CN113817090B - Triterpyridine-based transition metal ion fluorescence chemical sensor and preparation method thereof - Google Patents

Triterpyridine-based transition metal ion fluorescence chemical sensor and preparation method thereof Download PDF

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CN113817090B
CN113817090B CN202110902660.9A CN202110902660A CN113817090B CN 113817090 B CN113817090 B CN 113817090B CN 202110902660 A CN202110902660 A CN 202110902660A CN 113817090 B CN113817090 B CN 113817090B
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陈学刚
刘攀
马陈陈
迟政
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Abstract

The invention relates to a terpyridine-based transition metal ion fluorescence chemical sensor and a preparation method thereof, belonging to the technical field of transition metal ion fluorescence chemical sensors. The structural formula of the terpyridine-based transition metal ion fluorescence chemical sensor is shown in the specification
Figure DDA0003200552400000011
Wherein Ar is a hydrophilic monomer; n is the number of repeating units, and n is 0 to 6; r is an alkyl chain, and the number of C atoms is =6-30; x, y, z are the relative proportions of the three monomers, x + y + z =100%, wherein x = 0.2-10%, z = 0.2-10%; adding 9,9-dialkyl fluorene as a conjugated vinyl monomer of a structural unit, 4- (4 '-2,2':6', 2' -terpyridine) styrene, a hydrophilic monomer and azobisisobutyronitrile into 1,4-dioxane, stirring and reacting for 6-10 hours at the temperature of 75-85 ℃, and placing the mixture in dichloromethane for sedimentation to obtain a random copolymer, namely the terpyridine-based transition metal ion fluorescence chemical sensor; the structural formula of the conjugated alkene monomer taking 9,9-dialkyl fluorene as a structural unit is shown in the specification

Description

Triterpyridine-based transition metal ion fluorescence chemical sensor and preparation method thereof
Technical Field
The invention relates to a terpyridine-based transition metal ion fluorescence chemical sensor and a preparation method thereof, and belongs to the technical field of transition metal ion fluorescence chemical sensors.
Background
Transition metal ions are widely present in the environment and in living organisms, some ions being Fe 2+ 、Zn 2+ Etc. have very important effects on life process, and some ions such as Cd 2+ And the like have toxic action. In addition, the nature of action of many ions also depends on their specific concentration. Therefore, rapid, accurate and convenient detection of these ions is an important issue in the fields of environmental monitoring, industrial production, biomedicine, food safety, and the like.
The traditional chemical titration method has the defects of low monitoring speed, poor data repeatability, large influence of environmental factors, high operation requirement, limited detection lower limit concentration and the like; in addition, most of application scenes of some organic/polymer chemical sensors are organic solvents, so that the organic/polymer chemical sensors cannot be applied to a water medium system, and direct application of the organic/polymer chemical sensors in the life process and the environmental field is greatly limited.
Therefore, the development of the high-efficiency fluorescence sensor in the water system has important significance.
Disclosure of Invention
Aiming at the problems of the existing transition metal ion fluorescence chemical sensor, the invention provides a transition metal ion fluorescence chemical sensor based on terpyridine and a preparation method thereof, namely, a hydrophilic monomer is taken as a main monomer, and a fluorescence conjugated monomer fluorene derivative and 4- (4 '-2,2':6', 2' -terpyridine) styrene (TPY) are introduced to synthesize a hydrophilic copolymer, namely, the polymer metal ion fluorescence chemical sensor.
A terpyridine-based transition metal ion fluorescence chemical sensor has a structural formula as follows:
Figure BDA0003200552380000011
wherein Ar is a hydrophilic monomer; n is the number of repeating units, and n is 0 to 6; r is an alkyl chain, and the number of C atoms is =6-30; x, y, z are the relative proportions of the three monomers, x + y + z =100%, wherein x = 0.2-10%, z = 0.2-10%; the hydrophilic monomer is acrylic acid, methacrylic acid, acrylamide or methacrylamide.
The preparation method of the terpyridine-based transition metal ion fluorescence chemical sensor comprises the following specific steps:
adding 9,9-dialkyl fluorene as a conjugated vinyl monomer of a structural unit, 4- (4 '-2,2':6', 2' -terpyridine) styrene, a hydrophilic monomer and azobisisobutyronitrile into 1,4-dioxane, stirring and reacting for 6-10 hours at the temperature of 75-85 ℃, and placing the mixture in dichloromethane for sedimentation to obtain a random copolymer, namely the terpyridine-based transition metal ion fluorescence chemical sensor;
wherein the hydrophilic monomer is acrylic acid, methacrylic acid, acrylamide or methacrylamide;
the structural formula of the conjugated alkene monomer taking 9,9-dialkyl fluorene as a structural unit is shown in the specification
Figure BDA0003200552380000021
Wherein n is the number of repeating units, and n = 0-6;
r is an alkyl chain, and the number of C atoms is =6-30.
Further, when n is 1-6, the preparation method of the conjugated alkene monomer taking 9,9-dialkyl fluorene as a structural unit comprises the following steps
(1) Synthesis of 2-bromofluorene: dropwise adding the bromine/trichloromethane mixed solution into the fluorene/catalyst/trichloromethane mixed solution under the conditions of light resistance, nitrogen atmosphere and temperature of-5-10 ℃, stirring for reaction for 3-5 h, washing, filtering, drying, and recrystallizing in DCM-methanol to obtain 2-bromofluorene;
(2) Synthesis of 2-bromo-9,9-dialkylfluorene: under the conditions of light protection and nitrogen atmosphere, adding alkyl bromide and tetrabutylammonium bromide into a 2-bromofluorene/toluene mixed solution, stirring and reacting for 20-30 h at the temperature of 65-80 ℃, neutralizing with dilute hydrochloric acid in sequence, extracting with DCM, and purifying by column chromatography to obtain 2-bromo-9,9-dialkyl fluorene;
(3) Synthesis of 2-bromo-7-acetyl-9,9-dialkylfluorene: adding acetyl chloride and a catalyst into a mixed solution of 2-bromo-9,9-dialkyl fluorene/dichloromethane or 2-bromo-9,9-dialkyl fluorene/trichloromethane in a nitrogen atmosphere, stirring and reacting for 3-5 h at the temperature of-5-10 ℃, washing, filtering, drying, and purifying by column chromatography to obtain 2-bromo-7-acetyl-9,9-dialkyl fluorene;
(4) Synthesis of 2-bromo-7- (1-hydroxy) ethyl-9,9-dialkylfluorene: adding strong base into the mixed solution of 2-bromo-7-acetyl-9,9-dialkyl fluorene/absolute ethyl alcohol in the nitrogen atmosphere at the temperature of-5-10 ℃, uniformly mixing, heating to the temperature of 20-30 ℃, stirring for reaction for 0.5-1.5 h, and recrystallizing to obtain 2-bromo-7- (1-hydroxy) ethyl-9,9-dialkyl fluorene;
(5) Synthesis of 2-bromo-7-vinyl-9,9-dialkylfluorene: heating the 2-bromo-7- (1-hydroxy) ethyl-9,9-dialkyl fluorene/toluene mixed solution to reflux, adding a catalyst, stirring, refluxing and reacting for 10-30 min, and purifying by column chromatography to obtain 2-bromo-7-vinyl-9,9-dialkyl fluorene;
(6) 5363 Synthesis of conjugated olefin monomer with 9,9-dialkyl fluorene as structural unit: adding an alkaline solution into a 2-bromo-7-vinyl-9,9-dialkyl fluorene/monoboronic ester group substituted alkyl fluorene oligomer derivative/tetrahydrofuran mixed solution, adding a catalyst in a nitrogen atmosphere, reacting for 18-24 hours at a temperature of 60-85 ℃ in a dark place, and purifying by column chromatography to obtain a conjugated alkene monomer taking 9,9-dialkyl fluorene as a structural unit; wherein the structural formula of the oligomer derivative of the alkyl fluorene substituted by the single borate group is shown in the specification
Figure BDA0003200552380000031
Wherein n is the number of repeating units, and n =0 to 5;
r is an alkyl chain, and the number of C atoms =6-30.
