CN110143970B - Sulfur-rich dinaphthalene diimide derivative and preparation method and application thereof - Google Patents
Sulfur-rich dinaphthalene diimide derivative and preparation method and application thereof Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 40
- 239000011593 sulfur Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical class N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 title description 4
- HPJFXFRNEJHDFR-UHFFFAOYSA-N 22291-04-9 Chemical class C1=CC(C(N(CCN(C)C)C2=O)=O)=C3C2=CC=C2C(=O)N(CCN(C)C)C(=O)C1=C32 HPJFXFRNEJHDFR-UHFFFAOYSA-N 0.000 claims abstract description 53
- -1 binaphthyl diimide derivative Chemical class 0.000 claims abstract description 49
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 30
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- KVPDTCNNKWOGMZ-UHFFFAOYSA-N benzene-1,2,4,5-tetrathiol Chemical compound SC1=CC(S)=C(S)C=C1S KVPDTCNNKWOGMZ-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 239000003444 phase transfer catalyst Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 125000005842 heteroatom Chemical group 0.000 abstract description 4
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 2
- 150000003949 imides Chemical class 0.000 abstract description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 125000001624 naphthyl group Chemical group 0.000 abstract description 2
- 230000003595 spectral effect Effects 0.000 abstract description 2
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 57
- 239000000463 material Substances 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- OOYDTEGVMRPGRK-UHFFFAOYSA-N (9-octanoyl-8,10-dioxoheptadecan-9-yl)azanium;chloride Chemical group [Cl-].CCCCCCCC(=O)C([NH3+])(C(=O)CCCCCCC)C(=O)CCCCCCC OOYDTEGVMRPGRK-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000005669 field effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 2
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 2
- 235000010703 Modiola caroliniana Nutrition 0.000 description 2
- 244000038561 Modiola caroliniana Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NAZODJSYHDYJGP-UHFFFAOYSA-N 7,18-bis[2,6-di(propan-2-yl)phenyl]-7,18-diazaheptacyclo[14.6.2.22,5.03,12.04,9.013,23.020,24]hexacosa-1(23),2,4,9,11,13,15,20(24),21,25-decaene-6,8,17,19-tetrone Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N(C(=O)C=1C2=C3C4=CC=1)C(=O)C2=CC=C3C(C=C1)=C2C4=CC=C3C(=O)N(C=4C(=CC=CC=4C(C)C)C(C)C)C(=O)C1=C23 NAZODJSYHDYJGP-UHFFFAOYSA-N 0.000 description 1
- 241001600434 Plectroglyphidodon lacrymatus Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention relates to a sulfur-rich binaphthyl diAn imide derivative, a preparation method and an application thereof belong to the technical field of organic semiconductors. The sulfur-containing naphthalene diimide derivative, which is the sulfur-rich binaphthyl diimide derivative of the present invention, has a structure represented by the following formula (i). Wherein R is1And R2Is a cyano-containing group; r3、R4、R5、R6Each independently selected from alkyl groups having 1 to 20 carbon atoms. According to the sulfur-containing naphthalene diimide derivative, heteroatom functional groups (S) are introduced at 2,3,6 and 7 positions of a naphthalene ring, and cyano groups are introduced, so that the spectral absorption, HOMO and LUMO values of molecules of the naphthalene diimide derivative can be adjusted by the heteroatom functional groups, and the requirements of various functional materials are met.
Description
Technical Field
The invention relates to a sulfur-rich binaphthalene diimide derivative, and a preparation method and application thereof, and belongs to the technical field of organic semiconductors.
Background
Inorganic semiconductor materials have played an irreplaceable role as a cornerstone of information technology in the last century. Organic semiconductor materials have attracted attention since the 21 st century. In particular, many organic semiconductor materials are used in organic field effect transistors, organic solar cells, organic sensors, and the like.
