 4-aminopyridine, 3-aminopyridine, aniline, 2-aminoimidazole, 9-aminoacridine, and 5-aminotetrazole, and preferably include 4-aminopyridine, 9-aminoacridine, and 5-aminotetrazole.
According to embodiments of the invention, the mass to volume ratio (g/mL) of Compound 1 to the first organic solvent can be 1 (10-100), e.g., 1 (20-60), illustratively 1: 50.
According to an embodiment of the invention, the refluxing is carried out under nitrogen protection.
The invention also provides another preparation method of the supramolecular complex, which comprises the following steps: mixing and dissolving the supramolecular complex prepared by the method and a second organic solvent, and standing the mixture under the dark condition to obtain another supramolecular complex.
According to an embodiment of the invention, the second organic solvent is different from the first organic solvent, and is also an electron-rich organic molecule, for example an organic solvent containing a lone pair of electrons, preferably dimethylacetamide (DMAc), Dimethylformamide (DMF), Diethylformamide (DEF), N-methylpyrrolidone (NMP), Dimethylsulfoxide (DMSO), Tetrahydrofuran (THF), N-dimethylpropionamide, N-dimethylallylamine, N-diethylchloroformamide, N-diethylacrylamide or N, N-diethylbenzamide.
According to an embodiment of the invention, the mass to volume ratio (g/mL) of the supramolecular complex obtained by the aforementioned method to the second organic solvent may be 1 (10-200), such as 1 (50-180), exemplarily 1: 178.
According to an embodiment of the invention, the period of standing is 2 to 12 days, such as 3 to 8 days, exemplary 7 days.
The invention also provides a preparation method of the supramolecular complex, which comprises the following steps: mixing and dissolving an electron acceptor and an organic solvent, and standing under a dark condition to obtain the supramolecular complex;
the electron acceptor is prepared by a method comprising the following steps:
Figure BDA0002790173130000071
reacting compound 1, R1-NH2And/or R2-NH2Mixing with a solvent, and heating for melting reaction or reflux reaction to obtain an electron acceptor;
Figure BDA0002790173130000072
R1、R2having the definitions as described above.
Preferably, the first and second electrodes are formed of a metal,
Figure BDA0002790173130000073
selected from unsubstituted or optionally substituted by 1,2 or more RaSubstituted of the following groups:
Figure BDA0002790173130000074
Figure BDA0002790173130000075
is a linking site;
Rahave the meaning as described above.
According to an embodiment of the present invention, the solvent may be propionic acid, quinoline or fused imidazole.
According to an embodiment of the invention, an acetate salt, such as zinc acetate, may be added to the reaction.
According to an embodiment of the present invention, when
Figure BDA0002790173130000076
Selected from unsubstituted
Figure BDA0002790173130000077
When the compound 1, R1-NH2And/or R2-NH2Mixing with imidazole, heating for melting reaction, cooling, and washing the reaction product to obtain the electron acceptor.
According to an embodiment of the present invention, when
Figure BDA0002790173130000081
Selected from the group optionally substituted by 1,2 or more RaSubstituted by
Figure BDA0002790173130000082
When the compound 1, R1-NH2And/or R2-NH2Mixing with propionic acid or heating and refluxing with zinc acetate under quinoline condition, precipitating to separate out solid, and washing to obtain the electron acceptor. Preferably, the mass-to-volume ratio of the compound 1 to the propionic acid or the quinoline is 1g (15-40) ml, preferably 1g (20-30) ml.
According to an embodiment of the invention, said compound 1 and R1-NH2And/or R2-NH2The molar ratio of (A) may be 1 (1-10), such as 1 (1-4), illustratively 1: 2.
According to an embodiment of the invention, R1-NH2And R2-NH2Examples of the same include at least one of 3-aminopyridine, aniline, 2-aminoimidazole, and 9-aminoacridine.
According to an embodiment of the present invention, the organic solvent is a lone pair electron containing organic solvent, preferably dimethylacetamide (DMAc), Dimethylformamide (DMF), Diethylformamide (DEF), N-methylpyrrolidone (NMP), Dimethylsulfoxide (DMSO), Tetrahydrofuran (THF), N-dimethylpropionamide, N-dimethylallylamine, N-diethylchloroformamide, N-diethylacrylamide or N, N-diethylbenzamide.
According to an embodiment of the invention, the mass ratio of the compound 1 to the solid solvent is 1 (2-10), such as 1 (3-6), exemplarily 1: 4.
According to embodiments of the invention, the temperature of the heating and melting reaction is 100-.
According to an embodiment of the invention, the time of the heating melt reaction is 20 to 60min, such as 30 to 50 min.
According to an embodiment of the invention, the washing comprises: the reaction product is washed with a mixture of ethanol and hydrochloric acid and filtered, and then washed with ethanol. Preferably, the volume ratio of ethanol to hydrochloric acid in the mixed solution of ethanol and hydrochloric acid is 1 (0.5-2), for example 1: 1.
According to an embodiment of the invention, the period of standing is 2 to 12 days, such as 3 to 8 days, exemplary 7 days.
