CN110194734B - Chiral fluorescent compound based on cyclophane alkyl skeleton and preparation method and application thereof - Google Patents

Chiral fluorescent compound based on cyclophane alkyl skeleton and preparation method and application thereof Download PDF

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CN110194734B
CN110194734B CN201910265189.XA CN201910265189A CN110194734B CN 110194734 B CN110194734 B CN 110194734B CN 201910265189 A CN201910265189 A CN 201910265189A CN 110194734 B CN110194734 B CN 110194734B
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郑文华
廖晨
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Nanjing University
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Abstract

The invention relates to a chiral fluorescent compound based on a cyclophane skeleton and a preparation method and application thereof. The invention utilizes the rigid skeleton structure of cyclophane to well maintain the chirality of cyclophane in an excited state, thereby obtaining high luminous efficiency and good circular polarization luminous performance (high asymmetry factor). The luminous wavelength, the intensity of Circular Polarized Light (CPL) and the luminous intensity can be regulated and controlled by changing R1 and R2 substituents. By changing the R3 substituent, the molecule is in the state of electron donor/electron acceptor, so that the thermally activated delayed fluorescent material is obtained.

Description

Chiral fluorescent compound based on cyclophane alkyl skeleton and preparation method and application thereof
Technical Field
The invention relates to the field of organic materials and preparation thereof, in particular to a chiral fluorescent compound based on a cyclophane skeleton, and a preparation method and application thereof.
Background
Circular polarization luminescence is a phenomenon that a chiral luminescence system can emit left-handed or right-handed circularly polarized light with different intensities, and can be used for researching the chiral characteristics of chiral substances in an excited state. The study of whether to be able to generate circularly polarized light using organic light-emitting molecules is relatively still in the first place compared to the absorption of polarized light by chiral molecules. However, in recent years, circular Polarized Luminescence (CPL) has attracted wide attention for potential applications in 3D optical display, information storage and transmission, secret information recording, photoelectric devices, and even asymmetric photochemical synthesis, and besides the above applications, polarized light technology can also be used in the fields of aviation and satellite remote sensing. Therefore, the development of chiral optical functional materials with polarized luminescence property has important significance.
The materials used by CPL in the early days are mostly metal complexes, and the substances have higher circular polarization luminescence property. However, they have disadvantages such as low luminous efficiency and use of non-renewable resources such as noble metals.
Organic small molecule luminescent materials are a research hotspot in the field due to the advantages of simple structure, easy derivatization, wide variety and the like. However, it is still difficult to obtain materials with both high asymmetry factor and high quantum yield.
Cycloalane is an organic small molecular skeleton with high rigidity, which is favorable for the molecules in excited state to maintain good space structure and thus to obtain high asymmetry factor. Meanwhile, chromophore is introduced on the framework, so that higher fluorescence quantum yield can be obtained.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a chiral fluorescent compound based on a cyclophane skeleton, which has good Circular Polarized Luminescence (CPL) performance, changes the Luminescence wavelength, the CPL intensity and the fluorescence quantum yield by changing substituents at different positions, and can also prepare small organic molecules with thermal retardation performance based on the molecular skeleton.
The invention also aims to provide a preparation method of the chiral fluorescent compound based on the cyclophane skeleton.
The invention also aims to provide application of a chiral fluorescent compound based on a cyclophane skeleton.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a chiral fluorescent compound based on a chiral cyclophane alkyl skeleton is shown in the following structural general formula:
Figure BDA0002016561100000021
wherein R is 1 Selected from H or aryl; r 2 Selected from aryl or unsaturated conjugated groups; r 3 Selected from aryl groups with electron-withdrawing substituents.