Organic materials have significant advantages over inorganic materials: the organic material has good flexibility, toughness and elasticity, and is convenient to adapt to different processing requirements when being applied to various fields. In addition, the organic semiconductor material has higher mobility, and the application of the organic semiconductor material is promoted. At present, p-type organic semiconductor materials are developed more mature, and n-type organic semiconductor materials are developed relatively slowly. With the development of technology, n-type organic semiconductor materials are also gradually beginning to be researched and applied in various fields. The compound with the imide structure is a more n-type organic semiconductor material researched at present, wherein the Naphthalene Diimide (NDI) material attracts a great number of researchers by the characteristics of simple and convenient synthesis method, good solubility, good molecular planarity and the like.
In the last 70 th century, Hunig et al first conducted research on naphthalene diimide derivatives (NDIs). In the 90 s, naphthalene diimide derivatives (NDIs) have been widely recognized and developed, and more people use NDIs to prepare n-type organic semiconductor materials, so that the research of NDIs is more breakthrough.
The Naphthalene Diimide (NDI) compound has a unique structure, so that the naphthalene diimide compound has a good application prospect in the field of organic photoelectricity. The structural unit of the 1,4,5,8 naphthalene diimide has the conjugated characteristic of a plane four-membered ring, and the molecule of the naphthalene diimide has four amide groups which are electron withdrawing groups, so that the molecular unit of the naphthalene diimide can be used as an electron accepting unit. In addition, the naphthalene diimide has the characteristic of easy modification. This property provides a good basis for subsequent modification studies. Different groups may be modified on their N atoms to alter their properties. However, the current modification has a limited effect on the improvement of the mobility and field effect properties of the naphthalene diimide derivative.
In addition, compared with other aromatic systems with diimide structures (such as tereptarformamidinide and perylenetetracarboxylic diimide), the naphthalimide pi system is moderate, and the compound cannot have low solubility due to the large pi system, so that the synthesis, separation and purification of derivatives of the naphthalimide are difficult.
Disclosure of Invention
The invention provides a sulfur-containing naphthalene diimide derivative which has high mobility. The invention also provides a preparation method of the sulfur-containing naphthalene diimide derivative and application of the sulfur-containing naphthalene diimide derivative as an organic semiconductor.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a sulfur-containing naphthalene diimide derivative having a structure represented by the following formula (I):
wherein R is1And R2Is composed of
R3、R4、R5、R6Each independently selected from alkyl groups having 1 to 20 carbon atoms.
The sulfur-rich dinaphthalene diimide derivative is a sulfur-containing naphthaline diimide derivative, heteroatom functional groups (S) are introduced at 2,3,6 and 7 positions of a naphthalene ring, and cyano groups are introduced, so that the spectral absorption and HOMO and LUMO values of molecules of the naphthaline diimide derivative can be adjusted by the heteroatom functional groups, and the requirements of various functional materials are met.
Preferably, said R is3、R4、R5、R6At least one of them is C20H41. Further preferably, R3And R4 inAt least one is C20H41And/or R5And R6At least one of them is C20H41. Further preferably, R is3、R4、R5、R6Are all C20H41。
Preferably, C is20H41Is composed of
Wherein, C8H17And C10H21Both straight chain alkyl groups or branched alkyl groups, preferably both straight chain alkyl groups.
A preparation method of a sulfur-containing naphthalene diimide derivative comprises the following steps: mixing a cyano compound with a structure shown as a formula (II) and a DNDI compound with a structure shown as a formula (III) in an organic solvent for reaction to obtain the compound;
wherein R is3、R4、R5、R6Each independently selected from alkyl groups having 1 to 20 carbon atoms.
Preferably, said R is3、R4、R5、R6At least one of them is C20H41. Further preferably, R3And R4At least one of them is C20H41And/or R5And R6At least one of them is C20H41. Further preferably, R is3、R4、R5、R6Are all C20H41. Preferably C20H41The finally prepared sulfur-containing naphthalene diimide derivative has good solubility.
Preferably, C is20H41Is composed of
Wherein, C8H17And C10H21Both straight chain alkyl groups or branched alkyl groups, preferably both straight chain alkyl groups.
The molar ratio of the cyano compound with the structure shown as the formula (II) to the DNDI compound with the structure shown as the formula (III) is 2:1-3: 1.