The invention also provides the application of the electron acceptor and/or the supramolecular complex as photochromic materials.
The invention also provides a photochromic material which contains the electron acceptor or the supramolecular complex.
According to an embodiment of the present invention, the photochromic material may be a liquid, a solid, a polymer composite film, a polymer fiber, a polymer textile, a polymer composite coating layer containing the electron acceptor or the supramolecular complex.
The invention also provides a high-molecular composite film, which contains the supermolecular composite or the electron acceptor and a polymer.
According to an embodiment of the present invention, the polymer may be a polymer that is soluble in the above electron donor, such as an acrylic resin or polycarbonate, exemplified by at least one of polymethyl methacrylate, polyethyl methacrylate, polypropylene methacrylate, n-butyl methacrylate, polycarbonate.
According to an embodiment of the present invention, the polymer composite film is a colorless transparent film.
The invention also provides a preparation method of the polymer composite membrane, which comprises the steps of mixing the supramolecular complex or the electron acceptor with a polymer material in an electron donor to obtain the polymer composite membrane;
according to an embodiment of the invention, the polymeric material has the meaning as described above, preferably polymethylmethacrylate.
According to an embodiment of the invention, the electron acceptor and the electron donor have the meanings as described above.
According to embodiments of the invention, the mass ratio of the supramolecular complex or electron acceptor to the polymeric material may be 1 (10-130), such as 1 (20-60), exemplary 1:50, 1.5:100, 9: 100.
According to an embodiment of the invention, the mass to volume ratio of the polymeric material to the electron donor is 1g (3-10) ml, for example 1g (4-6) ml.
According to a preferred embodiment of the present invention, the method for preparing the polymer composite membrane comprises mixing the electron acceptor or the supramolecular complex with a polymer material in an electron donor, heating to obtain a clear solution, dripping or coating the clear solution on a substrate, and drying to obtain the polymer composite membrane;
preferably, the electron acceptor may be selected from 4-pyNDI, 3-pyNDI, 9-arnDI, 5-trzNDI, Cl4PDI or PhOPDI;
preferably, the electron donor has the meaning as described above, preferably DMF, DMAc.
Preferably, the temperature of the heating is 60-90 ℃, such as 70-80 ℃; preferably, the heating is for a period of time of 0.5 to 2 hours, for example 1 to 1.5 hours.
Preferably, the temperature of the drying is 50-60 ℃, e.g. 53-58 ℃; preferably, the drying time is 5-8 hours, such as 5-6 hours.
Preferably, the substrate may be a glass slide.
The invention also provides application of the electron receptor, the supramolecular complex, the photochromic material or the polymer composite film in the fields of erasable paper, transparent glass windows, organic glass intelligent windows, color-changing spectacle lenses, sun-proof spectacles, data storage, anti-aging and anti-counterfeiting.
The invention also provides application of the electron receptor, the supramolecular complex, the photochromic material, the polymer fiber, the polymer textile or the polymer composite coating in the field of military camouflage, such as environmental adaptability camouflage of clothes, equipment and the like.
Advantageous effects
In the supermolecule compound and the preparation method thereof provided by the invention, the organic solvent not only can dissolve the electron acceptor and most of macromolecules, but also can be used as the electron donor, and the obtained supermolecule compound can generate dynamic electron transfer so as to show dynamic color changing performance. The supramolecular complexes or electron acceptors exhibit photochromic behavior in the fresh solution and solid states as well as in the thin film state of the polymer complexes. In the preparation process of the polymer composite membrane, the solvent can dissolve the compound shown in the formula (I) and most polymers, and also can be used as an electron donor or a plasticizer to endow the material with dynamic electron transfer so as to show dynamic color change performance. The supermolecule compound or the electron acceptor and the macromolecule form a composite film in the electron donor, the color change behavior of the material is controlled through charge transfer interaction between the supermolecule compound or the electron acceptor and the electron donor, the color change is similar to the light stimulation color change of chameleon, the wavelength of incident light is controlled without manual intervention, the color change is fully automatic and intelligent, and the composite film has unique application in the fields of organic glass intelligent windows, sun-proof glasses, military anti-counterfeiting and the like. It is worth noting that the donor-acceptor supramolecular complexes can automatically respond to sunlight, and the doped polymer material shows unique photochromic behavior through photoinduced electron transfer. When the light intensity is weakened, the light source automatically recovers to the initial state under the action of oxygen in the air, the whole process does not need manual intervention, and the light source has a unique application prospect in the military field. For example, the material is applied to the preparation of a polymer coating, and the material can realize the function of automatic stealth after being coated on fighters, warships, armored vehicles, tanks and ordnance. By changing the substituent of the ligand, the photochromic conversion between colorless and blue can be realized, so that the warship can be automatically matched with the blue of seawater in the ocean, and the function of interactive stealth with the environment can be realized. In addition, the material can also be applied to the preparation of doped polymer fibers, so that the clothes of soldiers can be automatically matched with local colors in the field, and the photochromic textile is convenient for military camouflage.
