CN112390825B - Metal organic complex with near-infrared absorption and emission performance and preparation method thereof - Google Patents

Metal organic complex with near-infrared absorption and emission performance and preparation method thereof Download PDF

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CN112390825B
CN112390825B CN201910748067.6A CN201910748067A CN112390825B CN 112390825 B CN112390825 B CN 112390825B CN 201910748067 A CN201910748067 A CN 201910748067A CN 112390825 B CN112390825 B CN 112390825B
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夏江滨
许峰
罗琦
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Wuhan University WHU
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Abstract

The invention discloses a metal organic complex with near infrared absorption and emission performance and a preparation method thereof, wherein the metal organic complex is prepared by condensation reaction of an aldehyde group-containing ligand precursor and thiophene, furan, pyrrole, benzene ring or selenophene, and the ligand is further prepared by Pd (DMSO)2Cl2Or Pt (DMSO)2Cl2Preparing a complex monomer through coordination reaction, and obtaining the metal organic complex through condensation dimerization reaction of the complex monomer. The metal organic complex with near-infrared absorption and emission performance has near-infrared absorption and emission performance, and can be used as a wave-absorbing material in the fields of near-infrared imaging, invisible ink and anti-counterfeiting printing, near-infrared barcode invisible identification, plasma display panels, dye-sensitized solar cells, near-infrared light-emitting diodes and the like.

Description

Metal organic complex with near-infrared absorption and emission performance and preparation method thereof
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a metal organic complex with near-infrared absorption and emission performances and a preparation method thereof.
Background
Near-infrared absorbing and luminescent materials have important applications in energy, communication, biological imaging, sensing, catalysis, photoelectricity and other fields, and especially near-infrared imaging technology has great demands in military fields and civil applications. Typical organic near-infrared materials are broadly classified into metal-organic complexes, ionic dyes, pi-conjugated chromophores, charge transfer chromophores, and the like. Compared with the traditional inorganic material, the metal organic complex has the advantages of rich material sources, large adjustable range of optical characteristics and the like. The novel molecular structure is searched and designed, and the ligand and the complex are modified, so that the complex has excellent optical performance, and the method is a hot spot for researching near infrared materials.
Disclosure of Invention
The invention aims to provide a novel metal organic complex with near-infrared absorption and emission performance, which has the near-infrared absorption and emission performance, has larger red shift in a near-infrared region and shows excellent optical characteristics.
The second objective of the present invention is to provide a method for preparing the organometallic complex with near-infrared absorption and emission properties. Generally, the synthesis method of the metal organic complex comprises a solvothermal method, a hydrothermal method, an interface diffusion method, a gel diffusion method, a microwave method and an ultraviolet irradiation method, and compared with the method, the method is simple and rapid, the condition is mild, the yield is high, and the operability is strong.
One of the purposes of the invention adopts the following technical scheme:
a metal-organic complex with near infrared absorption and emission is prepared from the aldehyde group-containing ligand precursor and thiophene, furan, pyrrole, benzene ring or selenophene through condensation reaction to obtain ligand, and mixing it with Pd (DMSO)2Cl2Or Pt (DMSO)2Cl2Preparing a complex monomer through coordination reaction, and obtaining the metal organic complex through condensation dimerization reaction of the complex monomer.