As a further improvement of the technology, R 2 Some representative structures selected from the following list:
Figure BDA0002016561100000022
R 3 a structure of this type selected from the group consisting of:
Figure BDA0002016561100000023
as a further improvement in the art, the compound comprises enantiomers of both R/S configurations; wherein the structure of the S configuration enantiomer is shown as a general formula S-I:
Figure BDA0002016561100000024
wherein the structure of the enantiomer with the R configuration is shown as a general formula R-I:
Figure BDA0002016561100000025
as a further improvement of the technology, the basic skeleton of the compound is constructed by a two-step reaction from a raw material 1, wherein the structural formula of the raw material 1 is as follows:
Figure BDA0002016561100000031
as a further improvement of the technology, the raw material 1 reacts with o-chlorobromobenzene to obtain an intermediate 1, and a coupling reaction is carried out under the action of a metal palladium catalyst to obtain a compound 1, wherein the synthetic route is as follows:
Figure BDA0002016561100000032
as a further improvement of the technology, said intermediates 2 and 3 were prepared using the following synthetic route:
Figure BDA0002016561100000033
as a further improvement of the technology, the intermediate 2 and aryl boric acid are subjected to coupling reaction to obtain an analogue compound 2 of the compound 1, and the analogue compound 2 has the following structure:
Figure BDA0002016561100000034
as a further improvement of the art, said intermediate 2 is reacted with an olefinic compound to give an analogue compound 3 of said compound 1, having the structure:
Figure BDA0002016561100000035
as a further improvement of the technology, the intermediate 2 is coupled with an alkyne compound to give the analogue compound 4 of the compound 1, which has the following structure:
Figure BDA0002016561100000041
as a further improvement of the technology, the intermediate 3 and aryl boric acid are subjected to coupling reaction to obtain an analog compound 5 of the compound 1, and the structure of the analog compound is as follows:
Figure BDA0002016561100000042
as a further improvement of the technology, the compound 1 and aryl halide are subjected to coupling reaction to obtain an analog compound 6 of the compound 1, which has the following structure:
Figure BDA0002016561100000043
compared with the prior art, the invention has the beneficial effects that:
the invention utilizes the rigid skeleton structure of cyclophane to ensure that the chirality of cyclophane can be better maintained in an excited state, thereby obtaining a high asymmetric factor. We proceed by varying R 1 、R 2 The substituent can regulate and control the luminous interval, CPL intensity and luminous intensity. By varying R 3 And (4) substituent groups, so as to obtain the thermally activated delayed fluorescence material.
Drawings
FIG. 1 is a circular dichroism spectrum of the compound prepared in example 1.
FIG. 2 is a circular dichroism spectrum of the compound prepared in example 2.
FIG. 3 is a circular dichroism spectrum of the compound prepared in example 3.
FIG. 4 is a circular dichroism spectrum of the compound prepared in example 4.
FIG. 5 is a circular dichroism spectrum of the compound prepared in example 5.
FIG. 6 is a circular dichroism spectrum of the compound prepared in example 6.
FIG. 7 is a circular dichroism spectrum of the compound prepared in example 7.
FIG. 8 is a circular dichroism spectrum of the compound prepared in example 8.
Fig. 9 is a circular polarization luminescence spectrum of the compound prepared in example 1.
FIG. 10 is a circularly polarized luminescence spectrum of the compound prepared in example 2.
FIG. 11 is a circularly polarized luminescence spectrum of the compound prepared in example 3.
FIG. 12 is a circularly polarized luminescence spectrum of the compound prepared in example 4.
Fig. 13 is a circular polarization luminescence spectrum of the compound prepared in example 5.
FIG. 14 is a circularly polarized luminescence spectrum of the compound prepared in example 6.
FIG. 15 is a circularly polarized luminescence spectrum of the compound prepared in example 7.
FIG. 16 is a circularly polarized luminescence spectrum of the compound prepared in example 8.
Detailed Description
The present invention will be further described with reference to the following specific examples.
A chiral fluorescent compound based on a cyclophane skeleton has a structural general formula as follows:
Figure BDA0002016561100000051
wherein R is 1 Selected from H or aryl.
R 2 Selected from aryl or unsaturated conjugated groups such as some of the representative structures listed below:
Figure BDA0002016561100000052
R 3 selected from aryl groups bearing electron withdrawing substituents, such as the types of structures listed below:
Figure BDA0002016561100000053
according to certain embodiments of the invention, the compound comprises both R/S enantiomers; wherein the structure of the S enantiomer is shown as the general formula S-I:
Figure BDA0002016561100000061
the structure of the R-type enantiomer is shown as the general formula R-I:
Figure BDA0002016561100000062
wherein R is 1 Selected from H or aryl.