Definition and description of terms
Unless otherwise indicated, the numerical ranges set forth in the specification and claims are equivalent to at least each and every specific integer numerical value set forth therein. For example, a numerical range of "1-40" is equivalent to reciting each of the integer values in the numerical range of "1-10," i.e., 1,2, 3,4, 5, 6,7, 8, 9,10, and each of the integer values in the numerical range of "11-40," i.e., 11, 12, 13, 14, 15, 35, 36, 37, 38, 39, 40. Further, when certain numerical ranges are defined as "numbers," it should be understood to recite both the endpoints of the range, each integer within the range, and each decimal within the range.
It should be understood that in describing 1,2 or more herein, "more" shall mean an integer greater than 2, e.g., greater than or equal to 3, e.g., 3,4, 5, 6,7, 8, 9, or 10.
The term "halogen" denotes fluorine, chlorine, bromine and iodine.
The term "C1-40Alkyl is understood to mean a straight-chain or branched saturated monovalent hydrocarbon radical having from 1 to 40 carbon atoms. For example, "C1-10Alkyl "denotes straight-chain and branched alkyl groups having 1,2, 3,4, 5, 6,7, 8, 9 or 10 carbon atoms," C1-6Alkyl "denotes straight-chain and branched alkyl groups having 1,2, 3,4, 5 or 6 carbon atoms. The alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a 2-methylbutyl group, a 1-ethylpropyl group, a 1, 2-dimethylpropyl group, a neopentyl group, a 1, 1-dimethylpropyl group, a 4-methylpentyl group, a 3-methylpentyl group, a 2-ethylbutyl group, a 1-ethylbutyl group, a 3, 3-dimethylbutyl group, a 2, 2-dimethylbutyl group, a 1, 1-dimethylbutyl group, a 2, 3-dimethylbutyl group, a 1, 3-dimethylbutyl group or a 1, 2-dimethylbutyl group, or the like, or isomers thereof.
The term "C3-40Cycloalkyl is understood to mean a saturated monovalent monocyclic, bicyclic (e.g.fused, bridged, spiro) hydrocarbon or tricyclic hydrocarbon ring having 3 to 40 carbon atoms, preferablySelect "C3-10Cycloalkyl groups ". The term "C3-10Cycloalkyl "is understood to mean a saturated monovalent monocyclic, bicyclic (e.g. bridged, spiro) hydrocarbon ring or tricycloalkane having 3,4, 5, 6,7, 8, 9 or 10 carbon atoms. Said C is3-10Cycloalkyl can be monocyclic, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or bicyclic, such as bornyl, indolyl, hexahydroindolyl, tetrahydronaphthyl, decahydronaphthyl, bicyclo [2.1.1]Hexyl, bicyclo [2.2.1]Heptyl, bicyclo [2.2.1]Heptenyl, 6-dimethylbicyclo [3.1.1]Heptyl, 2,6, 6-trimethylbicyclo [3.1.1]Heptyl, bicyclo [2.2.2]Octyl, 2, 7-diazaspiro [3,5 ]]Nonanyl, 2, 6-diazaspiro [3,4 ]]An octyl group, or a tricyclic hydrocarbon group such as an adamantyl group.
The term "C6-20Aryl is understood to mean preferably a mono-, bi-, or tricyclic hydrocarbon ring of monovalent or partially aromatic character having 6 to 20 carbon atoms, which may be a mono-or polyaromatic ring, preferably "C", such as a fused, bridged, spiro ring6-14Aryl ". The term "C6-14Aryl "is to be understood as preferably meaning a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6,7, 8, 9,10, 11, 12, 13 or 14 carbon atoms (" C6-14Aryl group "), in particular a ring having 6 carbon atoms (" C6Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C9Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C10Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C13Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C)14Aryl), such as anthracenyl. When said C is6-20When the aryl group is substituted, it may be mono-or polysubstituted. And, the substitution site thereof is not limited, and may be, for example, ortho-, para-or meta-substitution.
The term "5-20 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic (e.g., fused, bridged, spiro) or tricyclic aromatic ring systems: having 5 to 20 ring atoms and comprising 1 to 5 heteroatoms independently selected from N, O and S, such as "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: which has 5, 6,7, 8, 9,10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and which comprises 1 to 5, preferably 1 to 3, heteroatoms each independently selected from N, O and S and, in addition, can be benzo-fused in each case. "heteroaryl" also refers to a group in which a heteroaromatic ring is fused to one or more aryl, alicyclic, or heterocyclic rings, wherein the radical or point of attachment is on the heteroaromatic ring.
