Organic phosphorus heteropolycyclic aromatic hydrocarbon with ylide bond and preparation and application of organic phosphorus heteropolycyclic aromatic hydrocarbon

Abstract

The invention belongs to the field of photoelectric materials, and particularly discloses an organic phosphorus heterocyclic aromatic hydrocarbon functional material which is at least one compound with the structural formula # imgabs0 # shown in the formula 1-A and the formula 1-B. In the formula 1-A and the formula 1-B, R1 and R2 are independently selected from C1-C24 alkyl groups, C3-C24 cycloalkyl groups, halogenated C1-C24 alkyl groups, aryl groups, heterocyclic rings or fused rings. The invention also provides preparation and application of the structure. The invention adopts a mild [2 + 3] or [3 + 3] phosphorus cyclization method to modularly prepare the phosphorus-doped five / six-membered ring lambda5-phosphine, and the modular synthesis of phosphorus ylide allows the regulation and control of the physicochemical properties of the phosphorus ylide to endow the phosphorus ylide with interesting electronic characteristics, such as strong visible-near infrared and ultraviolet visible light absorption, and the like. The redox characteristic can be regulated and controlled; and the dipole moment is relatively large.

Description

Technical Field

[0001] The present invention relates to the field of functional molecular materials, in particular to molecular materials with photoelectric properties Background Art

[0002] In the context of the rapid development of organophosphorus heterocyclic polycyclic aromatic hydrocarbons, less attention has been paid to the ylide bonds within the phosphorus heterocycle. This type of chemical bond is considered to be too reactive, but its ability to effectively separate charges has been discussed. 5 Various reports on the properties of -phosphines (also called phosphinophenyls) have shed new light on this "old" heterocycle. In related systems, the bonding topology can be described as a combination of two extreme forms: (1) a Hückel-type aromatic system (A); and (2) a phosphorus ylide ring with a negatively charged carbon skeleton (A').

[0003]

[0004] Phosphobenzene and its π-extended form have been widely reported, but the methods for synthesizing polycyclic phosphorus ylides are limited. The only synthetic methods require the use of relatively strong chemical conditions to synthesize phosphorus heterocyclic precursors or to carry out phosphorus cyclization, such as strong bases (n-butyl lithium, tert-butyl lithium and potassium tert-butoxide, etc.), high temperature and high pressure, etc.

[0005] In summary, the prior art does not have a relatively mild method for preparing phosphorus heterocyclic five-membered / six-membered ring λ 5 - Synthesis method of phosphine materials. Summary of the invention

[0006] In view of the problems existing in the prior art, the first purpose of the present invention is to provide an organic phosphorus heteropolycyclic aromatic hydrocarbon with a ylide bond, aiming to provide a material with a completely new structure and excellent photoelectric properties.

[0007] The second object of the present invention is to provide a method for preparing the organic phosphorus heteropolycyclic aromatic hydrocarbon having a ylide bond and its application in optoelectronic materials.

[0008] The invention also provides a photoelectric material.

[0009] An organic phosphorus heteropolycyclic aromatic hydrocarbon having a ylide bond, which is a compound having at least one of the structural formulas 1-A and 1-B:

[0010]

[0011] In formula 1-A and formula 1-B, R1 and R2 are independently selected from C1-C 24 Alkyl, C3-C 24 Cycloalkyl, halogenated C1-C 24 Alkyl, aryl, heterocyclic or condensed ring;

[0012] The R3, R4 and R5 are independently selected from H, halogen, C1-C 24 Alkyl, C3-C 24 Cycloalkyl, C2-C 24 Alkynyl, halogenated C1-C 24 Alkyl, aryl, heterocyclic or condensed ring;

[0013] The ring A is a monocyclic ring A including a five-membered heterocyclic ring, a benzene ring, or a six-membered heterocyclic ring, or a combined ring A formed by combining two or more monocyclic rings A;

[0014] The R6 and R7 are independently electron-withdrawing groups, or are cyclized to form a monocyclic ring B including a five-membered carbocyclic ring, a five-membered heterocyclic ring, a six-membered carbocyclic ring, or a six-membered heterocyclic ring, or a fused ring B formed by merging two or more monocyclic rings B;

[0015] The monocyclic ring A, monocyclic ring B, fused ring A and fused ring B are allowed to have electron withdrawing groups.