Furthermore, when n is 1-6, the molar ratio of bromine to fluorene in the step (1) in the preparation method of the conjugated alkene monomer taking 9,9-dialkyl fluorene as a structural unit is 0.95-1.05, the catalyst is ferric chloride, the adding amount of the catalyst is 2-3% of the molar amount of the fluorene, and the detergent is NaHSO 3 An aqueous solution and dichloromethane; the molar ratio of alkyl bromide to 2-bromofluorene in the step (2) is 2.1-3.0, the addition amount of tetrabutylammonium bromide is 6-15% of the molar amount of 2-bromofluorene, and the mobile phase of column chromatography is petroleum ether; the molar ratio of acetyl chloride to 2-bromo-9,9-dialkyl fluorene in the step (3) is 1.2-2.0, the catalyst is aluminum chloride, the molar ratio of 2-bromo-9,9-dialkyl fluorene to aluminum chloride is 1 (1.5-3), the washing agent is water and DCM, and the mobile phase of column chromatography is petroleum ether and ethyl acetate; the strong base in the step (4) is sodium borohydride, and the molar ratio of the sodium borohydride to the 2-bromo-7-acetyl-9,9-dialkyl fluorene is 2.5-1.8; the catalyst in the step (5) is toluenesulfonic acid, the molar ratio of the toluenesulfonic acid to the 2-bromo-7- (1-hydroxy) ethyl-9,9-dialkyl fluorene is 1 (8-15),the column chromatography mobile phase is petroleum ether or n-hexane; the molar ratio of the 2-bromo-7-vinyl-9,9-dialkyl fluorene to the 2-pinacol boronate-9,9-dialkyl fluorene in the step (6) is 0.80-1.2, and the catalyst is Pd (PPh 3 ) 4 Or Pd (dppf) Cl 2 The molar ratio of the catalyst to the 2-bromo-7-vinyl-9,9-dialkyl fluorene is 1 (6-25), the alkaline solution is potassium carbonate or sodium carbonate solution, and the molar ratio of the alkali in the alkaline solution to the 2-bromo-7-vinyl-9,9-dialkyl fluorene is (15-40) to 1;
furthermore, when n is 1-6, the preparation method of the oligomer derivative of alkylfluorene substituted by the single borate ester group in the step (6) in the preparation method of the conjugated alkene monomer taking 9,9-dialkylfluorene as the structural unit comprises the following steps
1) Synthesis of 2-pinacol boronate-9,9-dialkylfluorene: adding pinacol diboron and potassium ethoxide into a 2-bromo-9,9-dialkyl fluorene/dimethyl sulfoxide mixed solution, and adding Pd (dppf) Cl in the nitrogen atmosphere 2 Uniformly mixing, heating to 80-95 ℃, stirring and reacting for 20-36 h under the condition of keeping out of the sun, and purifying by column chromatography to obtain 2-pinacol borate-9,9-dialkyl fluorene, namely, the oligomer derivative of alkyl fluorene substituted by monoborate group with n being 0;
2) Synthesis of 2-pinacol boronate- (9,9-dialkylfluorene) n-mer: adding pinacol diboron and potassium ethoxide into a mixed solution of 2-bromo- (9,9-alkyl) fluorene (n-1) polymer/dimethyl sulfoxide, and adding Pd (dppf) Cl in the nitrogen atmosphere 2 Uniformly mixing, heating to 80-95 ℃, stirring and reacting for 20-36 h under the condition of keeping out of the sun, and purifying by column chromatography to obtain 2-pinacol borate- (9,9-dialkyl fluorene) n polymer;
furthermore, the molar ratio of the pinacol diboron ester in the step 1) to the 2-bromo-9,9-dialkyl fluorene is 1.5-3.0, and the catalyst is Pd (dppf) Cl 2 Or Pd (PPh) 3 ) 4 The mol ratio of the catalyst to the 2-bromo-9,9-dialkyl fluorene is 0.02-0.05, and the mobile phase of column chromatography is petroleum ether and ethyl acetate; step 2), the molar ratio of the pinacol diboron to the 2-bromo- (9,9-alkyl) fluorene (n-1) polymer is 1.5-3.0, and the catalyst is Pd (dppf) Cl 2 Or Pd (PPh) 3 ) 4 Catalysts andthe molar ratio of the 2-bromo-fluorene (n-1) polymer is 0.02-0.05, and the column chromatography mobile phase comprises petroleum ether and ethyl acetate;
further, when n is 0, the preparation method of the conjugated alkene monomer taking 9,9-dialkyl fluorene as a structural unit comprises the following steps
(1) Synthesis of 9,9-dialkylfluorene: dropwise adding n-butyllithium into a fluorene/THF system at the temperature of-78 to-50 ℃ in a nitrogen atmosphere to obtain a mixture A, dropwise adding a 1-bromoalkane/THF solution into the mixture A, reacting at room temperature for 20 to 36 hours under nitrogen, extracting with ethyl acetate, and purifying by column chromatography to obtain 9,9-dialkylfluorene;
(2) Synthesis of 2-acetyl-9,9-dialkylfluorene: adding acetyl chloride and a catalyst into 9,9-dialkyl fluorene/dichloromethane or 9,9-dialkyl fluorene/trichloromethane mixed solution in a nitrogen atmosphere, stirring and reacting for 3-5 h at the temperature of-5-10 ℃, washing, filtering, drying, and purifying by column chromatography to obtain 2-acetyl-9,9-dialkyl fluorene;
(3) Synthesis of 2-ethanolyl-9,9-dialkylfluorene: adding strong base into the mixed solution of 2-acetyl-9,9-dialkyl fluorene and absolute ethyl alcohol in the nitrogen atmosphere at the temperature of-5-10 ℃, uniformly mixing, heating to the temperature of 20-30 ℃, stirring for reaction for 0.5-1.5 h, and recrystallizing to obtain 2-ethanol-9,9-dialkyl fluorene;
(4) Synthesis of 2-vinyl-9,9-dialkylfluorene: heating the 2-ethanol-9,9-dialkyl fluorene/toluene mixed solution to reflux, adding a catalyst, stirring, refluxing and reacting for 10-30 min, and performing column chromatography purification to obtain 2-vinyl-9,9-dialkyl fluorene;
furthermore, when n is 0, the molar ratio of the n-butyllithium to the fluorene in the step (1) in the preparation method of the conjugated alkene monomer taking 9,9-dialkyl fluorene as a structural unit is 2.2-4.0; the molar ratio of acetyl chloride to 9,9-Xin Hu in the step (2) is 1.2-2.0, the catalyst is aluminum chloride, the molar ratio of 9,9-Xin Hu to aluminum chloride is 1 (1.5-3), the detergent is water and DCM, and the mobile phase of column chromatography is petroleum ether and ethyl acetate; the strong base in the step (3) is sodium borohydride, and the molar ratio of the sodium borohydride to the 2-acetyl-9,9-dioctyl fluorene is 2.5-1.8; the catalyst in the step (4) is toluenesulfonic acid, the molar ratio of the toluenesulfonic acid to the 2-ethanol-9,9-dioctyl fluorene is 1 (8-15), and the column chromatography mobile phase is petroleum ether or n-hexane.