Drawings
FIG. 1 is a graph showing the change in color of 4-pyNDI-DMAc crystal obtained in example 2 after irradiation with a 300-watt xenon lamp for three minutes in a solution state;
FIG. 2 shows the UV-VIS spectra of 4-pyNDI-DMAc crystal obtained in example 2 before and after irradiation in DMAc solution;
FIG. 3 is a graph showing the change in color of 4-pyNDI-DMAc crystal obtained in example 2 after it was irradiated with 300W xenon lamp for one minute;
FIG. 4 is a UV diffuse reflectance spectrum of 4-pyNDI-DMAc crystal obtained in example 2 before and after one minute of xenon lamp illumination at 300W;
FIG. 5 is the XRD spectrum of the 4-pyNDI-DMAc crystal obtained in example 2 and its different illumination time;
FIG. 6 is a photochromic plot of the composite film obtained in example 3;
FIG. 7 shows the absorption spectra of ultraviolet light and visible light before and after the irradiation of the composite film obtained in example 3;
FIG. 8 is a graph of the self-fading profile of the composite film obtained in example 3;
FIG. 9 is a color change chart of the composite film obtained in example 3 in six color fading experiments;
fig. 10 is a schematic view of charge transfer supramolecules.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
EXAMPLE 1 Synthesis of naphthalimide supramolecular Complex (4-pyNDI-DMF)
The 4-pyNDI-DMF complex is formed by complexing the compound 4-pyNDI and DMF, and the preparation process comprises the following steps:
Figure BDA0002790173130000141
1,4,5, 8-naphthalene tetracarboxylic anhydride (2g,7.4mmol) and 4-aminopyridine (1.54g,16.4mmol) are added into a reaction flask, 100 ml of anhydrous DMF is added, heating and refluxing are carried out for 15 hours under the protection of nitrogen, then cooling to room temperature is carried out, filtration is carried out to obtain 2g of brown supramolecular complex crystals, and vacuum drying is carried out at 100 ℃ for 8 hours for standby application.
The 4-pyNDI-DMF compound is a single crystal, and the unit cell parameters are as follows:
Figure BDA0002790173130000142
Figure BDA0002790173130000143
α＝90.110(16)°,β＝97.024(11)°,γ＝90.086(11)°,
Figure BDA0002790173130000144
the space group is P-1.
The single crystal and the spectra and paramagnetic spectra show that the 4-pyNDI-DMA eutectic forms intermolecular charge transfer, and the electron donating DMAc forms a path of charge transfer supramolecular complexes by transferring its O lone pair to the pi-plane of electron deficient NDI, and the charge transfer supramolecular schematic is shown in FIG. 10. The organic co-crystal exhibits reversible photochromic behavior by photoinduced electron transfer. Thermogravimetric analysis and repeated illumination powder diffraction show that the compound has better photo-thermal stability.
EXAMPLE 2 Synthesis of naphthalimide supramolecular Complex (4-pyNDI-DMAc)
The 4-pyNDI-DMAc compound is formed by compounding a compound 4-pyNDI and DMAc, and the preparation process comprises the following steps:
0.45g of the solid 4-pyNDI-DMF from example 1 was added to a 100 ml beaker and dissolved after addition of 80 ml of DMAc to give an orange-red solution. Sealing the solution with polyethylene preservative film, standing in the dark for one week to obtain organic supermolecular compound crystal (4-pyNDI-DMAc).
Infrared Spectrum (cm) of 4-pyNDI-DMAc-1) The characterization was as follows: 3375(w),3066(w),3036(w),2930(w),1997(w),1713(s),1668(s),1635(s),1577(s),1494(w),1449(s),1412(m),1341(s),1242(s),1197(s),1148(m),1119(m),1065(m),987(s),884(m),863(m),826(m),765(s),750(s),719(s),580 (m). The NDI-DMAc preparation is proved to be successful.
Thermogravimetric analysis shows that the compound is stable at room temperature and 100 ℃.
The unit cell parameters of 4-pyNDI-DMAc are:
Figure BDA0002790173130000151
Figure BDA0002790173130000152
α＝96.808(2)°,β＝90.660(2)°,γ＝91.724(2)°,
Figure BDA0002790173130000153
the space group is P-1.
FIG. 1 is a graph showing the change in color of 4-pyNDI-DMAc crystals after irradiation with a 300-watt xenon lamp for three minutes in the state of a solution, the solution changing from colorless to pale yellow.
FIG. 2 shows the UV-VIS spectra of 4-pyNDI-DMAc crystal obtained in example 2 before and after irradiation in DMAc solution;
FIG. 3 is a graph showing the change in color of 4-pyNDI-DMAc crystal obtained in example 2 after one minute exposure to 300W xenon lamp, as can be seen from FIG. 3: the supramolecular complex changes from colorless to dark black.
FIG. 4 is a UV diffuse reflectance spectrum of 4-pyNDI-DMAc crystal obtained in example 2 before and after one minute of xenon lamp illumination at 300W; fig. 3 and 4 show that the supramolecular complex changes color under light, but the structure remains stable.
FIG. 5 is the XRD spectrum of the 4-pyNDI-DMAc crystal obtained in example 2 and its different illumination time; indicating that the crystal form of the supramolecule remains stable before and after illumination.