[0016] The present invention provides a novel phosphorus-containing five-membered / six-membered ring λ 5 -phosphine, and the new compound has both excellent synthesizable advantages and photoelectric properties.

[0017] The C1-C 24 The alkyl group is a straight chain or branched chain alkane group having 1 to 24 carbon atoms, and may further be an isopropyl group, a tert-butyl group, or the like. 24 The cycloalkyl group is a three-membered to six-membered monocyclic alkane group of the above carbon number, or a spirocyclic hydrocarbon group or a bridged hydrocarbon group of the above carbon number; it may further be a cyclohexyl group. 24 The alkynyl group is preferably an ethynyl group having an aryl group.

[0018] The aryl group may be a benzene ring. The heterocycle may be at least one of a saturated heterocycle and an aromatic heterocycle. The heteroatom in the heterocycle may be N, S, O, etc. Further, the heterocycle may be a five-membered heterocycle, a six-membered heterocycle, etc. The five-membered heterocycle may be, for example, a succinimide ring, imidazole, thiadiazole, and triazole. The six-membered heterocycle may be, for example, an aromatic or non-aromatic ring containing one or more heteroatoms.

[0019] In the present invention, in Formula 1-A and Formula 1-B, R1 and R2 are independently selected from C1-C 24 Alkyl, C3-C 24 Cycloalkyl, halogenated C1-C 24 Alkyl, aryl, heterocyclic or condensed ring.

[0020] In the present invention, R1 and R2 may be the same substituent.

[0021] In the present invention, R3, R4 and R5 are independently selected from H, halogen, C1-C 24 Alkyl, C3-C 24 Cycloalkyl, C2-C 24 Alkynyl, halogenated C1-C 24 Alkyl, aryl, heterocyclic or condensed ring.

[0022] Furthermore, R3, R4 and R5 are independently H, bromine atoms or thiophene.

[0023] In the present invention, the ring A may be a five-membered ring with an electron-withdrawing group, a six-membered ring with an electron-withdrawing group, or a fused ring formed by merging 2 to 4 single rings. In the present invention, as an optional scheme, the ring A may include the following structural fragments:

[0024]

[0025] Wherein, the R is H, phenyl, alkyl-substituted phenyl or an electron-withdrawing group, and the electron-withdrawing group can further be cyano, carbonyl, nitro, ester, trifluoromethyl or amide.

[0026] Preferably, the compound of formula 1-A comprises at least one compound of the following structure;

[0027]

[0028] In the present invention, the R6 and R7 are cyclized to form a five-membered carbon ring or a six-membered carbon ring; and the five-membered carbon ring or the six-membered carbon ring is allowed to have an electron-withdrawing group, or be combined with at least one of other five-membered heterocycles, six-membered heterocycles, and benzene rings.

[0029] As an optional scheme of the present invention, the formula 1-B is at least one compound having the following structural formula; wherein the R is H, phenyl, alkyl-substituted phenyl or an electron-withdrawing group, and the electron-withdrawing group can further be a cyano group, a carbonyl group, a nitro group, an ester group, a trifluoromethyl group or an amide group:

[0030]

[0031] The present invention also provides a method for mildly preparing the phosphorus ylide functional compound, wherein raw materials a and raw materials b are subjected to a cyclization reaction to obtain product a, wherein the product a is of formula 1-A and / or formula 1-B in which R3 to R5 are H.

[0032] The raw material a is a compound having at least one structure of formula 2-A and formula 2-B; the raw material b is

[0033] A compound of formula 3;

[0034]

[0035] X in the formula 2-A and formula 2-B is Br, Cl or I; more preferably Br; the selection reactions of ring A, R1~R2 and R6~R7 in the formula 2-A, formula 2-B and formula 3 are the same as those in formula 1-A and formula 1-B.

[0036] The molar ratio of the raw material a to the raw material b is 1:1 to 1.3;

[0037] Preferably, the temperature of the cyclization reaction is 80 to 120°C, more preferably 110°C.

[0038] Preferably, the cyclization reaction is carried out under the catalysis of lithium acetate and / or palladium acetate.

[0039] Furthermore, the cyclization reaction is carried out in the presence of lithium acetate and palladium acetate, wherein the amount of lithium acetate added relative to the raw material a is 3 to 5 eqv, and the amount of palladium acetate added is 0.005 to 0.015 eqv.