R 2 Selected from aryl or unsaturated conjugated groups such as some of the representative structures listed below:
Figure BDA0002016561100000063
R 3 selected from aryl groups bearing electron withdrawing substituents, such as the types of structures listed below:
Figure BDA0002016561100000064
according to some embodiments of the invention, the building of the basic skeleton of the compound is prepared by a two-step reaction of starting material 1, wherein the starting material 1 has the following structural formula
Figure BDA0002016561100000065
According to some embodiments of the invention, the raw material 1 and the o-chlorobromobenzene are reacted to obtain the intermediate 1, and the intermediate 1 is subjected to oxidative coupling under the action of a metal palladium catalyst to obtain the compound 1, wherein the synthetic route is as follows:
Figure BDA0002016561100000071
according to certain embodiments of the present invention, the intermediates 2 and 3 are synthesized using the following synthetic route:
Figure BDA0002016561100000072
according to some embodiments of the invention, coupling of said intermediate 2 with an arylboronic acid gives said analogue compound 2 of compound 1, having the following structure:
Figure BDA0002016561100000073
according to some embodiments of the invention, the intermediate 2 is coupled with an olefinic compound to provide an analog compound 3 of the compound 1, having the following structure:
Figure BDA0002016561100000074
according to some embodiments of the present invention, intermediate 2 is coupled to an alkynyl compound to provide analog compound 4 of compound 1, which has the following structure:
Figure BDA0002016561100000075
according to some embodiments of the invention, said intermediate 3 is reacted with an arylboronic acid to give said compound 1 derivative compound 5, which has the following structure:
Figure BDA0002016561100000081
according to some embodiments of the invention, the compound 1 is reacted with an aryl halide to provide a compound 6 derivative of the compound 1 having the structure:
Figure BDA0002016561100000082
according to certain embodiments of the invention, the compounds of formula S-I have the following structures S-I1 through S-I8:
Figure BDA0002016561100000091
according to certain embodiments of the invention, the compounds of formula R-I have the following structures R-I1 through R-I8:
Figure BDA0002016561100000101
the compound shown in the formula R-I is a compound shown in R-I1 to R-I6, a cyclophane skeleton has a chiral induction effect on chromophore carbazole, and the chiral induction is complete, so that carbazole with surface chirality has optical activity and can generate good circular polarization luminescence.
The compounds shown in the formula R-I are compounds shown in R-I7 to R-I8, cyclophane has a chiral induction effect on chromophore carbazole, and the chiral induction is complete, so that carbazole with surface chirality has optical activity and can generate good circular polarization luminescence. Meanwhile, an electron acceptor/electron donor structure exists between the chromophore carbazole and the substituent group, so that the chromophore carbazole has the characteristic of thermal retardation luminescence.
According to some embodiments of the present invention, the basic skeleton of the compound is constructed by a two-step reaction of starting material 1, wherein the starting material 1 has the following structural formula
Figure BDA0002016561100000111
According to some embodiments of the invention, the raw material 1 is reacted with o-chlorobromobenzene to obtain an intermediate 1, and the intermediate 1 is coupled under the action of a metal palladium catalyst to obtain a compound 1, wherein the synthetic route is as follows:
Figure BDA0002016561100000112
according to certain embodiments of the present invention, the intermediates 2 and 3 are prepared using the following synthetic route:
Figure BDA0002016561100000113
according to some embodiments of the invention, coupling reaction of said intermediate 2 with an aryl boronic acid gives said analogue compound 2 of compound 1, having the following structure:
Figure BDA0002016561100000114
according to some embodiments of the invention, the intermediate 2 is coupled to an olefinic compound to provide an analog compound 3 of the compound 1, having the following structure:
Figure BDA0002016561100000115
according to some embodiments of the present invention, intermediate 2 is coupled with an alkynyl compound to provide analog compound 4 of said compound 1, having the following structure:
Figure BDA0002016561100000121
according to some embodiments of the invention, coupling of intermediate 3 with an arylboronic acid provides analog 5 of compound 1, having the structure:
Figure BDA0002016561100000122
according to certain embodiments of the present invention, the coupling reaction of compound 1 with an aryl halide provides compound 6, an analog of compound 1, having the structure:
Figure BDA0002016561100000123
as mentioned above, carbazole molecules based on cyclophane have good circular polarization luminescence characteristics, and have potential applications in 3D optical display, information storage and transmission, secret information recording, photoelectric devices and even asymmetric photochemical synthesis.
The following examples will further describe the present invention. The reagents used in the practice of the invention are commercially available unless otherwise specified.