The invention has the beneficial effects that:
(1) According to the invention, the fluorescent conjugated vinyl monomer and the hydrophilic monomer are subjected to free radical copolymerization, so that the final polymer is endowed with the property of high-efficiency fluorescence emission in a water system by a conventional copolymerization method;
(2) The terpyridine derivative alkene monomer unit with wide coordination with transition metal ions is introduced into the polymer, so that an action point capable of performing coordination with the transition metal is provided for the copolymer;
(3) The polymer sensor designed by the invention can be applied to an aqueous medium, and the high-efficiency detection of transition metal ions is realized;
(4) The copolymer designed by the invention is used for Fe 2+ 、Zn 2+ Has higher spectral selectivity and can carry out fluorescence spectrum detection on the fluorescent dye quantitatively.
Drawings
FIG. 1 shows a conjugated olefin monomer VOF having 9,9-dialkylfluorene as a structural unit in examples 1 and 2 1 And VOF 2 An infrared spectrum of (1);
FIG. 2 is the random copolymer PATF of example 1 and example 2 1 And PATF 2 -1 infrared spectrum;
FIG. 3 is a drawing of a monomer TPY 1 H nuclear magnetic spectrum;
FIG. 4 is the UV-VIS absorption spectrum of example 4;
FIG. 5 is a fluorescence emission spectrum of example 4;
FIG. 6 is the example 5 Polymer PATF 1 Color and fluorescence change pattern when reacting with different metal ions;
FIG. 7 is the example 5 Polymer PATF 2 -1 color and fluorescence change profiles with different metal ions;
FIG. 8 is the example 5 Polymer PATF 2 -1 UV-visible absorption by interaction with different metal ions(ii) a spectrum;
FIG. 9 is the example 5 Polymer PATF 2 -1 fluorescence emission spectra with different metal ions;
FIG. 10 is the example 5 Polymer PATF 2 -1 and Fe 2+ Quantitative fluorescence quenching response map of (1);
FIG. 11 is the example 5 Polymer PATF 2 -1 with Zn 2+ Quantitative fluorescence enhancement response map of (1).
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: the structural formula of the transition metal ion fluorescence chemical sensor based on terpyridine is shown in the specification
Figure BDA0003200552380000051
Is described as copolymer PATF 1 ；
5363A conjugated olefin monomer with structure unit of 9,9-dioctyl fluorene
Figure BDA0003200552380000052
Named 2-vinyl-9,9-dioctylfluorene and noted as compound VOF 1 ；
The synthetic route of the transition metal ion fluorescence chemical sensor based on terpyridine is
Figure BDA0003200552380000061
x is 0.5 and y is 5.0.z is 94.5;
the preparation method of the transition metal ion fluorescence chemical sensor based on terpyridine comprises the following specific steps:
adding 9,9-dioctyl fluorene as a conjugated vinyl monomer of a structural unit, 4- (4 '-2,2':6', 2' -terpyridine) styrene, acrylic acid and azobisisobutyronitrile into 1,4-dioxane, stirring and reacting for 8 hours at the temperature of 80 ℃, and placing the mixture in dichloromethane for sedimentation to obtain a random copolymer, namely the terpyridine-based transition metal ion fluorescence chemical sensor; wherein 9,9-dioctyl fluorene is a conjugated alkene monomer of a structural unit, 4- (4 '-2,2':6', 2' -terpyridine) styrene and acrylic acid are in a molar ratio of 0.5; the addition amount of the azodiisobutyronitrile is 0.5 to 2 percent of the mass of the monomer;
random copolymer (PATF) 1 ) The infrared spectrum of (A) is shown in FIG. 2:3130cm -1 Nearby absorption is υ OH ，2930cm -1 Nearby absorption is υ CH ，1716cm -1 Is upsilon C＝O ，1453cm -1 Near absorption is δ CH ，1530cm -1 Nearby absorption is upsilon on benzene ring C＝C V on pyridine heterocycle C＝N Absorption was at 1595cm -1 Nearby;
of monomeric TPY 1 The H nuclear magnetic spectrum is shown in FIG. 3:
1 H NMR(500MHz,CDCl 3 ):δ(ppm)8.75-8.67(6H,m),7.91-7.88(4H,m),7.56(2H,m),7.37-7.36(2H,m),6.76-6.81(1H,q),5.86(1H,d),5.34(1H,d).