[0040] In another embodiment of the present invention, product a is subjected to a halogenation reaction with a halogenating agent to obtain product b in which at least one substituent among R3 to R5 is a halogen;

[0041] Preferably, the halogenating agent is at least one of NBS, NCS, and NIS;

[0042] Preferably, the temperature of the halogenation reaction conditions is 50-90°C.

[0043] The present invention has shown that the reaction activities of halogens at different positions in R3 to R5 are different, and the halogenation reaction activities are respectively R3>R4>R5. Therefore, the present invention can be based on the use of a simple halogenation reagent reaction equivalent, that is, it can be considered to regulate the modification behavior.

[0044] For example, in the present invention, the dosage of the halogenating agent is 1 to 1.3 eqv, and the product b1 in which R3 is a halogen and R4 and R5 are H is synthesized;

[0045] Alternatively, the halogenating agent is added in an equivalent amount of 2 to 2.5 eqv to synthesize product b2 in which R3 and R4 are halogens and R5 is H;

[0046] Alternatively, the added equivalent of the halogenating agent is 3 eqv or more, and the product b3 in which R3, R4 and R5 are halogens is synthesized.

[0047] In another embodiment of the present invention, product b and a nucleophilic reagent that is a donor of substituent a are subjected to a nucleophilic coupling reaction to obtain product c in which at least one halogen in R3 to R5 of product b is replaced by substituent a; said substituent a includes C1-C24 Alkyl, C3-C 24 Cycloalkyl, C2-C 24 Alkynyl, halogenated C1-C 24 At least one of an alkyl group, an aryl group, a heterocyclic ring or a condensed ring;

[0048] Preferably, the substituent a donor is added in an equivalent amount of 1 to 1.3 eqv to synthesize product c1 in which R3 is substituent a;

[0049] Alternatively, the substituent a donor is added in an equivalent amount of 2 to 2.5 eqv to synthesize product c2 in which R3 and R4 are substituent a;

[0050] Alternatively, the substituent a donor is added in an equivalent amount of 3 equivalents or more (or further can be 3.3 to 3.6 eqv) to synthesize product c3 in which R3, R4, and R5 are substituent a.

[0051] In the present invention, the substituent a donor nucleophilic reagent can be an organic tin reagent containing substituent a, and its optional structural formula is shown in Formula 4; thus, the product b and the substituent a donor can be subjected to Stille coupling reaction to obtain product c. In the formula 4, R6 is a C1-C6 alkyl group; Ra is a substituent a.

[0052] In the present invention, the Stille coupling reaction is carried out in a catalyst, and the catalyst may include at least one of Pd(PPh3)4 and CuI.

[0053] Furthermore, the usage equivalent of the catalyst may be 0.01 to 0.1 eqv; further, it may be 0.03 to 0.06 eqv.

[0054] Preferably, the optimal temperature range of the Stille coupling reaction is 80-110°C; more preferably 105°C.

[0055] The present invention also provides the application of the phosphorus ylide functional compound, which is used for preparing photoelectric materials.

[0056] The present invention also provides a photoelectric material, which contains the phosphorus ylide functional compound of the present invention or is prepared by the phosphorus ylide functional compound.

[0057] Beneficial Effects

[0058] The phosphorus ylide functional molecule provided by the present invention is mainly characterized in that the phosphorus atom is highly involved in conjugation, so that the highly active phosphorus ylide molecule becomes stable.

[0059] The synthesis method provided by the present invention has relatively mild conditions and a wide range of substrate extension. More importantly, the modular synthesis of phosphorus ylides allows the regulation of their physicochemical properties, giving them interesting electronic characteristics, such as full coverage of ultraviolet-visible light absorption and tunable redox properties. Therefore, this method can prepare functional dyes with nonlinear optical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of formula 1-A-7-3H prepared in Example 1;

[0061] Figure 2 is the carbon NMR spectrum of formula 1-A-7-3H prepared in Example 1;

[0062] Figure 3 is the nuclear magnetic resonance phosphorus spectrum of formula 1-A-7-3H prepared in Example 1;

[0063] Figure 4 is the hydrogen nuclear magnetic resonance spectrum of formula 1-B-5-3H prepared in Example 2;

[0064] Figure 5 is the carbon NMR spectrum of formula 1-B-5-3H prepared in Example 2;