Example 1
Preparation of compounds of formula S-I1 and formula R-I1
The reaction formula is as follows:
Figure BDA0002016561100000131
the specific preparation process comprises the following steps:
1) In a 1L round bottom flask, 40.0g of bromocyclophane A was dissolved600mL of DMSO (dimethylsulfoxide) with nitrogen as a blanket gas, then 18.0g of NaN were added in sequence 3 ，20.0g Cu 2 O and 38.4g of Proline were stirred at 100 ℃ for 2 days. The light yellow product RAC-B is obtained by silica gel column separation and then is resolved by a chiral column, and the yield is 64 percent.
2) In a 250mL Schlenk tube, 6.0g of B was dissolved in 150mL of toluene, and 4.5g of o-chlorobromobenzene and 0.6g of Pd were added in this order under an argon atmosphere 2 (dba) 3 1.0g of XPhos and 3.0g of NaOt-Bu, and then stirred at 100 ℃ overnight, and the resulting material was subjected to column chromatography to obtain a white solid with a yield of 99%.
3) In a 100mL Schlenk tube, 4.0g of C was dissolved in 34Ml DMA with argon as the shielding gas, and then 1.1g of Pd were added in order 2 (dba) 3 1.8g XPhos,0.7g PivOH and 8.7g K 2 CO 3 Stirring at 100 deg.C overnight, and separating by column chromatography to obtain white solid with yield of 63%
The total yield of the final product R-I1 was 40%. The structure of the compound was examined as follows:
1 H NMR(400MHz,Chloroform-d)δ7.98(d,J＝7.9Hz,1H),7.80(bras,1H),7.38 (d,J＝8.0Hz,1H),7.32(t,J＝7.5Hz,1H),7.24–7.15(m,1H),6.55(d,J＝ 7.5Hz,1H),6.48(d,J＝7.5Hz,1H),6.45–6.39(m,1H),6.28(dd,J＝7.8,1.9 Hz,1H),5.85(dd,J＝7.7,1.9Hz,1H),5.14(dd,J＝7.8,1.9Hz,1H),3.93(dd, J＝12.5,9.7Hz,1H),3.32–3.20(m,1H),3.10–2.82(m,6H).
13 C NMR(126MHz,CDCl 3 )δ140.01,138.80,137.89,137.28,135.78,132.00,131.47, 130.97,126.46,126.29,125.39,125.22,124.85,124.55,122.41,122.19,119.66, 110.63,33.93,33.74,33.22,31.10.
Optical Rotation:R p [α] 22 D ＝6.8(c＝0.50,CHCl 3 )；
the results of the detection revealed that the above-mentioned compounds have correct structures.
The total yield of the final product S-I1 obtained was 40%. The structure of the compound was examined as follows:
1 H NMR(400MHz,Chloroform-d)δ7.98(d,J＝7.9Hz,1H),7.80(bras,1H),7.38 (d,J＝8.0Hz,1H),7.32(t,J＝7.5Hz,1H),7.24–7.15(m,1H),6.55(d,J＝ 7.5Hz,1H),6.48(d,J＝7.5Hz,1H),6.45–6.39(m,1H),6.28(dd,J＝7.8,1.9 Hz,1H),5.85(dd,J＝7.7,1.9Hz,1H),5.14(dd,J＝7.8,1.9Hz,1H),3.93(dd, J＝12.5,9.7Hz,1H),3.32–3.20(m,1H),3.10–2.82(m,6H).
13 C NMR(126MHz,CDCl 3 )δ140.01,138.80,137.89,137.28,135.78,132.00,131.47, 130.97,126.46,126.29,125.39,125.22,124.85,124.55,122.41,122.19,119.66, 110.63,33.93,33.74,33.22,31.10.
Optical Rotation:S p [α] 22 D ＝-4.8(c＝0.50,CHCl 3 )；
the results of the detection revealed that the above-mentioned compounds have correct structures.
Example 2
Preparation of compounds of formula S-I2 and formula R-I2
The reaction formula is as follows:
Figure BDA0002016561100000141
the preparation process comprises the following steps:
in a 500mL round-bottomed flask, compound I1 was dissolved in 200mL acetonitrile, 1.8g NBS was added at-20 ℃ and stirring was continued for 4h, and the resulting material was subjected to column chromatography to give a white solid in 61% yield
In a 10mL Schlenk tube, compound C was dissolved in 2mL DMF and 0.26mL H 2 To O, 31.8mg of phenylboronic acid and 7.0mg of Pd (PPh) were added in this order 4 ,82.8mg K 2 CO 3 The mixture was stirred at 100 ℃ overnight, and the resulting material was subjected to column chromatography to give a white solid with a yield of 61%.