EXAMPLE 3 preparation of a composite film of naphthalimide supramolecules (4-pyNDI-DMAc) and Polymethylmethacrylate (PMMA)
1g of polymethyl methacrylate (PMMA) resin is placed in a 20 ml glass bottle, 5 ml of DMAc is added, the bottle is covered and sealed, then the bottle is placed in a 100 ℃ oven and heated until the resin is completely dissolved to obtain colorless transparent viscous solution, 20 mg of the naphthalimide supramolecule (4-pyNDI-DMAc) prepared in the example 2 is added into the solution, then the solution is sealed, subjected to ultrasonic treatment for 10 minutes, then placed in an 80 ℃ oven and dried for 1 hour, and then the solution is dissolved to obtain clear solution. The solution is absorbed by a suction pipe in a small amount and then is dripped on a transparent glass slide, and then the transparent polymer composite membrane is obtained after the transparent glass slide is placed in a vacuum drying oven at the temperature of 50 ℃ for 8 hours. The photochromic diagram is shown in figure 6, and the color of the photochromic material changes from colorless to reddish brown after being illuminated by a 300 watt xenon lamp for one minute, and then the photochromic material is placed in indoor air and changes from reddish brown to colorless after 20 minutes.
FIG. 7 shows the UV-VIS absorption spectra before and after illumination of the composite film obtained in example 3;
FIG. 8 is a graph showing that the composite film obtained in example 3 was changed into a reddish brown film by exposure to 300W xenon light for 3 minutes, and the self-fading curve in the air at room temperature was examined, and the color gradually faded with time to form a colorless transparent film. Further studies have shown that the film can undergo reversible coloration and discoloration multiple times.
Fig. 9 is a graph of six consecutive cycles of coloration and discoloration for the composite film prepared in this example, showing that the polymer film doped with supramolecular complexes has good resistance to photochromic fatigue and good cycling stability.
The research shows that the supramolecular complex formed by the naphthalimide and the solvent molecules has photochromic behavior in a solution state and is more obvious in a solid state and a high-molecular film state.
Those skilled in the art will appreciate that acrylic resins such as polyethyl methacrylate, poly propyl methacrylate, poly n-butyl methacrylate, and the like may be used in place of polymethyl methacrylate to provide other composite films having properties similar to those of example 3.
EXAMPLE 4 Synthesis of naphthalimide supramolecular Complex (4-pyNDI-DMAc)
1,4,5, 8-naphthalene tetracarboxylic anhydride (2g,7.4mmol), 4-aminopyridine (1.54g,16.4mmol) and 8g of imidazole are added into a reaction flask, the mixture is heated to 130 ℃ in an oil bath under the protection of nitrogen, is heated for 30 minutes and then is cooled to room temperature, and then is washed by a mixed solution of ethanol and 2mol/L hydrochloric acid (10:10, V/V) and filtered, and then is washed by 20 ml of ethanol to obtain a brown product, and is dried in vacuum at 100 ℃ to obtain the compound 4-pyNDI.
Figure BDA0002790173130000171
4-pyNDI compound 4-pyNDI was added to a 100 ml beaker and dissolved after addition of 80 ml DMAc to give an orange-red solution. Sealing the solution with polyethylene preservative film, standing in dark for one week to obtain organic supermolecular complex crystal (4-pyNDI-DMAc).
EXAMPLE 5 Synthesis of supramolecular complexes (9-arnDI-DMF)
The supramolecular complex in the embodiment is formed by complexing compound 9-arNDI with DMF, and compound 9-arNDI has the following structure:
Figure BDA0002790173130000172
the specific preparation process of the supramolecular complex of the present example is as follows:
1,4,5, 8-naphthalene tetracarboxylic anhydride (2g,7.4mmol) and 9-aminoacridine (3.2g,16.5mmol) were added to a reaction flask, 100 ml of anhydrous DMF was added, heated under reflux for 15 hours under nitrogen protection, cooled to room temperature, filtered to obtain brown supramolecular complex crystals 3.2g, and vacuum dried at 100 ℃ for 8 hours to obtain supramolecular complexes.
Example 6 example 5 preparation of a supramolecular complex and PMMA composite film
1g of polymethyl methacrylate (PMMA) resin is placed in a 20 ml glass bottle, 5 ml of DMAc is added, the bottle is covered and sealed, the bottle is placed in a 100 ℃ oven and heated until the resin is completely dissolved to obtain a colorless transparent viscous solution, 15 mg of the supermolecular complex of the example 5 is added into the solution, the solution is sealed, ultrasonic treatment is carried out for 10 minutes, then the solution is placed in an 80 ℃ oven and dried for 1 hour, and then the solution is dissolved to obtain a clear solution. The solution is absorbed by a suction pipe in a small amount and then is dripped on a transparent glass slide, and then the transparent polymer composite membrane is obtained after the transparent glass slide is placed in a vacuum drying oven at the temperature of 50 ℃ for 8 hours. The color of the mixture turns from colorless to reddish brown after being illuminated by a 300 watt xenon lamp for one minute, and then the mixture is placed in the air in a room and turns from reddish brown to colorless after 20 minutes.