[0065] Figure 6 is the nuclear magnetic resonance phosphorus spectrum of formula 1-B-5-3H prepared in Example 2;

[0066] Figure 7 is the single crystal structure of formula 1-A-7-3H obtained in Example 1;

[0067] Figure 8 is the single crystal structure of formula 1-B-5-3H obtained in Example 2;

[0068] Fig. 9 It is the electrochemical test diagram of the compound prepared in Example 1 and Example 2;

[0069] Fig.10 It is the nonlinear optical test result diagram of Formula 1-B-5 and Formula 1-B-7. DETAILED DESCRIPTION

[0070] Part I: Synthesis of Product A Where R3-R5 is H

[0071] Example 1 Synthesis of Formula 1-A-7-3H:

[0072]

[0073] Under an inert atmosphere, raw material a (Formula 2-A-1, 465 mg, 1 mmol) and lithium acetate (264 mg, 4 mmol) were dissolved in 20 mL of anhydrous dimethyl sulfoxide, stirred at room temperature for 1 h, and raw material b (1,1'-bis(diphenylphosphino)ferrocene, 554 mg, 1 mmol) and palladium acetate (2 mg, 0.01 mmol) were added, and the mixture was stirred magnetically and heated to 110 °C for overnight reaction. After the reaction was completed, 15 mL of water was added to quench the reaction, and the mixture was extracted with dichloromethane (30 mL), and the organic phase was collected and dried with anhydrous sodium sulfate. The obtained organic solution was dried by rotary evaporation, and the crude product was purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 2:1) to obtain a purple solid formula 1-A-7-3H (194 mg, 35%).

[0074] 1 H NMR (400MHz, CDCl3) δ7.84(m,5H),7.75(s,1H),7.71(m,2H),7.59(m,4H),7.46(m,1 H),7.29(m,2H),6.70(m,1H),6.58(m,1H),6.53(m,1H),2.75(m,2H),1.17(m,12H);

[0075] 13 C NMR (100MHz, CDCl3) δ167.5,153.8,147.3,137.6,133.7,132.9,132.8,130.2,12 9.8,129.7,124.0,122.8,117.5,117.4,113.9,113.8,112.4,112.3,29.3,24.1;

[0076] 31 P NMR (162MHz, CDCl3): δ4.1; HR-MS (MALDI-TOF) m / z: Calcd for C 37 H 32 NO2P[M] + :553.2171, Found:553.2173(error=0.04ppm).

[0077] Example 2 Synthesis of Formula 1-B-5-3H:

[0078]

[0079] Compared with Example 1, the difference is that the raw material a is replaced (in this case, an equimolar amount of formula 2-B-1), and finally a blue solid formula 1-B-5-3H is obtained with a yield of 75%.

[0080] 1 H NMR (400MHz, CDCl3) δ8.66(d,J=7.3Hz,1H),8.50(d,J=8.2Hz,1H),8.10(d,J=8.2Hz,1H),7.88(m,1H),7.50(m,1H),7.35 (d,J=7.7Hz,2H),7.21(s,1H),6.66(s,1H),6.58(m,1H),2.86(m,4H),1.35(d,J=5.2Hz,4H),1.31(m,8H),1.20(m,12H);

[0081] 13 C NMR (100MHz, CDCl3) δ163.9,163.2,146.0,139.9,139.9,133.9,130.9,130.7,130.7,129.3,128.9,128.8,128.8,128.6,127.9,127.9,126.9 ,126.1,126.0,123.9,121.9,121.1,120.7,120.5,120.4,119.2,119.1 ,116.1,116.0,114.0,,29.6,29.0,27.0,26.5,24.0,23.9,16.1,15.4;

[0082] 31 P NMR (162MHz, CDCl3): δ15.5; HR-MS (MALDI-TOF) m / z: Calcd for C 35 H 38 NO2P[M] + :535.2640, Found:535.2639 (error=-0.02ppm).