The structural formula of the ligand precursor containing aldehyde group is any one of the following formulas L1-L20,
Figure BDA0002166260600000021
wherein the content of the first and second substances,
R1is H, CH3、C2H5、C3H7、C4H9、C5H11、C6H13、C7H15、C8H17、CH(C5H11)2、OH、OCH3、OC2H5、OC3H7、OC4H9、OC8H17、C6H13Any of nitro, cyano, phenyl, and a substituent having an aromatic structure;
a is an aromatic structure having a coordinating atom, and has any one of the following structures, wherein E represents an amino group (-NH)2) Or a mercapto (-SH) or hydroxyl (-OH) functional group:
Figure BDA0002166260600000031
when the structural formula of the ligand precursor containing aldehyde groups is L1 or L2 or L5 or L6 or L7, the structural formula of the ligand comprises any one of the following formulas S1-S12,
Figure BDA0002166260600000032
Figure BDA0002166260600000041
wherein the content of the first and second substances,
X1、X2、X3、X4each independently is any one of N, O, S, Se;
R1is H, CH3、C2H5、C3H7、C4H9、C5H11、C6H13、C7H15、C8H17、CH(C5H11)2、OH、OCH3、OC2H5、OC3H7、OC4H9、OC8H17、C6H13Any of nitro, cyano, phenyl, and a substituent having an aromatic structure;
R2is any one of H, F, Cl, Br and I;
R3is any one of the following heterocyclic aromatic hydrocarbons, n is 0, 1, 2,
Figure BDA0002166260600000051
a is an aromatic structure having a coordinating atom, and has any one of the following structures, wherein E represents an amino group (-NH)2) Or a mercapto (-SH) or hydroxyl (-OH) functional group:
Figure BDA0002166260600000052
when the structural formula of the ligand precursor containing aldehyde group is L1 or L2 or L5 or L6 or L7, the structural formula of the complex monomer comprises any one of the following formulas Y1-Y12,
Figure BDA0002166260600000061
Figure BDA0002166260600000071
wherein the content of the first and second substances,
X1、X2、X3、X4each independently is any one of N, O, S, Se;
R1is H, CH3、C2H5、C3H7、C4H9、C5H11、C6H13、C7H15、C8H17、CH(C5H11)2、OH、OCH3、OC2H5、OC3H7、OC4H9、OC8H17、C6H13Any of nitro, cyano, phenyl, and a substituent having an aromatic structure;
R2is any one of H, F, Cl, Br and I;
R3is any one of the following heterocyclic aromatic hydrocarbonsWherein n is 0, 1, 2,
Figure BDA0002166260600000072
m is any one of metal elements with coordination function of Sc, Ti, Fe, Co, Cu, Pd, Pt, Ir, Ru, Rh, Ni and Au;
a is an aromatic structure having a coordinating atom, and has any one of the following structures, wherein E represents an amino group (-NH)2) Or a mercapto (-SH) or hydroxyl (-OH) functional group:
Figure BDA0002166260600000081
when the structural formula of the ligand precursor containing aldehyde groups is L1 or L2 or L5 or L6 or L7, the structural formula of the metal organic complex comprises any one of the following formulas (I) to (XII):
Figure BDA0002166260600000091
Figure BDA0002166260600000101
Figure BDA0002166260600000111
Figure BDA0002166260600000121
wherein the content of the first and second substances,
X1、X2、X3、X4、X5、X6、X7、X8each independently is any one of N, O, S, Se;
R1is H, CH3、C2H5、C3H7、C4H9、C5H11、C6H13、C7H15、C8H17、CH(C5H11)2、OH、OCH3、OC2H5、OC3H7、OC4H9、OC8H17、C6H13Any of nitro, cyano, phenyl, and a substituent having an aromatic structure;
R2is any one of H, F, Cl, Br and I;
R3is any one of the following heterocyclic aromatic hydrocarbons, n is 0, 1, 2,
Figure BDA0002166260600000131
m is any one of metal elements with coordination function of Sc, Ti, Fe, Co, Cu, Pd, Pt, Ir, Ru, Rh, Ni and Au;
a is an aromatic structure having a coordinating atom, and has any one of the following structures, wherein E represents an amino group (-NH)2) Or a mercapto (-SH) or hydroxyl (-OH) functional group:
Figure BDA0002166260600000132
the second purpose of the invention is realized by the following technical scheme:
a preparation method of the metal organic complex with near infrared absorption and emission performance mainly comprises the following steps:
(1) taking a synthesized ligand precursor containing aldehyde groups as a raw material, adding the synthesized ligand precursor and thiophene or furan or pyrrole or benzene ring or selenophene into a glacial acetic acid solvent together, adding a catalyst, and carrying out condensation reaction to obtain a ligand containing thiophene or furan or pyrrole or benzene ring or selenophene units;
(2) the ligand obtained in the step (1) is mixed with Pd (DMSO)2Cl2Or Pt (DMSO)2Cl2Adding the mixture into a methanol solution according to an equal molar ratio to obtain a precipitate, namely a complex monomer;
(3) dissolving the complex monomer obtained in the step (2) in a solvent D, stirring for 12-14 hours, filtering the stirred solvent D in which the complex monomer is dissolved, washing the obtained filter residue with methanol, and drying in a vacuum drying oven to obtain a complex dimer, wherein the complex dimer is a metal organic complex with near-infrared absorption and emission properties.