The organic solvent is at least one of dichloromethane and tetrahydrofuran. Preferably, the organic solvent is tetrahydrofuran.
When a cyano compound with a structure shown as a formula (II) reacts with a DNDI compound with a structure shown as a formula (III), a catalyst is added, and the catalyst is a phase transfer catalyst. Preferably, the catalyst is aliquat336 phase transfer catalyst.
When the cyano compound with the structure shown in the formula (II) reacts with the DNDI compound with the structure shown in the formula (III), sodium carbonate is added. The mass ratio of sodium carbonate to the cyano compound was 0.25: 0.034.
The DNDI reagent is prepared by reacting an NDI compound shown as a formula (IV) with 1,2,4, 5-benzene tetrathiol;
wherein R is3、R4Each independently selected from alkyl groups having 1 to 20 carbon atoms.
Preferably, said R is3、R4At least one of them is C20H41. Further preferably, R is3、R4Are all C20H41。
Preferably, C is20H41Is composed of
Wherein, C8H17And C10H21Both straight chain alkyl groups or branched alkyl groups, preferably both straight chain alkyl groups.
The molar ratio of the NDI compound to 1,2,4, 5-benzenetetrathiol is 2: 1.
When the NDI compound shown as the formula (IV) reacts with 1,2,4, 5-benzene tetrathiol, a catalyst is added, and the catalyst is a phase transfer catalyst. Preferably, the catalyst is aliquat336 phase transfer catalyst.
Sodium carbonate is added when the NDI compound shown as the formula (IV) reacts with 1,2,4, 5-benzene tetrathiol.
The mass ratio of the sodium carbonate to the 1,2,4, 5-benzene tetrathiol is 0.25: 0.031.
The reaction of the NDI compound shown as the formula (IV) and 1,2,4, 5-benzene tetrathiol is a combination reaction.
The reaction of the NDI compound shown as the formula (IV) and 1,2,4, 5-benzene tetrathiol is carried out in an organic solvent. The organic solvent is at least one of dichloromethane and tetrahydrofuran. Preferably, the organic solvent is tetrahydrofuran.
The organic solvent used in the reaction of the cyano compound having the structure shown in the formula (II) and the DNDI compound having the structure shown in the formula (III) is the first organic solvent. The organic solvent adopted in the reaction of the NDI compound shown as the formula (IV) and 1,2,4, 5-benzene tetrathiol is a second organic solvent. The first organic solvent and the second organic solvent may be the same or different. Preferably, the first organic solvent and the second organic solvent are both tetrahydrofuran.
The amount of the first organic solvent used was 20L per 34g of the cyano compound represented by (II).
The amount of the second organic solvent used was 20L per 0.3mol of the NDI compound represented by the formula (IV).
The temperature of the reaction of the cyano compound with the structure shown as the formula (II) and the DNDI compound with the structure shown as the formula (III) is 10-40 ℃. The reaction time is 30-50 min.
When the cyano compound with the structure shown in the formula (II) reacts with the DNDI compound with the structure shown in the formula (III), a solution of the DNDI compound with the structure shown in the formula (III) and a solution of the cyano compound with the structure shown in the formula (II) are mixed for reaction.
The mixing is to drop the solution of the cyano compound with the structure shown in the formula (II) into the solution of the DNDI compound with the structure shown in the formula (III).
The solvent in the solution of the cyano compound with the structure shown in the formula (II) is dichloromethane or tetrahydrofuran. Preferably, tetrahydrofuran is used.
The solvent in the solution of the DNDI compound with the structure shown in the formula (III) is dichloromethane or tetrahydrofuran. Preferably, tetrahydrofuran is used.
When a cyano compound with a structure shown as a formula (II) reacts with a DNDI compound with a structure shown as a formula (III), spot plate detection is carried out every 10 min.
The temperature of the NDI compound shown in the formula (IV) and 1,2,4, 5-benzene tetrathiol in the reaction is 10-40 ℃. The reaction time is 30-50 min.