[0083] According to the method of Example 1 above, the raw materials of raw material a (Formula 2-A, Formula 2-B) and raw material b (Formula 3) are replaced to synthesize the following products of Formula 1-A and Formula 1-B, respectively, and the yield of each product is as follows:

[0084]

[0085]

[0086] Part II: Case of Product B where some or all of R3 to R5 are halogens

[0087] Example 3 Synthesis of Formula 1-B-5-1Br:

[0088]

[0089] Under an inert atmosphere, formula 1-B-5-3H (603 mg, 1 mmol) was dissolved in 30 mL of anhydrous carbon tetrachloride, and N-bromosuccinimide (196 mg, 1.1 mmol) was added to the reaction solution in batches within 10 minutes, stirred on a stirring device and kept at 75°C for 4 hours. After the reaction was completed, 15 mL of ultrapure water was added to quench the reaction, extracted with dichloromethane (30 mL), the organic phase was collected and dried with anhydrous sodium sulfate, the organic solvent was removed by a rotary evaporator, and the crude product was separated and purified by column chromatography, and the polarity of the eluent used was petroleum ether: dichloromethane = 1:1, and finally a blue solid formula 1-B-5-1Br (562 mg, 83%) was obtained.

[0090] 1 H NMR (400MHz, CDCl3) δ8.64(m,1H),8.54(m,1H),8.13(m,1H),7.94(m,1H),7.82(m,3H),7.72(m,3H),7.59( m,4H),7.47(m,1H),7.32(d,J=8.3Hz,2H),7.14(d,J=9.0Hz,1H),6.50(m,1H),2.76(m,2H),1.16(m,12H);

[0091] 13 C NMR (100MHz, CDCl3) δ163.3,162.7,145.5,137.4,133.9,133.9,133.8,132.5,131.9,130.4,129.7,129. 5,129.5,129.0,128.9,128.6,127.4,126.7,123.9,123.5,122.6,121.8,119.0,117.1,29.6,29.0,23.9;

[0092] 31 P NMR (162MHz, CDCl3): δ-4.4; HR-MS (MALDI-TOF) m / z: Calcd for C 41 H 33 BrNO2P[M] + :681.1432, Found:681.1433(error=+0.01ppm).

[0093] Example 4 Synthesis of Formula 1-B-5-2Br:

[0094]

[0095] Compared with Example 3, the only difference is that the equivalent of N-bromosuccinimide used is 2eqv, and the other operations are the same as Example 3. Finally, a blue solid formula 1-B-5-2Br is obtained with a yield of 89%.

[0096] 1 H NMR (400MHz, CDCl3) δ8.63(d,J=7.6Hz,1H),8.57(d,J=8.1Hz,1H),8.09(d,J=8.2Hz,1H),7.93(m,1H), 7.83(m,4H),7.72(m,3H),7.61(m,4H),7.48(m,1H),7.32(d,J=7.8Hz,2H),2.74(m,2H),1.16(m,12H);

[0097] 13 C NMR (100MHz, CDCl3) δ163.6,163.2,145.1,137.0,133.9,133.8,132.6,132.6,130.6,130.1,129.7,129. 7,129.6,129.5,129.5,129.4,127.2,126.3,125.1,124.8,123.9,123.1,120.6,116.2,29.6,29.1,23.9;

[0098] 31 P NMR (162MHz, CDCl3): δ-4.7; HR-MS (MALDI-TOF) m / z: Calcd for C 41 H 32 Br2NO2P[M] + :761.0517, Found:761.0518(error=+0.01ppm).

[0099] Example 5 Synthesis of Formula 1-B-5-3Br:

[0100]

[0101] Compared with Example 3, the only difference is that the equivalent of N-bromosuccinimide used is 3eqv, and the other operations are the same as Example 3 to obtain a blue solid formula 1-B-5-3Br with a yield of 99%.

[0102] 1H NMR(400MHz, CDCl3)δ9.40(d,J=8.5Hz,1H),8.75(d,J=8.6Hz,2H),8.04(s,1H),7.85(m,1H)7.79(m,4H),7.72( m,2H),7.60(m,4H),7.31(s,1H),4.17(m,2H),4.10(m,2H),1.93(m,4H),1.38(m,8H),1.26(s,4H),0.94(m,6H);

[0103] 13 C NMR (100MHz, CDCl3) δ163.6,163.0,145.6,136.0,134.0,133.9,133.8,132.6,130.5,129.7,129.6,1 29.5,129.1,129.0,127.5,124.4,124.0,123.8,123.6,122.7,121.9,118.9,117.2,29.7,29.1,24.0;

[0104] 31 P NMR (162MHz, CDCl3): δ-4.9; HR-MS (MALDI-TOF) m / z: Calcd for C 47 H 42 Br3N2O3P[M] + :952.0463, Found:952.0461 (error=-0.02ppm).