The total yield of the final product R-I2 was 36%. The structure of the compound was examined as follows:
1 H NMR(500MHz,Chloroform-d)δ8.27(d,J＝1.7Hz,1H),7.91(s,1H),7.78 –7.72(m,2H),7.66(dd,J＝8.3,1.7Hz,1H),7.55–7.48(m,3H),7.40–7.35 (m,1H),6.65(d,J＝7.5Hz,1H),6.59(d,J＝7.5Hz,1H),6.52(dd,J＝7.7,1.9 Hz,1H),6.38(dd,J＝7.8,2.0Hz,1H),5.99(dd,J＝7.8,2.0Hz,1H),5.36–5.26 (m,1H),4.07(dd,J＝12.8,9.7Hz,1H),3.43–3.29(m,1H),3.19–2.93(m,6H).
13 C NMR(126MHz,CDCl 3 )δ142.42,140.51,138.31,137.92,137.33,135.88,133.23, 132.08,131.55,131.19,128.82,127.43,126.67,126.49,126.41,125.77,125.54, 124.62,124.60,122.34,120.88,110.83,33.95,33.83,33.30,31.10.
Optical Rotation:R p [α] 22 D ＝107.2(c＝1.34,CHCl 3 )；
HRMS(ESI)calc for C 28 H 22 N[M-H] - 372.1752.found 372.1756.
the results of the detection revealed that the above compound had a correct structure.
The overall yield of the final product S-I2 was 36%. The structure of the compound was examined as follows:
1 H NMR(500MHz,Chloroform-d)δ8.27(d,J＝1.7Hz,1H),7.91(s,1H),7.78 –7.72(m,2H),7.66(dd,J＝8.3,1.7Hz,1H),7.55–7.48(m,3H),7.40–7.35 (m,1H),6.65(d,J＝7.5Hz,1H),6.59(d,J＝7.5Hz,1H),6.52(dd,J＝7.7,1.9 Hz,1H),6.38(dd,J＝7.8,2.0Hz,1H),5.99(dd,J＝7.8,2.0Hz,1H),5.36–5.26 (m,1H),4.07(dd,J＝12.8,9.7Hz,1H),3.43–3.29(m,1H),3.19–2.93(m,6H).
13 C NMR(126MHz,CDCl 3 )δ142.42,140.51,138.31,137.92,137.33,135.88,133.23, 132.08,131.55,131.19,128.82,127.43,126.67,126.49,126.41,125.77,125.54, 124.62,124.60,122.34,120.88,110.83,33.95,33.83,33.30,31.10.
Optical Rotation:S p [α] 22 D ＝-87.4(c＝0.57,CHCl 3 )；
HRMS(ESI)calc for C 28 H 22 N[M-H] - 372.1752.found 372.1756.
the results of the detection revealed that the above compound had a correct structure.
Example 3
Preparation of Compounds of formula S-I3 and R-I3
The reaction formula is as follows:
Figure BDA0002016561100000161
the specific preparation process comprises the following steps:
in a 10mL Schlenk tube, C was dissolved in 2mL DMF and 0.26mL H 2 To O, 38.2mg of p-cyanophenylboronic acid and 7.0mg of Pd (PPh) were added in this order 4 ,82.8mg K 2 CO 3 The resulting material was subjected to column chromatography to give a white solid with a yield of 57%.
The structure of the compound R-I3 is detected as follows:
1 H NMR(500MHz,Chloroform-d)δ8.26(d,J＝1.6Hz,1H),8.03(s,1H),7.83(d, J＝8.6Hz,2H),7.78(d,J＝8.2Hz,2H),7.65(dd,J＝8.4,1.6Hz,1H),7.56(d, J＝8.3Hz,1H),6.68(d,J＝7.4Hz,1H),6.61(d,J＝7.5Hz,1H),6.53(dd,J＝ 7.9,1.8Hz,1H),6.39(dd,J＝7.8,1.8Hz,1H),5.98(dd,J＝7.7,1.8Hz,1H), 5.30(d,J＝1.3Hz,1H),4.05(dd,J＝12.8,10.0Hz,1H),3.42–3.31(m,1H), 3.22–2.91(m,6H).