When the NDI compound shown as the formula (IV) reacts with 1,2,4, 5-benzene tetrathiol, a solution of the NDI compound shown as the formula (IV) is mixed with a solution of the 1,2,4, 5-benzene tetrathiol, a sodium carbonate solution and a catalyst for reaction.
During mixing, dropwise adding a solution of 1,2,4, 5-benzene tetrathiol into a mixed solution of a solution of an NDI compound shown as a formula (IV), a sodium carbonate aqueous solution and a catalyst.
The solvent in the solution of the NDI compound shown in the formula (IV) is dichloromethane or tetrahydrofuran. Preferably, tetrahydrofuran is used.
The solvent in the solution of the 1,2,4, 5-benzene tetrathiol is dichloromethane or tetrahydrofuran. Preferably, tetrahydrofuran is used.
When the NDI compound shown as the formula (IV) reacts with 1,2,4, 5-benzene tetrathiol, the spot plate detection is carried out every 10 min.
The application of the sulfur-containing naphthalene diimide derivative as an organic semiconductor.
The sulfur-containing naphthalene diimide derivative of the present invention has high mobility and good field effect performance. The preparation method of the sulfur-containing naphthalene diimide derivative has simple steps, and is convenient for large-scale popularization for industrial production. The invention introduces dicyano group on DNDI nucleus by simple chemical combination and nucleophilic substitution reaction, greatly enhances the interaction between molecules, is beneficial to molecule accumulation and forms long-range ordered electron transmission channel.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention easier to understand, the present invention will be described in detail with reference to specific embodiments.
Example 1
The structure of the sulfur-containing naphthalene diimide derivative (DCNDNDI) of this example is shown as follows:
the preparation principle of the sulfur-containing naphthalene diimide derivative of this example is as follows:
the preparation method of the sulfur-containing naphthalene diimide derivative of the present embodiment includes the following steps:
1) taking a 100mL eggplant-shaped reaction bottle, adding magnetons with proper sizes, and then adding 20mL dichloromethane; 345mg (0.3mmol, 1equiv) of tetrabromo-substituted naphthalene diimide compound (NDI reagent) shown in the formula 1 and 5g of Na with the mass fraction of 5 percent are sequentially added into an eggplant-shaped reaction bottle2CO3Aqueous solution, 1-2 drops of aliquat336 phase transfer catalyst;
dissolving 31mg (0.15mmol, 0.5equiv) of 1,2,4, 5-benzenetetrathiol in 30mL of dichloromethane to prepare a dichloromethane solution of 1,2,4, 5-benzenetetrathiol; the prepared dichloromethane solution of 1,2,4, 5-benzene tetrathiol is transferred to a liquid separator, and slowly dropped into the eggplant-shaped reaction bottle, so that the reaction liquid immediately turns into light red. Stirring at normal temperature to react; and then performing plate detection every 10min, wherein the chromatographic solution adopted during the plate detection is petroleum ether and dichloromethane in a volume ratio of 1: 1, and (b) a mixed solution. Little yellow tail was detected by dot plate after 40min of reaction. At this time, only a small amount of tetrabromo-substituted naphthalene diimide compound (NDI reagent) was contained in the reaction mixture, and the reaction was stopped. Namely the reaction is finished after 40min of reaction.
The reacted reaction solution was spin-dried using a rotary evaporator. And dissolving the obtained chromatographic solution, purifying by a chromatographic column (silica gel column, wet column loading) to obtain purified mauve liquid, and spin-drying by a rotary evaporator to obtain a mauve solid DNDI intermediate (shown in formula 2).
2) A reaction flask is taken, a magneton with a proper size is added, and weighed 5ml of malononitrile (d ═ 1.049g/ml,1eq.) and 4.8ml of carbon disulfide (d ═ 1.26g/ml,1eq.) and 6.35g of NaOH (2eq.) are sequentially added, and nitrogen is filled for protection. Then 30ml of ultra-dry 1, 4-dioxane is extracted by an injector and injected into a reaction bottle, the reaction is stirred at normal temperature, NaOH particles are continuously dissolved in the stirring process, the solution becomes light yellow, and a large amount of light yellow precipitate is generated in the reaction bottle after 1.5 hours. And (3) spin-drying the mixture in the reaction flask by using a rotary evaporator, and then recrystallizing to obtain the cyano compound (shown in the formula 3).