EXAMPLE 7 Synthesis of supramolecular complexes (3-pyNDI-DMF)
1,4,5, 8-naphthalene tetracarboxylic anhydride (2g,7.4mmol) and 3-aminopyridine (1.54g,16.4mmol) were added to a reaction flask, 100 ml of anhydrous DMF was added, heated under reflux for 15 hours under nitrogen protection, cooled to room temperature, filtered to give a brown compound 1.8g, and dried in a vacuum oven at 100 ℃ for 8 hours to give a supramolecular complex.
EXAMPLE 8 Synthesis of supramolecular complexes (5-trzNDI-DMF)
Adding 1,4,5, 8-naphthalene tetracarboxylic anhydride (2g,7.4mmol) and 5-aminotetrazole (1.7g,16.5mmol) into a reaction flask, adding 100 ml of anhydrous DMF, heating and refluxing for 15 hours under the protection of nitrogen, cooling to room temperature, filtering to obtain a brown compound 1.8g, and vacuum drying at 100 ℃ for 8 hours to obtain the supramolecular complex.
EXAMPLE 9 Synthesis of Compound Cl4PDI
1,6,7, 12-tetrachloro-3, 4,9, 10-perylene imide dianhydride (1g,1.81mmol), 4-aminopyridine (1.8g,19mmol) were added to the flask, then 20 ml of propionic acid was added, refluxing was carried out at 155 ℃ for 3 days under a nitrogen atmosphere, then 100 ml of methanol was added to precipitate a solid, the solid precipitate was filtered, then washed with methanol until the filtrate was colorless, and the red solid was dried in a vacuum drying oven to obtain 1.2g of the product.
EXAMPLE 10 Synthesis of the Compound PhOPDI
1,6,7, 12-tetra-tert-butylphenol-3, 4,9, 10-perylenebisimide dianhydride (0.6g,0.62mmol), 4-aminopyridine (1.9 mg, 2.1mmol), zinc acetate (60 mg, 0.32mmol), and 20 ml of quinoline were added to the flask, refluxed at 180 ℃ for 16 hours under nitrogen protection, then 100 ml of 2mol/L hydrochloric acid solution was added, and then filtered to obtain a solid precipitate, which was washed repeatedly with water and methanol, dried, and then eluted with dichloromethane and methanol in volume ratio (98/2) to obtain 0.45g of pure product.
The electron acceptor compounds obtained in examples 7 to 10 were mixed with polymethyl methacrylate as an electron donor, and a transparent polymer composite film having photochromic properties was prepared by the method described in example 6.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A donor-acceptor charge transfer supramolecular complex is formed by assembling an electron acceptor and an electron donor, wherein the electron acceptor has an electron acceptor framework with a structure shown as a formula (I), and the electron acceptor and the electron donor realize charge transfer through an interaction path of a lone pair electron and a pi-plane so as to show photochromic behavior;
Figure FDA0002790173120000011
wherein R is1、R2Identical or different, independently of one another, from the group consisting of unsubstituted or optionally substituted by 1,2 or more halogen, C1-40Alkyl radical, C1-40Alkoxy-substituted the following groups: c6-20Aryl, 5-20 membered heteroaryl;
Figure FDA0002790173120000012
selected from unsubstituted or optionally substituted by 1,2 or more RaSubstituted of the following groups:
Figure FDA0002790173120000013
Figure FDA0002790173120000014
is a linking site;
each RaIdentical or different, independently of one another, from H, halogen, C1-40Alkyl radical, C3-40Cycloalkyl radical, C1-40Alkoxy, and optionally halogen, C1-40Alkyl radical, C3-40Cycloalkyl radical, C1-40Alkoxy substituted or unsubstituted C6-20Aryl, 5-20 membered heteroaryl, C6-20Aryloxy, 5-20 membered heteroaryloxy;
the electron donor is an electron-rich organic molecule, such as an organic solvent molecule containing a lone pair of electrons.