Preferably, in the step (3), after the complex monomer obtained in the step (2) is dissolved in the solvent D, adding a proper amount of an inducer to make the solution alkaline, then stirring for 12 hours to 14 hours, filtering the stirred solvent D in which the complex monomer is dissolved, in which the inducer is added, washing the obtained filter residue with methanol, and drying to obtain a complex dimer, wherein the complex dimer is a metal-organic complex with near-infrared absorption and emission properties.
The inducer is triethylamine or ethylenediamine.
In the step (1), the catalyst is any one of boron trifluoride diethyl etherate, hydrofluoric acid and trifluoroacetic acid.
In the step (3), the solvent D is any one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, pyridine and aniline.
For a better understanding of the invention, the following are illustrated:
when the selected ligand precursor containing aldehyde group has a structural formula of L14, R1Is CH3，R2Is Br, R3Where n is 0, X1～X8When the element is S and M is Pd,
the ligand structural formula:
Figure BDA0002166260600000141
the monomer structural formula of the complex is as follows:
Figure BDA0002166260600000151
the structural formula of the complex dimer is as follows:
Figure BDA0002166260600000152
compared with the prior art, the invention has the following beneficial effects:
(1) the invention relates to a preparation method of metal organic complexes with near infrared absorption and emission performances, which takes synthesized bipyridine or phenanthroline or pyridine Schiff base and the like as a framework, contains ligands of heterocyclic units, and generates complex monomers with metals with catalytic activity such as metal Pd/Pt and the like.
(2) Under the alkaline condition, the complex monomer is induced to generate the complex dimer, the method is simple, the condition is mild, the yield is high, the obtained complex dimer has larger red shift in a near infrared region than the monomer, so that the complex dimer shows excellent optical characteristics, and can be used as a wave-absorbing material in the fields of near infrared imaging, invisible ink and anti-counterfeiting printing, near infrared barcode invisible identification, plasma display panels, dye-sensitized solar cells, near infrared light-emitting diodes and the like.
Drawings
FIG. 1 is a schematic diagram of a synthetic process of a metal organic complex with near infrared absorption and emission properties, which contains a thiophene unit 2, 2' -bipyridyl framework;
FIG. 2 is a nuclear magnetic hydrogen spectrum of Compound A in example (one) of the present invention;
FIG. 3 is a nuclear magnetic hydrogen spectrum of compound B in example (one) of the present invention;
FIG. 4 is a nuclear magnetic hydrogen spectrum of compound D in example (one) of the present invention;
FIG. 5 is a nuclear magnetic hydrogen spectrum of compound E in example (one) of the present invention;
FIG. 6 is a nuclear magnetic hydrogen spectrum of compound F in example (one) of the present invention;
FIG. 7 is a nuclear magnetic hydrogen spectrum of compound G in example (one) of the present invention;
FIG. 8 is a nuclear magnetic hydrogen spectrum of Compound H in example (one) of the present invention;
FIG. 9 shows the UV absorption and fluorescence emission spectra of compound H and compound I in dichloromethane solution in example (one) of the present invention;
FIG. 10 is a flow chart of synthesizing a Schiff base structure-containing metal-organic complex having near infrared absorption and emission properties using 2, 6-pyridinedicarboxylic acid as a raw material in example (II) of the present invention;
FIG. 11 is a nuclear magnetic hydrogen spectrum of Compound J in example (II) of the present invention;
FIG. 12 is a nuclear magnetic hydrogen spectrum of Compound K in example (II) of the present invention;
FIG. 13 is a nuclear magnetic hydrogen spectrum of Compound L in example (II) of the present invention;
FIG. 14 is a nuclear magnetic hydrogen spectrum of Compound M in example (II) of the present invention;
FIG. 15 is a nuclear magnetic hydrogen spectrum of Compound N in example (II) of the present invention;
FIG. 16 is a nuclear magnetic hydrogen spectrum of Compound O in example (II) of the present invention.