3) Adding magnetons with proper size into a 100mL eggplant-shaped reaction bottle, and injecting 20mL dichloromethane; then 34mg (3eq.) of the cyano compound obtained in step 2), 5g of Na with a mass fraction of 5%, are added to an eggplant-shaped reaction flask2CO3Aqueous solution, 1-2 drops of aliquat336 phase transfer catalyst; stirring to mix them uniformly.
Then, a weighed amount of 116mg (1eq.) of the DNDI intermediate obtained in step 1) above was dissolved in 30mL of dichloromethane to prepare a solution, which was transferred to a dispenser and then slowly added dropwise to the eggplant-shaped reaction flask (to which dichloromethane, a cyano compound, an aqueous sodium carbonate solution, and a catalyst had been added), and the reaction solution was stirred at room temperature to change from purple to purple and then to blue.
The spot plate detection is carried out every 10min during the reaction process. The chromatographic solution adopted in the spot plate detection is petroleum ether and dichloromethane in a volume ratio of 1: 1, and (b) a mixed solution. After 40min of reaction, the plate was spotted and the purple tail was found to be very small. At this point, the reaction was stopped with only a small amount of DNDI intermediate in the reaction mixture. Namely the reaction is finished after 50 min.
And (3) carrying out spin-drying on the reaction liquid by using a rotary evaporator, dissolving by using the chromatographic solution, purifying by using a chromatographic column (silica gel column) to obtain a dark blue liquid in which the target product is located, and carrying out spin-drying by using the rotary evaporator to obtain a dark blue solid, namely the target product, namely the naphthalimide derivative DCNDI (shown in formula 4).
The yield of the sulfur-containing naphthalene diimide derivative (DCNDNDI) of this example was calculated to be 48%.
The nuclear magnetic data of the sulfur-containing naphthalene diimide derivative (DCNDNDI) of this example are as follows:
1H NMR(400MHz,CDCl3)7.26(s，2H)，4.20(d,J＝4Hz,8H)，1.98-1.96(m, 4H),1.25(d,J＝12Hz,128H),0.87-0.84(m,24H)。
example 2
The sulfur-containing naphthalene diimide derivative of this example was the same as the naphthalene diimide derivative of example 1.
The method for preparing the sulfur-containing naphthalene diimide derivative of this example differs from the method for preparing the naphthalene diimide derivative of example 1 only in that 20mL of tetrahydrofuran is used instead of 20mL of dichloromethane in step 1), and the others are the same as those in example 1.
The yield of the sulfur-containing naphthalene diimide derivative (DCNDNDI) in this example was 51%.
The nuclear magnetic data of the sulfur-containing naphthalene diimide derivative (DCNDNDI) of this example are as follows:
1H NMR(400MHz,CDCl3)7.26(s，2H)，4.20(d,J＝4Hz,8H)，1.98-1.96(m, 4H),1.25(d,J＝12Hz,128H),0.87-0.84(m,24H)。
example 3
The sulfur-containing naphthalene diimide derivative of this example was the same as the naphthalene diimide derivative of example 1.
The method for preparing the sulfur-containing naphthalene diimide derivative of this example differs from the method for preparing the naphthalene diimide derivative of example 1 only in that 20mL of tetrahydrofuran is used instead of 20mL of dichloromethane in step 3), and the others are the same as those in example 1.
The yield of the sulfur-containing naphthalene diimide derivative (DCNDNDI) in this example was 49%.
The nuclear magnetic data of the sulfur-containing naphthalene diimide derivative (DCNDNDI) of this example are as follows:
1H NMR(400MHz,CDCl3)7.26(s，2H)，4.20(d,J＝4Hz,8H)，1.98-1.96(m, 4H),1.25(d,J＝12Hz,128H),0.87-0.84(m,24H)。
example 4
The sulfur-containing naphthalene diimide derivative of this example was the same as the naphthalene diimide derivative of example 1.