the molecular weight of the random copolymer PATF1 was 2.93X 10 5 g/mol；
5363A synthetic route of conjugated olefin monomer with 9,9-dioctyl fluorene as a structural unit is as follows:
Figure BDA0003200552380000071
the preparation method of the conjugated alkene monomer taking 9,9-dioctyl fluorene as a structural unit comprises the following steps
(1) Synthesis of 9,9-dioctylfluorene (Compound 8): dropwise adding n-butyllithium into a fluorene/THF system under the nitrogen atmosphere at-78 ℃ to obtain a mixture A, dropwise adding a 1-bromooctane/THF solution into the mixture A, reacting at room temperature for 24 hours under nitrogen, extracting with ethyl acetate, and purifying by column chromatography to obtain 9,9-Xin Hu; wherein the mol ratio of n-butyllithium to fluorene is 3;
(2) Synthesis of 2-acetyl-9,9-dioctylfluorene (Compound 9): adding acetyl chloride and a catalyst into a 9,9-Xin Hu/dichloromethane or 9,9-Xin Hu/trichloromethane mixed solution in a nitrogen atmosphere, stirring and reacting for 4 hours at the temperature of 0 ℃, washing, filtering, drying, and purifying by column chromatography to obtain 2-acetyl-9,9-dioctyl fluorene; wherein the molar ratio of acetyl chloride to 9,9-Xin Hu is 1.5, the catalyst is aluminum chloride, the molar ratio of 9,9-Xin Hu to aluminum chloride is 1:2, the detergent is water and DCM, and the mobile phase of column chromatography is petroleum ether and ethyl acetate;
(3) Synthesis of 2-EtOH-9,9-dioctylfluorene (Compound 10): under the conditions of nitrogen atmosphere and 0 ℃, adding strong base into the mixed solution of 2-acetyl-9,9-dioctyl fluorene/absolute ethyl alcohol, uniformly mixing, heating to the temperature of 25 ℃, stirring for reaction for 1.0h, and recrystallizing to obtain 2-ethanol-9,9-dioctyl fluorene; wherein the strong base is sodium borohydride, and the molar ratio of the sodium borohydride to the 2-acetyl-9,9-dioctylfluorene is 2.0;
(4) 2-vinyl-9,9-dioctylfluorene (compound VOF) 1 ) The synthesis of (2): heating the 2-ethanol-9,9-dioctylfluorene/toluene mixed solution to reflux, adding catalyst, stirring, refluxing, reacting for 20min, and purifying by column chromatography to obtain 2-vinyl-9,9-dioctylfluorene (see figure 1); wherein the catalyst is toluenesulfonic acid, the molar ratio of the toluenesulfonic acid to 2-ethanol-9,9-dioctyl fluorene is 1;
as can be seen from fig. 1: 3060cm -1 Absorption v ＝CH ，2920cm -1 And 2854cm -1 Near absorption v CH And furthermore 1370cm -1 -1460cm -1 Range and 827cm -1 Near absorption is δ CH . V in the molecular Structure C＝C Absorption was at 1623cm -1 -1570cm -1 Nearby, the rest of the framework vibration absorption peaks are weak because the molecules have certain symmetry. Omega ＝CH Absorption of (2) is at 988cm -1 Near, and ω ＝CH2 Absorption of (2) is located at 892cm -1 Near, free VOF 1 And VOF 2 The molecular structure of the compound contains long alkyl chain in (CH) 2 ) n In the structure of CH 2 In-plane rocking vibration absorption peak ofLocated at 738cm -1 Nearby;
VOF of the present embodiment 1 Is/are as follows 1 H nuclear magnetic spectrum: 1 H NMR(500MHz,CDCl 3 ):δ(ppm)7.68-7.63(2H,m),7.40-7.28(5H,m),6.81(1H,m),5.82(1H,d,J＝8.8Hz),5.27(1H,d,J＝5.4Hz),1.95(4H,t,J＝6.0Hz),1.26-1.04(20H,m),0.81(6H,t,J＝7.1Hz),0.62(4H,m).
VOF of the present embodiment 1 Is/are as follows 13 C nuclear magnetic spectrum: 13 C NMR(100MHz,CDCl 3 ):δ(ppm)151.1,151.0,141.1,140.8,137.5,136.5,129.1,128.2,127.0,126.7,125.2,122.9,120.5,119.7,112.9,55.0,40.4,31.8,30.0,29.3,23.7,22.6,14.1.MS(ESI + ,CH 3 CN):m/z 418.27(M+H) + .
this example is 2-vinyl-9,9-dioctylfluorene VOF 1 The yield of (a) was 73%.
Example 2: the structural formula of the transition metal ion fluorescence chemical sensor based on terpyridine is shown in the specification
Figure BDA0003200552380000081
Is described as copolymer PATF 2 1,x of 0.5, y of 94.5, z of 5.0;
5363A conjugated olefin monomer with structure unit of 9,9-dialkyl fluorene
Figure BDA0003200552380000082
Is named as 7-vinyl-9,9,9 ',9' -dioctyl- [2,2']Bifluorene, noted as compound VOF 2 ；
The synthetic route of the transition metal ion fluorescence chemical sensor based on terpyridine is
Figure BDA0003200552380000091
The preparation method of the terpyridine-based transition metal ion fluorescence chemical sensor comprises the following specific steps:
a conjugated olefin monomer taking 9,9-dialkyl fluorene as a structural unit, 4- (4 ' -2,2':6', 2-Terpyridine) styrene, acrylic acid and azobisisobutyronitrile into 1,4-dioxane, stirring and reacting at 80 ℃ for 8h, and settling in dichloromethane to obtain random copolymer (PATF) 2 -1) transition metal ion fluorescence chemical sensors based on terpyridine; wherein 9,9-dialkyl fluorene is a conjugated alkene monomer of a structural unit, 4- (4 '-2,2':6', 2' -terpyridine) styrene and acrylic acid are in a molar ratio of 0.5; the addition amount of the azodiisobutyronitrile is 0.5 to 1 percent of the mass of the monomer;
random copolymer (PATF) 2 The IR spectrum of-1) is shown in FIG. 2:3130cm -1 Nearby absorption is υ OH ，2930cm -1 The nearby absorption is upsilon CH ，1716cm -1 Is upsilon C＝O ，1453cm -1 Near absorption is δ CH ，1530cm -1 Nearby absorption is upsilon on benzene ring C＝C V on pyridine heterocycle C＝N Absorption was at 1595cm -1 Nearby;
random copolymer PATF 2 -1 molecular weight 2.25X 10 5 g/mol；
The synthesis route of the conjugated alkene monomer taking 9,9-dialkyl fluorene as a structural unit is as follows:
Figure BDA0003200552380000101
5363A synthetic method of conjugated olefin monomer with 9,9-dialkyl fluorene as structural unit comprises the following steps:
(1) Synthesis of 2-bromofluorene (Compound 2): under the conditions of light protection and nitrogen atmosphere and at the temperature of 0 ℃, bromine (7.67mL, 0.15mol) is dissolved in anhydrous trichloromethane solution (50 mL) to obtain bromine/trichloromethane mixed solution, the bromine/trichloromethane mixed solution is dropwise added into the fluorene/ferric chloride/trichloromethane mixed solution and stirred for reaction for 3 hours, wherein in the fluorene/ferric chloride/trichloromethane mixed solution, 0.65g of ferric chloride, 25.00g of fluorene (0.15 mol) and CHCl are contained 3 300mL, the reaction system is subjected to NaHSO 3 The aqueous solution and Dichloromethane (DCM) were washed to light yellow, filtered and spun dry, and recrystallized in DCM-methanol to give 33.83g of a light yellow crystalline solid (92%);fluorene is denoted as compound 1;
the nuclear magnetic resonance hydrogen spectrum of the light yellow crystalline solid is
1 H NMR(500MHz,CDCl 3 ):δ(ppm)7.76(1H,d,J＝7.5Hz),7.68(1H,s),7.65(2H,d,J＝7.5Hz),7.54(2H,d,J＝7.4Hz),7.51(2H,d,J＝8Hz),7.38(2H,d,J＝7.4Hz),7.32(2H,d,J＝7.3Hz),3.89(2H,s).