13 C NMR(126MHz,CDCl 3 )δ146.88,140.63,139.01,137.79,137.42,135.89,132.66, 132.21,131.65,131.58,130.94,127.78,126.99,126.34,125.93,125.29,124.64, 124.37,122.55,121.10,119.35,111.25,109.80,33.93,33.84,33.30,31.07.
Optical Rotation:R p [α] 22 D ＝100.3(c＝0.73,CHCl 3 )；
HRMS(ESI)calc for C 29 H 21 N 2 [M-H] - 397.1705.found 397.1694.
the results of the detection revealed that the above-mentioned compounds have correct structures.
The structure of the compound R-I3 is detected as follows:
1 H NMR(500MHz,Chloroform-d)δ8.26(d,J＝1.6Hz,1H),8.03(s,1H),7.83 (d,J＝8.6Hz,2H),7.78(d,J＝8.2Hz,2H),7.65(dd,J＝8.4,1.6Hz,1H),7.56 (d,J＝8.3Hz,1H),6.68(d,J＝7.4Hz,1H),6.61(d,J＝7.5Hz,1H),6.53(dd, J＝7.9,1.8Hz,1H),6.39(dd,J＝7.8,1.8Hz,1H),5.98(dd,J＝7.7,1.8Hz,1H), 5.30(d,J＝1.3Hz,1H),4.05(dd,J＝12.8,10.0Hz,1H),3.42–3.31(m,1H), 3.22–2.91(m,6H).
13 C NMR(126MHz,CDCl 3 )δ146.88,140.63,139.01,137.79,137.42,135.89,132.66, 132.21,131.65,131.58,130.94,127.78,126.99,126.34,125.93,125.29,124.64, 124.37,122.55,121.10,119.35,111.25,109.80,33.93,33.84,33.30,31.07.
Optical Rotation:S p [α] 22 D ＝-124.3(c＝0.79,CHCl 3 )；
HRMS(ESI)calc for C 29 H 21 N 2 [M-H] - 397.1705.found 397.1694.
the results of the detection revealed that the above compound had a correct structure.
Example 4
Preparation of compounds of formula S-I4 and formula R-I4
The reaction formula is as follows:
Figure BDA0002016561100000171
the specific preparation process comprises the following steps:
in a 10mL Schlenk tube, 37.5mg of Compound C was dissolved in 0.5mL of DMA, and 12.7mg of p-cyanostyrene, 0.6mg of Pd (OAc) were added thereto 2 ,28.1uL Et 3 N and 15.2mg PPh 3 The mixture was stirred overnight at 110 ℃ and the resulting material was isolated by column chromatography to give a white solid in 63% yield.
Example 5
Preparation of compounds of formula S-I5 and formula R-I5
The reaction formula is as follows:
Figure BDA0002016561100000172
the preparation process comprises the following steps:
in a 10mL Schlenk tube, 37.5mg of Compound C was dissolved in 0.25mL of DMF, and 15.3mg of p-cyanophenylethyl acetate was added in that orderAlkyne, 1.0mg Pd (PPh) 3 Cl 2 ,0.4mg CuI,0.12mL Et 3 N and 7.9mg PPh 3 Stirring overnight at 110 deg.C, and separating by column chromatography to obtain white solid with yield of 60%.
Example 6
Preparation of compounds of formula S-I6 and formula R-I6
The reaction formula is as follows:
Figure BDA0002016561100000181
the preparation process comprises the following steps:
in a 10mL Schlenk tube, 22.6mg of Compound D was dissolved in 1mL of DMF and 0.3mL of H 2 To O, 18.3mg of phenylboronic acid and 1.0mg of Pd (PPh) were added in this order 4 ,41.4mg K 2 CO 3 After stirring overnight at 110 ℃, the material was column chromatographed to give a white solid in 46% yield.