Detailed Description
The features and advantages of the present invention will be further understood from the following detailed description taken in conjunction with the accompanying drawings. The examples provided are merely illustrative of the method of the present invention and do not limit the remainder of the disclosure in any way.
In the following examples, the specific operations are carried out at room temperature without reference to temperature.
The design of the synthesis of aldehyde group-containing ligand precursors differs due to the choice of starting compound substrate.
In the embodiment (I), 2 ' -bipyridyl is used as a raw material, m-chloroperoxybenzoic acid (m-CPBA) is added to obtain 2,2 ' -bipyridyl-1-oxide, and then trimethylsilyl cyanide and benzoyl chloride are added to obtain colorless oily 6-cyano-2, 2 ' -bipyridyl; the obtained product is subjected to water under alkaline conditionsDecomposing and then esterifying in an acid environment; adding sodium borohydride into the product obtained in the last step, reducing and purifying to obtain 6-methanol-2, 2 ' -bipyridine, and oxidizing the 6-methanol-2, 2 ' -bipyridine by selenium dioxide to obtain the aldehyde group-containing ligand precursor 6-aldehyde-2, 2 ' -bipyridine; then taking aldehyde-containing double ligand precursor 6-aldehyde-2, 2' -bipyridine as a raw material, adding the raw material and 2-bromothiophene into a glacial acetic acid solvent together, and adding boron trifluoride diethyl etherate complex to obtain a ligand containing thiophene units; the obtained ligand containing thiophene unit is mixed with Pt (DMSO)2Cl2Adding the mixture into a methanol solution according to equal proportion to obtain a precipitate, namely a complex monomer; dissolving the obtained complex monomer in an N, N-dimethylformamide solution, stirring overnight, filtering, washing the obtained filter residue with methanol, and drying in a vacuum drying oven to obtain a complex dimer, wherein the complex dimer is a metal organic complex with near infrared absorption and emission properties.
In this embodiment (two), 2, 6-dipicolinic acid is used as a raw material, ethanol is added to react in a concentrated sulfuric acid environment to obtain 2, 6-ethyl-2-dicarboxylate pyridine, the ethyl-2, 6-dihydroxymethylpyridine is obtained by reduction in a methanol solution with sodium borohydride, and then 1, 4-dioxane is used as a solvent, and selenium dioxide is oxidized to obtain 2, 6-dialdehyde pyridine. Adding the product obtained in the last step and 2-chlorothiophene into a glacial acetic acid solvent together, uniformly stirring, and adding boron trifluoride diethyl etherate complex to obtain a 6- (bis (5-chlorothiophene-2-yl) methyl) pyridylaldehyde containing aldehyde groups and thiophene units; adding tetraphenylethenylamino into the obtained product in an absolute ethyl alcohol solvent to obtain a Schiff base-containing ligand, dissolving the obtained ligand into dichloromethane, and dropwise adding the dichloromethane into Pd (DMSO)2Cl2In the methanol solution, the obtained precipitate is a complex monomer; dissolving the obtained complex monomer in N, N-dimethylformamide solution, stirring overnight, filtering, washing the obtained filter residue with methanol, and drying in a vacuum drying oven to obtain complex dimer, wherein the complex dimer is Schiff base metal-containing organic complex with near infrared absorption and emission properties.