Therefore, the light yellow crystalline solid is 2-bromofluorene;
(2) Synthesis of 2-bromo-9,9-dioctylfluorene (Compound 3): under the conditions of light protection and nitrogen atmosphere, adding 1-bromooctane and tetrabutylammonium bromide into a 2-bromofluorene/toluene mixed solution, stirring and reacting for 20 hours at the temperature of 65 ℃, neutralizing with dilute hydrochloric acid and extracting with DCM sequentially, drying, filtering, distilling under reduced pressure to remove redundant toluene and 1-bromooctane, and purifying by column chromatography (the mobile phase is petroleum ether) to obtain 24.00g of oily product (87%); wherein the mass of the 2-bromofluorene is 14.77g, namely 0.06mol, the toluene solution is 100mL, the tetrabutylammonium bromide is 2.00g, and the 1-bromooctane is 26mL;
the NMR spectrum of the oily product is
1 H NMR(500MHz,CDCl 3 ):δ(ppm)7.71(1H,d,J＝7.3Hz),7.68(1H,s),7.56(1H,d,J＝8.1Hz),7.43(2H,t,J＝8.4Hz),7.36(2H,m),1.97(4H,t,J＝7.2Hz),1.19(24H,m),0.85(6H,t,J＝7.8Hz).
So that the oily product is 2-bromo-9,9-dioctylfluorene;
(3) Synthesis of 2-bromo-7-acetyl-9,9-dioctylfluorene (Compound 4): dissolving 2-bromo-9,9-dioctylfluorene (3.07g, 6.60mmol) in DCM solution to obtain 2-bromo-7-acetyl-9,9-dioctylfluorene/DCM mixed solution, adding acetyl chloride (0.70ml, 9.90mmol) and anhydrous aluminum trichloride (1.76g, 13.20mmol) to the 2-bromo-7-acetyl-9,9-dioctylfluorene/DCM mixed solution at 0 ℃ under nitrogen atmosphere and temperature of 0 ℃ and stirring for reaction for 3h, quenching the dark blue suspension to light yellow with ice water, washing with water and DCM, filtering and evaporating the solvent, and purifying by column chromatography (mobile phase is petroleum ether and ethyl acetate, petroleum ether: ethyl acetate = 10) to obtain light yellow solid (3.03g, 90%);
the nuclear magnetic resonance hydrogen spectrum of the light yellow solid is
1 H NMR(500MHz,CDCl 3 ):δ(ppm)7.97(2H,t,J＝5.6Hz),7.73(1H,d,J＝7.8Hz),7.60(1H,d,J＝8.7Hz),7.50(2H,d,J＝6.6Hz),2.66(3H,s),1.96(4H,m),1.26-1.05(24H,m),0.81(6H,t,J＝7.2Hz).
Therefore, the light yellow solid is 2-bromo-7-acetyl-9,9-dioctyl fluorene;
(4) Synthesis of 2-bromo-7-ethanolyl-9,9-dioctylfluorene (Compound 5): under the condition of nitrogen atmosphere and 0 ℃, adding sodium borohydride (0.22g, 5.70mmol) into a mixed solution of 2-bromo-7-acetyl-9,9-dioctylfluorene/absolute ethyl alcohol, uniformly mixing, heating to 20 ℃, stirring and reacting for 1.0h, removing absolute ethyl alcohol in the system, extracting with DCM, and recrystallizing to obtain white crystals (1.23g, 86%); wherein the mass of the 2-bromo-7-acetyl-9,9-dioctyl fluorene is 1.45g, namely 2.80mmol, and the absolute ethyl alcohol is 80mL;
the nuclear magnetic resonance hydrogen spectrum of the white crystal is
1 H NMR(500MHz,CDCl 3 ):δ(ppm)7.63(1H,d,J＝8.2Hz),7.54(1H,d,J＝8.2Hz),7.44(2H,s),7.33(2H,m),4.99(1H,m),1.93(4H,m),1.72(1H,m),1.57-1.53(4H,m),1.22-1.04(20H,m),0.82(6H,t,J＝8.7Hz).
So that the white crystal is 2-bromo-7-ethanol-9,9-dioctyl fluorene;
(5) Synthesis of 2-bromo-7-vinyl-9,9-dioctylfluorene (Compound 6): dissolving 2-bromo-7-ethanol-9,9-dioctylfluorene (1.024g, 2.00mmol) in toluene (25 mL) to obtain 2-bromo-7-ethanol-9,9-dioctylfluorene/toluene mixed solution, heating 2-bromo-7-ethanol-9,9-dioctylfluorene/toluene mixed solution to boiling reflux, continuously distilling off toluene for 5min in a distillation head, adding catalyst toluenesulfonic acid (0.035g, 0.20mmol) and stirring reflux reacting for 10min, quenching the reaction system by using ice water, washing the reaction system by brine and DCM, drying, filtering and spin-drying the solvent, purifying by column chromatography (the mobile phase is petroleum ether) to obtain a transparent oily product (0.90g, 92%);
the NMR spectrum of the transparent oily product is
1 H NMR(500MHz,CDCl 3 ):δ(ppm)7.64(1H,d,J＝7.9Hz),7.57(1H,d,J＝8.6Hz),7.49(2H,m),7.44(1H,d,J＝7.8Hz),7.38(1H,s),6.84(1H,m),5.86(1H,d,J＝8.8Hz),5.32(1H,d,J＝5.4Hz),1.98(4H,t,J＝9.7Hz),1.30-1.09(24H,m),0.85(6H,t,J＝7.2Hz).
The clear oily product was 2-bromo-7-vinyl-9,9-dioctylfluorene;
(6) Synthesis of 2-p-pinacol boronate-9,9-dioctylfluorene (Compound 7): dissolving 2-bromo-9,9-dioctylfluorene (14.05g, 0.03mol) in dimethyl sulfoxide (DMSO) solution to obtain 2-bromo-9,9-dialkylfluorene/dimethyl sulfoxide mixed solution, adding pinacol diborate (15.23g, 0.06mol) and potassium ethoxide (8.83g, 0.09mol) to 2-bromo-9,9-dialkylfluorene/dimethyl sulfoxide mixed solution, adding Pd (dppf) Cl under nitrogen atmosphere 2 (0.53g, 0.73mmol) and heating to 80 ℃, stirring and reacting for 20h under dark conditions, extracting with DCM, drying, filtering and spin-drying the solvent, purifying by column chromatography (mobile phase is petroleum ether and ethyl acetate, petroleum ether: ethyl acetate = 10) to obtain a clear oily product (12.05g, 78%);
the NMR spectrum of the transparent oily product is
1 H NMR(500MHz,CDCl 3 ):δ(ppm)7.79(1H,d,J＝7.8Hz),7.73-7.68(3H,m),7.32-7.31(3H,m),1.96(4H,t,J＝5.6Hz),1.39(12H,s),1.23-1.01(24H,m),0.81(6H,t,J＝7.1Hz).