[0105] Part III: Stille coupling of halogens at positions R3 to R5 in product B

[0106] Example 6 Synthesis of Formula 1-B-5-Th:

[0107]

[0108] Under an inert atmosphere, 1-B-5-Br (50 mg, 0.073 mmol), tributyl (2-thienyl) tin (33 mg, 0.088 mmol), tetrakis triphenylphosphine palladium (4 mg, 0.004 mmol) were dissolved in 3 mL of anhydrous toluene, stirred magnetically and refluxed for 3 h. After the reaction was completed, the reaction solution was concentrated, and the crude product was purified by column chromatography on silica gel (eluent polarity was petroleum ether: dichloromethane = 1:1), and finally a blue solid formula 1-B-5-Th (10.5 mg, 21%) was obtained.

[0109] 1H NMR (400MHz, CDCl3) δ8.61(d,J=7.5Hz,1H),8.51(d,J=8.1Hz,1H),8.13(m,1H),7.92(m,1H),7.75(m,8H),7.5 9(m,4H),7.47(m,1H),7.39(m,1H),7.32(d,J=8.4Hz,2H),6.65(d,J=10.4Hz,2H),2.79(m,2H),1.17(m,12H);

[0110] 13 C NMR (100MHz, CDCl3) δ164.2,163.1,146.1,140.1,134.5,134.1,133.9,133.8,133.7,133.6,133.2,133.1,132.4,130.7 ,130.4,130.3,129.8,129.7,129.5,129.5,129.0,121.4,121.2,120.5,120.4,120.2,120.1,116.9,115.8,29.1,24.0;

[0111] 31 P NMR (162MHz, CDCl3): δ-4.9; HR-MS (MALDI-TOF) m / z: Calcd for C 45 H 36 NO2PS[M] + :685.2204, Found:685.2205(error=+0.01ppm).

[0112] Example 7 Synthesis of Formula 1-B-5-2Th:

[0113]

[0114] Synthesis process: The synthesis process is the same as that of 1-B-5-Th, except that the amount of tributyl(2-thienyl)tin is 2 eqv, and the other operations are the same as those of Example 6. Finally, a blue solid formula 1-B-5-2Th is obtained with a yield of 57%.

[0115] 1H NMR (400MHz, CDCl3) δ8.57(d,J=8.0Hz,2H),8.14(d,J=10.5Hz,1H),7.85(m,2H),7.82(m,2H),7.62(m,6H),7. 51(m,6H),7.32(d,J=7.8Hz,2H),7.10(d,J=5.1Hz,1H),6.73(m,1H),6.33(s,1H),2.75(m,2H),1.17(m,12H);

[0116] 13 C NMR (100MHz, CDCl3) δ164.0,163.2,145.6,140.4,137.0,133.9,133.9,133.8,133.6,132.6,130.6,130.1,129.7,129.6,129. 5,129.5,129.2,127.3,127.2,126.3,126.2,125.2,125.1,124.6,124.0,123.9,123.3,120.6,115.0,116.3,29.6,29.1,24.0;

[0117] 31 P NMR (162MHz, CDCl3): δ-4.6; HR-MS (MALDI-TOF) m / z: Calcd for C 49 H 38 NO2PS2[M] + :767.2082, Found:767.2084(error=+0.03ppm).

[0118] Example 8 Synthesis of Formula 1-B-5-3Th:

[0119]

[0120] Synthesis process: The same as the synthesis process of 1-B-5-Th, the amount of tributyl (2-thienyl) tin is 3eqv, and the other operations are the same as Example 6. Finally, a blue solid formula 1-B-5-3Th is obtained with a yield of 85%

[0121] 1H NMR (400MHz, CDCl3) δ8.57(d,J=8.0Hz,2H),8.14(d,J=10.5Hz,1H),7.85(m,2H),7.82(m,2H),7.62(m,6H),7. 51(m,6H),7.32(d,J=7.8Hz,2H),7.10(d,J=5.1Hz,1H),6.73(m,1H),6.33(s,1H),2.75(m,2H),1.17(m,12H);

[0122] 13 C NMR (100MHz, CDCl3) δ164.0,163.2,145.6,140.4,137.0,133.9,133.9,133.8,133.6,132.6,130.6,130.1,129.7,129.6,129. 5,129.5,129.2,127.3,127.2,126.3,126.2,125.2,125.1,124.6,124.0,123.9,123.3,120.6,115.0,116.3,29.6,29.1,24.0;

[0123] 31 P NMR (162MHz, CDCl3): δ-4.6; HR-MS (MALDI-TOF) m / z: Calcd for C 49 H 38 NO2PS2[M] + :767.2082, Found:767.2084(error=+0.03ppm).