The method for producing the sulfur-containing naphthalene diimide derivative of this example differs from the method for producing the naphthalene diimide derivative of example 1 in that:
step 1) was performed using 20mL of tetrahydrofuran instead of 20mL of dichloromethane. Step 3) was performed using 20mL of tetrahydrofuran instead of 20mL of dichloromethane. The others are the same as in example 1.
The yield of the sulfur-containing naphthalene diimide derivative (DCNDNDI) in this example was 53%.
The nuclear magnetic data of the sulfur-containing naphthalene diimide derivative (DCNDNDI) of this example are as follows:
1H NMR(600MHz,CDCl3)7.18(s,2H),7.05(d,J＝35.7Hz,3H),6.86(s, 4H),4.21(s,8H),1.94(s,4H),1.21(s,135H),0.94-0.71(m,25H)。
test examples
The sulfur-containing naphthalene diimide derivative (DCNDI) obtained in example 1 was subjected to the following tests:
the sulfur-containing naphthalene diimide derivative (DCNDNDI) prepared in example 1 was used to prepare a one-electron solar device: ITO/Al/DCNDI/Al, the electron mobility was measured to be 0.051cm2/Vs。
It can be seen that the sulfur-containing naphthalene diimide derivative (DCNDNDI) prepared by the method of the present invention has high electron mobility.
Claims (1)
1. A method for preparing a sulfur-containing naphthalene diimide derivative, characterized in that the sulfur-containing naphthalene diimide derivative has a structure represented by the following formula (I):
wherein R is1And R2Is composed of
R3、R4、R5、R6Are all C20H41Said C is20H41Is composed of
C8H17And C10H21Are all straight chain alkyl;
the preparation method comprises the following steps: mixing a cyano compound with a structure shown as a formula (II) and a DNDI compound with a structure shown as a formula (III) in an organic solvent for reaction to obtain the compound;
wherein R is3、R4、R5、R6Are all C20H41Said C is20H41Is composed of
C8H17And C10H21Are all straight chain alkyl;
the molar ratio of the cyano compound with the structure shown in the formula (II) to the DNDI compound with the structure shown in the formula (III) is 3: 1;
the organic solvent is tetrahydrofuran;
adding a catalyst when a cyano compound with a structure shown as a formula (II) reacts with a DNDI compound with a structure shown as a formula (III), wherein the catalyst is a phase transfer catalyst;
when a cyano compound with a structure shown as a formula (II) reacts with a DNDI compound with a structure shown as a formula (III), sodium carbonate is added;
the temperature of the reaction of the cyano compound with the structure shown as the formula (II) and the DNDI compound with the structure shown as the formula (III) is 10-40 ℃; the reaction time is 30-50 min;
the DNDI compound is prepared by reacting an NDI compound shown as a formula (IV) with 1,2,4, 5-benzenetetrathiol;
wherein R is3、R4Are all C20H41Said C is20H41Is composed of
C8H17And C10H21Are all straight chain alkyl;
when the NDI compound shown as the formula (IV) reacts with 1,2,4, 5-benzene tetrathiol, a solution of the NDI compound shown as the formula (IV) is mixed with a solution of the 1,2,4, 5-benzene tetrathiol, a sodium carbonate solution and a catalyst for reaction;
during the mixing, dropwise adding a solution of 1,2,4, 5-benzene tetrathiol into a mixed solution of a solution of an NDI compound shown as a formula (IV), a sodium carbonate aqueous solution and a catalyst;
the catalyst is a phase transfer catalyst;
the temperature of the NDI compound shown as a formula (IV) in the reaction with 1,2,4, 5-benzene tetrathiol is 10-40 ℃; the reaction time is 30-50 min;
the mass ratio of sodium carbonate to the cyano compound is 0.25: 0.034; the mass ratio of the sodium carbonate to the 1,2,4, 5-benzene tetrathiol is 0.25: 0.031;
the molar ratio of the NDI compound to 1,2,4, 5-benzenetetrathiol is 2: 1.
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