So the transparent oily product is 2-p-pinacol borate-9,9-dioctyl fluorene;
(7) 7-vinyl-9,9,9 ',9' -dioctyl- [2,2']Bifluorene (VOF) 2 ) Synthesis: adding 2-bromo-7-vinyl-9,9-dioctylfluorene (1.17g, 2.40mmol) and 2-p-pinacol boronate-9,9-dioctylfluorene (1.35g, 2.60mmol) to a THF (100 mL) solution to obtain a 2-bromo-7-vinyl-9,9-dioctylfluorene/2-p-pinacol boronate-9,9-dioctylfluorene/THF mixed solution, adding an aqueous sodium carbonate solution (1.6M, 35mL) to a 2-bromo-7-vinyl-9,9-dioctylfluorene/2-p-pinacol boronate-9,9-dioctylfluorene/THF mixed solution, rapidly adding a catalyst Pd (dppf) Cl under nitrogen atmosphere 2 (0.26g, 0.36mmol) and refluxing reaction at 75 deg.C in the dark for 20h, extraction with DCM, drying, filtration and evaporation of the solventPurifying by column chromatography (petroleum ether as mobile phase) to obtain target product;
nuclear magnetic resonance hydrogen spectrum of the target product:
1 H NMR(500MHz,CDCl 3 ):δ(ppm)7.78-7.73(3H,m),7.67(1H,d,J＝7.7Hz),7.64(2H,d,J＝7.9Hz),7.60(2H,s),7.43(1H,d,J＝7.9Hz),7.39(1H,s),7.37-7.30(3H,m),6.86-6.80(1H,m),5.84(1H,d,J＝8.8Hz),5.28(1H,d,J＝5.4Hz),2.03(8H,t,J＝7.7Hz),1.25-1.08(48H,m),0.80(12H,t,J＝7.2Hz).
nuclear magnetic resonance carbon spectrum of target product:
13 C NMR(100MHz,CDCl 3 ):δ(ppm)151.8,151.5,151.4,151.0,140.8,140.5,140.4,140.3,140.0,137.5,136.5,129.0,128.8,128.2,127.2,127.0,126.8,126.1,126.0,125.3,123.0,121.5,121.4,120.6,119.9,119.7,113.0,55.17,55.14,31.8,30.0,29.2,23.8,22.6,14.0.MS(ESI + ,CH 3 CN):m/z 827.69(M+Na) + .
the infrared spectrum of the target product is shown in figure 1, 3060cm-1 is C-H stretching vibration peak on unsaturated carbon, 2920cm -1 、2854cm -1 Is a saturated C-H stretching vibration peak, 1623cm -1 Is C = C stretching vibration peak, 1457cm -1 892-738 cm as C-H deformation vibration peak -1 Is the C-H deformation vibration peak of the aromatic ring;
therefore, the target product is 7-vinyl-9,9,9 ',9' -dioctyl- [2,2']Bifluorene (VOF) 2 )。
Example 3: the structural formula of the terpyridine-based transition metal ion fluorescence chemical sensor is shown in the specification
Figure BDA0003200552380000131
Is described as copolymer PATF 2 2,x of 0.5, y of 98.0, z of 1.5;
the preparation method of the terpyridine-based transition metal ion fluorescence chemical sensor comprises the following specific steps:
adding a conjugated vinyl monomer taking 9,9-dialkyl fluorene as a structural unit, 4- (4 '-2,2':6', 2' -terpyridine) styrene, acrylic acid and azobisisobutyronitrile into 1,4-dioxane, stirring and reacting at 80 ℃ for 8 hours, and settling in dichloromethane to obtain a random copolymer (PATF) 2 -1) transition metal ion fluorescence chemical sensors based on terpyridine; wherein 9,9-dialkyl fluorene is a conjugated alkene monomer of a structural unit, 4- (4 '-2,2':6', 2' -terpyridine) styrene and acrylic acid are in a molar ratio of 0.5; the addition amount of the azodiisobutyronitrile is 0.8 percent of the mass of the monomer;
random copolymer PATF 2 -2 molecular weight 2.56X 10 5 g/mol；
In this example 9,9-dialkylfluorene as a conjugated olefinic monomer having a structural unit, 7-vinyl-9,9,9 ',9' -dioctyl- [2,2']Bifluorene (VOF) 2 )。
Comparative example 1: adding 4- (4 '-2,2':6', 2' -terpyridine) styrene, acrylic acid and azobisisobutyronitrile into 1,4-dioxane, stirring and reacting for 8 hours at the temperature of 80 ℃, and placing in dichloromethane for settling to obtain a random copolymer, which is marked as PAT; wherein the mol ratio of 4- (4 '-2,2':6', 2' -terpyridine) styrene to acrylic acid is 5.0; the addition amount of the azodiisobutyronitrile is 0.8 percent of the mass of the monomer; the molecular weight of the random copolymer PAT was 3.78X 10 5 g/mol。
Comparative example 2: conjugated olefin monomer (VOF) with 9,9-dialkyl fluorene as structural unit 2 ) Adding acrylic acid and azodiisobutyronitrile into 1,4-dioxane, stirring at 80 deg.C for 8 hr, and settling in dichloromethane to obtain random copolymer (PAF) 2 (ii) a Wherein 9,9-dialkyl fluorene is a conjugated alkene monomer of a structural unit, and the molar ratio of acrylic acid is 0.5; the addition amount of the azodiisobutyronitrile is 0.8 percent of the mass of the monomer; random copolymer PAF 2 Molecular weight of 3.12X 10 5 g/mol。
Example 4: random copolymer PATF of example 1 1 Example 2 random copolymer PATF 2 Random copolymer PAT of comparative example 1 and random copolymer PAF of comparative example 2 2 The photophysical property characterization of (a);
the polymer skeleton structure mainly comprises hydrophilic monomer acrylic acid, so that the polymer skeleton structure has good solubility in a water system, and the copolymer is prepared into a solution with the concentration of 2.5g/L to characterize the ultraviolet-visible absorption spectrum and the fluorescence emission spectrum of the copolymer;
the polymer has an ultraviolet-visible absorption spectrum shown in FIG. 4, wherein the polymer PAT has a strong absorption peak near 284nm, and the polymer PAF 2 The main absorption peak appears only at 335nm, the benzene ring in the TPY is used as a weak electron-donating group caused by pi-pi transition of a strong conjugated unit TPY contained in the polymer, and the polymer solution has a weak absorption shoulder peak at 335nm due to an intramolecular charge transfer process (ICT) of bipyridyl heterocycle with electroabsorptivity; PATF 1 -1 and PATF 2 1 absorption spectrum, it can be seen that the intensity of the weak absorption peak at 335nm increases with the degree of conjugation of the VOF moiety after the VOF moiety is added to the polymer backbone, the Intramolecular Charge Transfer (ICT) is enhanced due to the introduction of the VOF group, and in the aqueous polymer solution, the VOF group is made to approach each other due to its hydrophobic interaction, and the stacking interaction aggravates the absorption phenomenon by affecting the distribution of the electron cloud;
the fluorescence emission spectrum is shown in FIG. 5, the emission peak of the polymer PAT is located near 365nm, and the peak shape is broad and slow, caused by the intramolecular charge transfer process (ICT) of the TPY part; polymer PATF 1 -1 and PATF 2 -1 fluorescence emission peaks around 378nm and 400nm, respectively, red-shifted by 13nm and 35nm with respect to PAT due to the addition of VOF increasing the conjugation of the polymer and the red-shifted degree increases with increasing conjugation, and the polymer PATF 1 -1 and PATF 2 The peak shape of the fluorescence emission peak of-1 becomes wider and slower, and the introduction of the conjugated group enhances the ICT process; while the polymer PAF does not contain TPY groups 2 The emission peak of (2) is located in the vicinity of 400nm, and the peak type is relatively sharp.