[0124] Part 4: Testing and Application

[0125] The phosphorus ylide functional molecule of the structural formula of the present invention is studied to study the characteristics of integrating optoelectronic multifunctions. In the single crystal unit cell, the phosphorus ylide adopts the head-to-tail dimer form to form a π-π stacking form. The π skeleton has good planarity, and there is no strong π-π force between the phosphorus ylide molecules due to the presence of multiple substituents.

[0126] The phosphorus ylide formula 1-A-7-3H has a moderate absorption characteristic broadband in the range of 450-700 nm; the phosphorus ylide formula 1-B-5-3H has a moderate absorption characteristic broadband in the range of 450-800 nm.

[0127] Phosphorus ylide 1-A-7-3H exhibits a reversible reduction peak and an irreversible oxidation peak in electrochemical tests; ylide 1-B-5-3H exhibits two reversible reduction peaks and one irreversible oxidation peak.

[0128] Calculation of the electrostatic potential distribution of phosphorus ylides shows that the positive charge is mainly concentrated in the diphenylphosphine part, and the negative charge is mainly concentrated in the cyclopentadiene and amide parts, indicating that phosphorus ylides have a large dipole moment.

[0129] The cyclopentadiene in phosphorus ylide is aromatic, and the phosphorus heterocycles all have moderate antiaromatic properties, so this functional series of molecules are highly stable to air and water.

[0130] Compound Nonlinear optical testing was performed, and the results were as follows Fig.10 shown.

Claims

1. An organic phosphorus heteropolycyclic aromatic hydrocarbon having a ylide bond, characterized in that It is a compound having at least one of the structural formulas 1-A and 1-B: In formula 1-A and formula 1-B, R1 and R2 are independently selected from C1-C 24 Alkyl, C3-C 24 Cycloalkyl, halogenated C1-C 24 Alkyl, aryl, heterocyclic or condensed ring; The R3, R4 and R5 are independently selected from H, halogen, C1-C 24 Alkyl, C3-C 24 Cycloalkyl, C2-C 24 Alkynyl, halogenated C1-C 24 Alkyl, aryl, heterocyclic or condensed ring; The ring A is a monocyclic ring A including a five-membered heterocyclic ring, a benzene ring, or a six-membered heterocyclic ring, or a combined ring A formed by combining two or more monocyclic rings A; The R6 and R7 are independently electron-withdrawing groups, or are cyclized to form a monocyclic ring B including a five-membered carbocyclic ring, a five-membered heterocyclic ring, a six-membered carbocyclic ring, or a six-membered heterocyclic ring, or a fused ring B formed by merging two or more monocyclic rings B; The monocyclic ring A, monocyclic ring B, fused ring A and fused ring B are allowed to have electron withdrawing groups.

2. The organophosphorus heteropolycyclic aromatic hydrocarbon having a ylide bond according to claim 1, characterized in that In Formula 1-A and Formula 1-B, R1 and R2 are independently selected from C1-C 24 Alkyl, C3-C 24 Cycloalkyl, halogenated C1-C 24 Alkyl, aryl, heterocyclic or condensed ring; Preferably, R1 and R2 are the same substituents.

3. The organophosphorus heteropolycyclic aromatic hydrocarbon having a ylide bond according to claim 1, characterized in that The R3, R4 and R5 are independently selected from H, halogen, C1-C 24 Alkyl, C3-C 24 Cycloalkyl, C2-C 24 Alkynyl, halogenated C1-C 24 Alkyl, aryl, heterocyclic or condensed ring; Furthermore, R3, R4 and R5 are independently H, bromine atoms or thiophene.