2. The supramolecular complex as claimed in claim 1, wherein said organic solvent molecule containing a lone pair of electrons is preferably one, two or more of dimethylacetamide, dimethylformamide, diethylformamide, N-dimethylpropionamide, N-dimethylallylamine, N-diethylchloroformamide, N-diethylacrylamide, N-diethylbenzamide, N-methylpyrrolidone, dimethylsulfoxide and tetrahydrofuran;
preferably, R1、R2Identical or different, independently of one another, from C6-10Aryl, 5-14 membered heteroaryl; such as pyridyl, phenyl, imidazolyl, triazole, tetrazole, acridinyl;
preferably, each RaSame or different, independently from each other selected from H, C1-8Alkyl radical, C6-10Aryl, 5-10 membered heteroaryl; for example, each RaSame, are all H, methyl, ethyl, phenyl, mercapto, amino or
Figure FDA0002790173120000021
Preferably, the electron acceptor is selected from any one of the compounds represented by formulae (I-1) to (I-3):
Figure FDA0002790173120000022
R1、R2、Raboth having the definitions as defined in claim 1 or 2;
preferably, the electron acceptor is selected from at least one of the following compounds:
Figure FDA0002790173120000031
3. the supramolecular complex as claimed in claim 1 or 2, characterized in that the donor-acceptor charge transfer supramolecular complex is formed by assembly of an electron acceptor and an electron donor;
preferably, the electron acceptor is selected from a compound with a structure shown in a formula (I-1) or a compound with a structure shown in a formula (I-2), and is preferably a compound 4-pyNDI or 9-arnDI;
preferably, the electron donor is selected from organic solvent molecules containing a lone pair of electrons, preferably DMF or DMAc;
preferably, the supramolecular complex can be a eutectic crystal formed by an electron acceptor and organic solvent molecules, and can also be a conjugated structure formed by the electron acceptor;
preferably, the supramolecular complex formed by charge transfer assembly of the compound 4-pyNDI and DMAc molecules, which is denoted as 4-pyNDI-DMAc, the unit cell parameters of the 4-pyNDI-DMAc crystal include:
Figure FDA0002790173120000041
Figure FDA0002790173120000042
α＝96.808(2)°,β＝90.660(2)°,γ＝91.724(2)°,
Figure FDA0002790173120000043
the space group is P-1;
preferably, the supramolecular complex formed by charge transfer assembly of the compound 4-pyNDI and DMF molecules, taken as the crystal unit cell parameters of 4-pyNDI-DMF, comprises:
Figure FDA0002790173120000044
Figure FDA0002790173120000045
α＝90.110(16)°,β＝97.024(11)°,γ＝90.086(11)°,
Figure FDA0002790173120000046
the space group is P-1.
4. A method for the preparation of the supramolecular complex as claimed in any of claims 1 to 3, characterized in that said method comprises the following steps: reacting compound 1 with R1-NH2And/or R2-NH2Mixing the materials in a first organic solvent, refluxing, standing and crystallizing to obtain the supramolecular complex;
wherein, the compound 1 is
Figure FDA0002790173120000047
Figure FDA0002790173120000048
R1、R2Having the definition as set forth in any one of claims 1 to 3;
preferably, the first and second electrodes are formed of a metal,
Figure FDA0002790173120000049
selected from unsubstituted or optionally substituted by 1,2 or more RaSubstituted of the following groups:
Figure FDA00027901731200000410
the R isaHaving the definition set forth in any one of claims 1 to 3;
preferably, the first organic solvent is an electron-rich organic molecule or an acetic acid molecule, for example, an organic solvent or an acetic acid molecule containing a lone pair of electrons, preferably the organic solvent containing a lone pair of electrons is dimethylacetamide, dimethylformamide, diethylformamide, N-dimethylpropionamide, N-dimethylallylamine, N-diethylchloroformamide, N-diethylacrylamide, N-diethylbenzamide, N-methylpyrrolidone, dimethylsulfoxide, or tetrahydrofuran;
preferably, when R isaWhen H, the first organic solvent is an electron-rich organic molecule; when R isaWhen not H, the first organic solvent is an acetic acid molecule;
preferably, said compound 1 and R1-NH2And/or R2-NH2In a molar ratio of 1 (1-10), e.g. 1 (1-4);
preferably, said R is1-NH2And R2-NH2The same, for example, is at least one of 4-aminopyridine, 3-aminopyridine, aniline, 2-aminoimidazole, 9-aminoacridine and 5-aminotetrazole;
preferably, the mass-to-volume ratio of the compound 1 to the first organic solvent is 1 (10-100) g/mL, such as 1 (20-60) g/mL.
5. A method for the preparation of the supramolecular complex as claimed in any of claims 1 to 3, characterized in that said method comprises the following steps: mixing the supramolecular complex obtained by the method of claim 4 with a second organic solvent and allowing the mixture to stand in the dark to obtain another supramolecular complex;
preferably, the second organic solvent is different from the first organic solvent, and is also an electron-rich organic molecule, such as an organic solvent containing a lone pair of electrons, preferably dimethylacetamide, dimethylformamide, diethylformamide, N-methylpyrrolidone, N-dimethylpropionamide, N-dimethylallylamine, N-diethylchloroformamide, N-diethylacrylamide, N-diethylbenzamide, dimethyl sulfoxide, or tetrahydrofuran;
preferably, the mass-to-volume ratio (g/mL) of the supramolecular complex obtained by the method of claim 4 to the second organic solvent is 1 (10-200), such as 1 (50-180);
preferably, the standing time is 2 to 12 days.