Example 5: random copolymer PATF of example 1 1 Example 2 random copolymer PATF 2 Sensing and detecting transition metal ions;
prepared at a concentration of2.5g﹒L -1 Of the polymer PATF 1 And PATF 2 -1 aqueous solutions, respectively, in the polymer PATF 1 And PATF 2 1X 10 concentration of the aqueous solution -3 Different type of metal ion (Fe) of M 2+ ，Cu 2+ ，Co 2+ ，Sn 2+ ，Ni 2+ ，Zn 2+ ，Cd 2+ )；
Polymer PATF 1 Color and fluorescence change pattern with different metal ions (see FIG. 6), polymer PATF 2 1 color and fluorescence change diagram with different metal ions (see FIG. 7), two polymer solutions having different color responses to different metal ions, adding Fe 2+ Then all the polymer solution is changed into violet from colorless, and Co is added into the polymer solution 2+ Then turns brown, cu is added 2+ Then becomes light blue;
addition of Zn to Polymer solutions 2+ And Cd 2+ Fluorescence enhancement phenomena can be observed, in which Zn 2+ The fluorescence enhancement phenomenon caused by the fluorescent dye is more obvious, and the fluorescent color is more deviated from white; and Fe 2+ ，Co 2+ ，Cu 2+ ，Sn 2+ And Ni 2+ The addition of plasma metal ions allows to observe the phenomenon of fluorescence quenching, in which Fe 2+ The addition of (A) results in the most intense phenomenon of fluorescence quenching, whereas Sn 2 + The resulting quenching of fluorescence is not as severe as the rest of the metal ions;
concentration of 2.5 g- -1 PATF (A) 1 Solutions and PATF 2 -1 adding different metal ions (Fe) into the solution respectively 2+ ，Cu 2+ ，Co 2+ ，Sn 2+ ，Ni 2+ ，Zn 2+ ，Cd 2+ ) Measuring the ultraviolet-visible absorption spectrum of the sample by taking pure water as a blank reference sample;
polymer PATF 2 -1 uv-vis absorption spectra of the action with different metal ions see fig. 8, the solution of the copolymer ligand without complexing with metal ions shows a strong absorption peak around 284nm due to the pi-pi transition of the strongly conjugated units in the polymer, including VOF and TPY; after addition of different kinds of metal ions, appear around 325nmSlight red shift is generated, a secondary absorption peak is generated at the same time, the distance of a conjugated part is shortened by the coordination relationship between metal ions and ligands, so that the conjugation effect of the whole metal copolymer is enhanced, the delocalization of pi electrons can reduce the gap between an emission state and a ground state, the intensity of the secondary absorption peak at 325nm is obviously enhanced along with the addition of the metal ions, and the electron withdrawing property of a bipyridine heterocyclic ring part is increased after the metal ions are coordinated with TPY, so that the intramolecular charge transfer process (ICT) between the bipyridine heterocyclic ring part and a benzene ring with weak power supply property is enhanced, and the intensity of the secondary absorption peak is increased; addition of Fe to the polymer solution 2+ A new characteristic absorption peak at 570nm later, due to the metal-ligand charge transfer (MLCT) process;
polymer PATF 2 -1 fluorescence emission spectra of interaction with different metal ions are shown in figure 9; zn in contrast to other ions 2+ And Cd 2+ The ICT is strengthened by adding metal ions, so that the fluorescence emission peak of the polymer solution is wide and slow, wherein Zn is used 2+ The peak type of (A) is most representative, and the coverage range of an emission spectrum can explain that the polymer solution is observed by naked eyes when Zn is added 2+ The back color is changed from blue to white green; zn 2+ With Cd 2+ In the same group of the periodic Table of the elements and thus have similar spectral properties, but Zn 2+ Interactions with ligand solutions are distinguished from Cd 2+ A unique broad slow peak-type variation of; the interaction of other metal ions and a ligand solution can cause fluorescence quenching, and the coordination relationship between the metal ions and the ligand can change the configuration of an electron cloud, so that the fluorescence emission is influenced and even completely quenched;
polymer PATF 1 And PATF 2 -1 action of solution with metal ions photophysical data are shown in table 2;
TABLE 2 Polymer PATF 1 And PATF 2 -1 action of solution with metal ions photophysical data
Figure BDA0003200552380000151
Fluorescent quantum yield Φ quinine sulfate (0.1M H) 2 SO 4 ) Solution as control, PATF 2 1 as an example, ligand-Zn 2+ With ligand-Cd 2+ The fluorescence quantum yield of the solution is 0.318 and 0.236, the fluorescence enhancement effect is very obvious, and Fe 2+ 、Cu 2+ 、Co 2 + 、Sn 2+ And Ni 2+ The fluorescence quantum yields after interaction with the ligand solution were 0.017, 0.016, 0.055, 0.027, and 0.040, respectively, showing strong fluorescence quenching;
polymer PATF 2 -1 and Fe 2+ The quantitative fluorescence quenching response of (1) is shown in FIG. 10, low concentration of metal ion Fe 2+ Namely, the fluorescence quenching can be triggered, and the quenching degree and the metal ion Fe 2+ The concentration is in positive correlation, and the metal ion Fe with high concentration 2+ Can completely quench the fluorescence emission of the ligand solution;
polymer PATF 2 -1 with Zn 2+ Quantitative fluorescence enhancement response of (1) see FIG. 11, with Zn 2+ The concentration is increased so that the polymer PATF 2 -1 ligand solution producing fluorescence enhancement effect, copolymer PATF 2 Emission peak of-1 in addition of Zn 2+ After all, a clear red shift is shown and the peak shape becomes broader, i.e. the polymer PATF 2 -1 the emission spectrum of the solution is red-shifted from 377nm to about 475nm, which is caused by the increase of coplanarity of the fluorescence emitting group due to the enhancement of intramolecular conjugation, and the energy gap between the excited state and the ground state is also reduced, resulting in a relatively wide emission wavelength range, the degree of the fluorescence enhancement and the red shift of the spectrum and Zn 2+ There is a strong concentration dependence, which provides support for the quantitative detection of metal ions.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.

Claims (5)

1. A transition metal ion fluorescence chemical sensor based on terpyridine is characterized in that: the structural formula is as follows:
Figure FDA0003815925820000011
wherein Ar is a hydrophilic monomer, and the hydrophilic monomer is acrylic acid, methacrylic acid, acrylamide or methacrylamide; n is the number of repeating units, and n is 0 to 6; r is an alkyl chain, and the number of C atoms is =6-30; x, y, z are the relative proportions of the three monomers, x + y + z =100%, where x = 0.2-10%, z = 0.2-10%.
2. The preparation method of the terpyridine-based transition metal ion fluorescence chemical sensor in claim 1 is characterized by comprising the following specific steps:
adding 9,9-dialkyl fluorene as a conjugated vinyl monomer of a structural unit, 4- (4 '-2,2':6', 2' -terpyridine) styrene, a hydrophilic monomer and azobisisobutyronitrile into 1,4-dioxane, stirring and reacting for 6-10 hours at the temperature of 75-85 ℃, and placing the mixture in dichloromethane for sedimentation to obtain a random copolymer, namely the terpyridine-based transition metal ion fluorescence chemical sensor;
wherein the hydrophilic monomer is acrylic acid, methacrylic acid, acrylamide or methacrylamide;
5363A conjugated olefin monomer with structure unit of 9,9-dialkyl fluorene
Figure FDA0003815925820000012
Wherein n is the number of repeating units, and n =0 to 6;
r is an alkyl chain, and the number of C atoms =6-30.