4. The organophosphorus heteropolycyclic aromatic hydrocarbon having a ylide bond according to claim 1, characterized in that The ring A includes the following structural fragments: Wherein, R is H, phenyl, alkyl-substituted phenyl or an electron-withdrawing group, and the electron-withdrawing group is cyano, carbonyl, nitro, ester, trifluoromethyl or amide; Preferably, the compound of formula 1-A comprises at least one compound of the following structure; 5. The organophosphorus heteropolycyclic aromatic hydrocarbon having a ylide bond according to claim 1, characterized in that The R6 and R7 are cyclized to form a five-membered carbon ring or a six-membered carbon ring; and the five-membered carbon ring or the six-membered carbon ring is allowed to have an electron-withdrawing group, or is combined with at least one of a five-membered heterocycle, a six-membered heterocycle, and a benzene ring; Preferably, the formula 1-B is at least one compound having the following structural formula: The R is H, phenyl, alkyl-substituted phenyl or an electron-withdrawing group, and the electron-withdrawing group is cyano, carbonyl, nitro, ester, trifluoromethyl or amide.

6. A method for preparing an organophosphorus heteropolycyclic aromatic hydrocarbon having a ylide bond according to any one of claims 1 to 5, characterized in that: Carrying out a cyclization reaction between raw material a and raw material b to obtain product a, wherein the product a is of formula 1-A and / or formula 1-B in which R3 to R5 are H; The raw material a is a compound having at least one structure of formula 2-A and formula 2-B; the raw material b is a compound having a structure of formula 3; Preferably, X in Formula 2-A and Formula 2-B is Br, Cl or I; more preferably Br; The molar ratio of the raw material a to the raw material b is 1:1 to 1.3; Preferably, the temperature of the cyclization reaction is preferably 80 to 120°C; Preferably, the cyclization reaction is carried out under the catalysis of lithium acetate and / or palladium acetate.

7. The preparation method according to claim 6, characterized in that: The product a is subjected to a halogenation reaction with a halogenating agent to obtain a product b in which at least one substituent among R3 to R5 is a halogen; Preferably, the halogenating agent is at least one of NBS, NCS, and NIS; Preferably, the temperature of the halogenation reaction conditions is 50 to 90°C; Preferably, the halogenating agent is added in an equivalent amount of 1 to 1.3 eqv to synthesize product b1 in which R3 is a halogen; R4 and R5 are H; Alternatively, the halogenating agent is added in an equivalent amount of 2 to 2.5 eqv to synthesize product b2 in which R3 and R4 are halogens and R5 is H; Alternatively, the added equivalent of the halogenating agent is 3 eqv or more, and the product b3 in which R3, R4 and R5 are halogens is synthesized.

8. The preparation method according to claim 7, characterized in that: The product b and the substituent a donor nucleophilic reagent are subjected to a nucleophilic coupling reaction to obtain a product c in which at least one halogen in R3 to R5 of the product b is replaced by a substituent a; the substituent a includes C1-C 24 Alkyl, C3-C 24 Cycloalkyl, C2-C 24 Alkynyl, halogenated C1-C 24 At least one of an alkyl group, an aryl group, a heterocyclic ring or a condensed ring; Preferably, the substituent a donor is added in an equivalent amount of 1 to 1.3 eqv to synthesize product c1 in which R3 is substituent a; Alternatively, the substituent a donor is added in an equivalent amount of 2 to 2.5 eqv to synthesize product c2 in which R3 and R4 are substituent a; Alternatively, the substituent a donor is added in an equivalent amount of 3 eqv or more to synthesize product c3 in which R3, R4, and R5 are substituent a; Preferably, the substituent a donor nucleophilic reagent is an organic tin reagent containing substituent a; its structural formula is Formula 4; the product b and the substituent a donor are subjected to Stille coupling reaction to obtain product c. In the formula 4, R6 is a C1-C6 alkyl group; Ra is a substituent a; Preferably, the Stille coupling reaction is carried out in a catalyst, and the catalyst may include Pd(PPh3)4 and CuI; wherein the molar ratio of Pd(PPh3)4 to CuI may preferably be 1:1.5 to 2.5; Preferably, the optimal temperature range of the Stille coupling reaction is 80-110°C.

9. The use of the organophosphorus heteropolycyclic aromatic hydrocarbon having a ylide bond as claimed in any one of claims 1 to 5, characterized in that: It is used to prepare optoelectronic materials.

10. A photoelectric material, characterized in that: The organic phosphorus heteropolycyclic aromatic hydrocarbon having a ylide bond as claimed in any one of claims 1 to 5 is prepared therefrom.

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