6. A method for the preparation of the supramolecular complex as claimed in any of claims 1 to 3, characterized in that said method comprises the following steps: mixing and dissolving an electron acceptor and an organic solvent, and standing under a dark condition to obtain the supramolecular complex;
the compound of the electron acceptor is prepared by a method comprising the following steps:
Figure FDA0002790173120000061
reacting compound 1, R1-NH2And/or R2-NH2Mixing with a solid solvent, heating for melting reaction, cooling and washing a reaction product to obtain a compound with a structure shown in a formula (I);
Figure FDA0002790173120000062
R1、R2having the definition as set forth in any one of claims 1 to 3;
preferably, the first and second electrodes are formed of a metal,
Figure FDA0002790173120000063
selected from the group consisting ofSubstituted or optionally substituted by 1,2 or more RaSubstituted of the following groups:
Figure FDA0002790173120000064
Figure FDA0002790173120000065
is a linking site;
Rahas the meaning as claimed in any of claims 1 to 3;
preferably, the solvent may be propionic acid, quinoline or fused imidazole;
preferably, an acetate salt, such as zinc acetate;
preferably, when
Figure FDA0002790173120000066
Selected from unsubstituted
Figure FDA0002790173120000067
When the compound 1, R1-NH2And/or R2-NH2Mixing with imidazole, heating for melting reaction, cooling, and washing a reaction product to obtain an electron acceptor;
preferably, when
Figure FDA0002790173120000068
Selected from the group optionally substituted by 1,2 or more RaSubstituted by
Figure FDA0002790173120000069
When the compound 1, R1-NH2And/or R2-NH2Mixing with propionic acid or heating and refluxing with zinc acetate under quinoline condition, precipitating to separate out solid, and washing to obtain electron acceptor;
preferably, said compound 1 and R1-NH2And/or R2-NH2The molar ratio of (A) to (B) may be 1 (1-10), for example1:(1-4)；
Preferably, R1-NH2And R2-NH2The same, for example, is at least one of 3-aminopyridine, aniline, 2-aminoimidazole and 9-aminoacridine;
preferably, the organic solvent is an organic solvent as an electron donor, for example, an organic solvent containing a lone pair of electrons, preferably dimethylacetamide, dimethylformamide, diethylformamide, N-methylpyrrolidone, dimethylsulfoxide, tetrahydrofuran, N-dimethylpropionamide, N-dimethylallylamine, N-diethylchloroformamide, N-diethylacrylamide, or N, N-diethylbenzamide;
preferably, the mass ratio of the compound 1 to the solid solvent is 1 (2-10);
preferably, the temperature of the heating and melting reaction is 100-160 ℃;
preferably, the time of the heating melting reaction is 20-60 min;
preferably, the washing comprises: the reaction product is washed with a mixture of ethanol and hydrochloric acid and filtered, and then washed with ethanol.
7. Use of the electron acceptor and/or the supramolecular complex as claimed in any one of claims 1 to 3 as photochromic material.
8. A photochromic material, characterized in that it comprises an electron acceptor according to any one of claims 1 to 3 or said supramolecular complex;
preferably, the photochromic material is a liquid, a solid, a polymer composite film, a polymer fiber, a polymer textile or a polymer composite coating containing the electron acceptor or the supramolecular complex.
9. A polymer composite film comprising the supramolecular complex or electron acceptor according to any one of claims 1 to 3 and a polymer;
preferably, the polymer may be a polymer that is soluble in the electron donor of any one of claims 1 to 3, such as an acrylic resin or polycarbonate, exemplified by at least one of polymethyl methacrylate, polyethyl methacrylate, polypropylene methacrylate, poly n-butyl methacrylate, polycarbonate;
preferably, the preparation method of the polymer composite membrane comprises the steps of mixing the supramolecular complex or the electron acceptor with a polymer material in an electron donor to obtain the polymer composite membrane;
preferably, the mass ratio of the supramolecular complex to the polymeric material may be 1 (10-130), such as 1 (20-60);
preferably, the mass to volume ratio of the polymeric material to the electron donor is 1g (3-10) ml, for example 1g (4-6) ml;
preferably, the preparation method of the polymer composite membrane comprises the steps of mixing the electron acceptor or the supramolecular complex with a polymer material in an electron donor, heating to obtain a clear solution, dropwise adding or coating the clear solution on a base material, and drying to obtain the polymer composite membrane;
preferably, the electron acceptor may be selected from 4-pyNDI, 3-pyNDI, 9-ardDI, 5-trzNDI, Cl4PDI or PhOPDI;
preferably, the electron donor has the meaning as described above, preferably DMF, DMAc;
preferably, the temperature of the heating is 60-90 ℃, such as 70-80 ℃; preferably, the heating is for a period of 0.5 to 2 hours, such as 1 to 1.5 hours;
preferably, the temperature of the drying is 50-60 ℃, e.g. 53-58 ℃; preferably, the drying time is from 5 to 8 hours, such as from 5 to 6 hours;
preferably, the substrate may be a glass slide.
10. Use of the supramolecular complex and electron acceptor according to any one of claims 1 to 3, the photochromic material according to claim 8 or the polymer composite film according to claim 9 in the fields of erasable paper, transparent glass window, organic glass smart window, photochromic spectacle lens, sun protection glasses, data storage and anti-aging and anti-counterfeiting, and use of the supramolecular complex and electron acceptor according to any one of claims 1 to 3, the photochromic material according to claim 8, polymer fiber, polymer textile or polymer composite coating in the field of military camouflage, such as clothing, equipment and the like, for environmental adaptation camouflage.
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