3. The preparation method of the terpyridine-based transition metal ion fluorescence chemical sensor according to claim 2, wherein the preparation method comprises the following steps: when n is 1-6, 9,9-dialkyl fluorine is used as structural unit
(1) Synthesis of 2-bromofluorene: dropwise adding the bromine/trichloromethane mixed solution into the fluorene/catalyst/trichloromethane mixed solution under the conditions of light resistance, nitrogen atmosphere and temperature of-5-10 ℃, stirring for reaction for 3-5 h, washing, filtering, drying, and recrystallizing in DCM-methanol to obtain 2-bromofluorene;
(2) Synthesis of 2-bromo-9,9-dialkylfluorene: under the conditions of light protection and nitrogen atmosphere, adding alkyl bromide and tetrabutylammonium bromide into a 2-bromofluorene/toluene mixed solution, stirring and reacting for 20-30 h at the temperature of 65-80 ℃, neutralizing with dilute hydrochloric acid in sequence, extracting with DCM, and purifying by column chromatography to obtain 2-bromo-9,9-dialkyl fluorene;
(3) Synthesis of 2-bromo-7-acetyl-9,9-dialkylfluorene: adding acetyl chloride and a catalyst into a mixed solution of 2-bromo-9,9-dialkyl fluorene/dichloromethane or 2-bromo-9,9-dialkyl fluorene/trichloromethane in a nitrogen atmosphere, stirring and reacting for 3-5 h at the temperature of-5-10 ℃, washing, filtering, drying, and purifying by column chromatography to obtain 2-bromo-7-acetyl-9,9-dialkyl fluorene;
(4) Synthesis of 2-bromo-7- (1-hydroxy) ethyl-9,9-dialkylfluorene: under the conditions of nitrogen atmosphere and temperature of-5-10 ℃, adding strong base into the mixed solution of 2-bromo-7-acetyl-9,9-dialkyl fluorene/absolute ethyl alcohol, uniformly mixing, heating to 20-30 ℃, stirring for reaction for 0.5-1.5 h, and recrystallizing to obtain 2-bromo-7- (1-hydroxy) ethyl-9,9-dialkyl fluorene;
(5) Synthesis of 2-bromo-7-vinyl-9,9-dialkylfluorene: heating the 2-bromo-7- (1-hydroxy) ethyl-9,9-dialkyl fluorene/toluene mixed solution to reflux, adding a catalyst, stirring, refluxing and reacting for 10-30 min, and purifying by column chromatography to obtain 2-bromo-7-vinyl-9,9-dialkyl fluorene;
(6) 9,9-dialkyl fluorene is used as a conjugated alkene monomer of a structural unit for synthesis: adding an alkaline solution into a 2-bromo-7-vinyl-9,9-dialkyl fluorene/monoboronic ester group substituted alkyl fluorene oligomer derivative/tetrahydrofuran mixed solution, adding a catalyst in a nitrogen atmosphere, reacting for 18-24 hours at a temperature of 60-85 ℃ in a dark place, and purifying by column chromatography to obtain a conjugated alkene monomer taking 9,9-dialkyl fluorene as a structural unit; wherein the structural formula of the oligomer derivative of the alkyl fluorene substituted by the single borate group is shown in the specification
Figure FDA0003815925820000021
Wherein n is the number of repeating units, and n = 0-5;
r is an alkyl chain, and the number of C atoms is =6-30.
4. The preparation method of the terpyridine-based transition metal ion fluorescence chemical sensor, according to claim 3, is characterized in that: the preparation method of the oligomer derivative of the alkyl fluorene substituted by the single borate group in the step (6) comprises the following steps
1) Synthesis of 2-pinacol boronate-9,9-dialkylfluorene: adding pinacol diboron ester and potassium ethoxide into the mixed solution of 2-bromo-9,9-dialkyl fluorene/dimethyl sulfoxide, and adding Pd (dppf) Cl in the nitrogen atmosphere 2 Uniformly mixing, heating to 80-95 ℃, stirring and reacting for 20-36 h under the condition of keeping out of the sun, and purifying by column chromatography to obtain 2-pinacol borate-9,9-dialkyl fluorene, namely, the oligomer derivative of alkyl fluorene substituted by monoboronate with n being 0;
2) Synthesis of 2-pinacol boronate- (9,9-dialkylfluorene) n-mer: adding pinacol diboron and potassium ethoxide into a 2-bromo-fluorene (n-1) polymer/dimethyl sulfoxide mixed solution, and adding Pd (dppf) Cl in the nitrogen atmosphere 2 Uniformly mixing, heating to 80-95 ℃, stirring and reacting for 20-36 h under the condition of keeping out of the sun, and purifying by column chromatography to obtain the 2-pinacol borate- (9,9-dialkyl fluorene) n polymer.
5. The preparation method of the terpyridine-based transition metal ion fluorescence chemical sensor according to claim 2, wherein the preparation method comprises the following steps: when n is 0, 9,9-dialkyl fluorene is used as structural unit and its preparation method is
(1) Synthesis of 9,9-dialkylfluorene: dropwise adding n-butyllithium into a fluorene/THF system at the temperature of-78 to-50 ℃ in a nitrogen atmosphere to obtain a mixture A, dropwise adding a 1-bromoalkane/THF solution into the mixture A, reacting at room temperature for 20-36 hours under nitrogen, extracting with ethyl acetate, and purifying by column chromatography to obtain 9,9-dialkylfluorene;
(2) Synthesis of 2-acetyl-9,9-dialkylfluorene: adding acetyl chloride and a catalyst into 9,9-dialkyl fluorene/dichloromethane or 9,9-dialkyl fluorene/trichloromethane mixed solution in a nitrogen atmosphere, stirring and reacting for 3-5 h at the temperature of-5-10 ℃, washing, filtering, drying, and purifying by column chromatography to obtain 2-acetyl-9,9-dialkyl fluorene;
(3) Synthesis of 2-ethanolyl-9,9-dialkylfluorene: adding strong base into the mixed solution of 2-acetyl-9,9-dialkyl fluorene/absolute ethyl alcohol under the conditions of nitrogen atmosphere and temperature of-5-10 ℃, uniformly mixing, heating to 20-30 ℃, stirring for reaction for 0.5-1.5 h, and recrystallizing to obtain 2-ethanol-9,9-dialkyl fluorene;
(4) Synthesis of 2-vinyl-9,9-dialkylfluorene: heating the 2-ethanol-9,9-dialkyl fluorene/toluene mixed solution to reflux, adding a catalyst, stirring, refluxing and reacting for 10-30 min, and performing column chromatography purification to obtain 2-vinyl-9,9-dialkyl fluorene.
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