Example 7
Preparation of Compounds of formula S-I7 and R-I7
The reaction formula is as follows:
Figure BDA0002016561100000182
the preparation process comprises the following steps:
in a 10mL Schlenk tube, 89.1mg of Compound 1 was dissolved in 0.5mL of 1,4-dioxane, and 97.2mg of Trz-PhBr,11.3mg of Pd (OAc) were added in this order 2 30.0mg XPhos and 52.7mg NaOt-Bu, stirred at 80 ℃ overnight, and the resulting material was subjected to column chromatography to give a white solid with a yield of 49%.
Example 8
Preparation of compounds of formula S-I8 and formula R-I8
The reaction formula is as follows:
Figure BDA0002016561100000183
the preparation process comprises the following steps:
in a 10mL Schlenk tube, 148.5mg of Compound 1 was dissolved in 0.5mL of DMSO, 72.7mg of p-fluorophenylacetonitrile was added, and the mixture was stirred overnight at 140 ℃ to conduct column chromatography, whereby the obtained substance was isolated as a white solid in 47% yield. TABLE EXAMPLES 1-3 optical Properties of Compounds prepared
Figure BDA0002016561100000191
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make any simple modification, equivalent replacement, and improvement on the above embodiment without departing from the technical spirit of the present invention, and still fall within the protection scope of the technical solution of the present invention.

Claims (5)

1. A chiral fluorescent compound based on a cyclophane alkyl skeleton is characterized in that: the structure of the compound is shown as one of the following formulas S-I1 to S-I8:
Figure FDA0003909751760000011
or the structure of the compound shown in the formula R-I is one of the following formulas R-I2 to R-I7:
Figure FDA0003909751760000021
2. chiral fluorescent compound based on the cyclophane skeleton according to claim 1, characterized in that: the basic skeleton of the compound is constructed by two-step reaction from raw materials 1Rp-B and Sp-B, wherein the structural formulas of the raw materials 1Rp-B and Sp-B are as follows:
Figure FDA0003909751760000031
3. chiral fluorescent compound based on the cyclophane scaffold according to claim 2, characterized in that: compounds 1Rp-I1, sp-I1 were prepared using the following synthetic route:
Figure FDA0003909751760000032
4. chiral fluorescent compound based on the cyclophane scaffold according to claim 3, characterized in that: intermediate 2 Rp-intermediate 2, sp-intermediate 2 and intermediate 3 Rp-intermediate 3, sp-intermediate 3 were prepared using the following synthetic route:
Figure FDA0003909751760000041
。
5. use of chiral fluorescent compounds based on cyclophane skeletons according to claim 1 as fluorescent substances.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108117506A (en) * 2017-12-19 2018-06-05 中国科学院化学研究所 A kind of optical voidness hot activation delayed fluorescence material based on chiral 1,2- cyclohexanediamine and preparation method and application
CN109320507A (en) * 2018-09-14 2019-02-12 北京师范大学 Chiral fluorescent chemicals and the preparation method and application thereof based on quinoline amides folded formation
CN109400587A (en) * 2018-11-12 2019-03-01 中国科学院化学研究所 A kind of red hot activation delayed fluorescence material and the preparation method and application thereof with circular polarised luminescence property
CN110357880A (en) * 2019-05-31 2019-10-22 北京师范大学 The chiral fluorescent chemicals and the preparation method and application thereof with circular polarised luminescence property based on folded formation

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016196885A1 (en) * 2015-06-05 2016-12-08 Massachusetts Institute Of Technology [2-2]paracyclophane-derived donor/acceptor-type molecules for oled applications

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108117506A (en) * 2017-12-19 2018-06-05 中国科学院化学研究所 A kind of optical voidness hot activation delayed fluorescence material based on chiral 1,2- cyclohexanediamine and preparation method and application
CN109320507A (en) * 2018-09-14 2019-02-12 北京师范大学 Chiral fluorescent chemicals and the preparation method and application thereof based on quinoline amides folded formation
CN109400587A (en) * 2018-11-12 2019-03-01 中国科学院化学研究所 A kind of red hot activation delayed fluorescence material and the preparation method and application thereof with circular polarised luminescence property
CN110357880A (en) * 2019-05-31 2019-10-22 北京师范大学 The chiral fluorescent chemicals and the preparation method and application thereof with circular polarised luminescence property based on folded formation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Synthesis of Planar Chiral Carbazole Derivatives Bearing a [2.2]Paracyclophane Skeleton;Petra Lennartz，等;《Isr. J. Chem》;20121231;第52卷;171-179 *

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