Example (a): the synthesis steps of each compound are explained in detail by using 4,4 '-dimethyl-2, 2' -bipyridine as a raw material.
(1) Synthesis of Compound A
A250 mL three-necked flask was charged with 2.76g (15mmol) of 4,4 '-dimethyl-2, 2' -bipyridine, purged with nitrogen to remove oxygen, 100mL of tetrahydrofuran was added, the temperature was lowered to-78 deg.C, 30mmol of lithium diisopropylamide was added dropwise, stirring was carried out for 2 hours, and 90mmol of ethyl bromide was added dropwise. After the dropwise addition, the temperature was slowly raised to room temperature, and the mixture was stirred for 12 hours. The reaction was quenched by addition of ammonium chloride solution, extracted by addition of mixed organic phases (petroleum ether: ethyl acetate ═ 2:1), combined organic phases, dried over anhydrous sodium sulfate, solvent removed under reduced pressure, and passed through a silica gel column with mobile phase (petroleum ether: ethyl acetate ═ 10:1) to give a colorless oil, compound a, in 95% yield.1H NMR(400MHz,CDCl3)δ8.56(d,J＝8Hz,2H),8.24(s,2H),7.13(d,J＝8Hz,2H),2.67(t,J＝8Hz,4H),1.70-1.75(m,4H),0.97(t,J＝8Hz,6H)ppm；13C NMR(101MHz,CDCl3)δ156.15,152.62,148.97,123.96,121.38,37.50,23.59,13.79ppm.ESI-MS:m/z 241.17[M+1]+.
(2) Synthesis of Compound B
Dissolving the obtained compound A in 15mL of dichloromethane, dissolving m-chloroperoxybenzoic acid (m-CPBA) (2.03g, 85%, 10mmol) in 20mL of dichloromethane, dropwise adding into the above solution at 5 deg.C, stirring at room temperature for 12 hr after dropwise addition, adding Na at 0 deg.C2CO3The solution was stirred for 30 minutes, extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the mixture was passed through a silica gel column using ethyl acetate as the mobile phase to give 2, 2' -bipyridine-1-oxide compound B as a colorless oil in 45% yield.1H NMR(400MHz,CDCl3)δ8.74(s,1H),8.60(d,J＝4Hz,1H),8.24(d,J＝4Hz,1H),7.95(s,1H),7.17(d,J＝8Hz,1H),7.09(d,J＝8Hz,1H),2.62-2.70(m,4H),1.67-1.74(m,4H),0.97-0.99(m,6H)ppm；13C NMR(101MHz,CDCl3)δ151.92,149.64,149.09,146.70,142.09,140.06,127.62,125.87,125.22,124.52,37.44,36.51,23.48,23.39,13.74,13.65ppm.ESI-MS:m/z 256.18[M]-.
(3) Synthesis of Compound C
Under nitrogen atmosphere, the obtained B substance5.6mmol and 3.16mL (23.7mmol) of trimethylsilyl cyanide were added to 20mL of anhydrous tetrahydrofuran, and benzoyl chloride (1.29mL,11.2mmol) was added at 0 ℃. After the addition, the mixture was stirred at room temperature overnight, and Na was carefully added2CO3And stirred for 30min, extracted with dichloromethane, the organic phases were combined, the solvent was removed under reduced pressure and the resulting oil containing compound C was directly subjected to the next reaction.
(4) Synthesis of Compound D
The mixture of C from the top and 0.33g (6.1mmol) of sodium methoxide were dissolved in 15mL of dry methanol, stirred at room temperature overnight, glacial acetic acid (0.367g,6.1mmol) and the appropriate amount of sodium bicarbonate were added, stirred for 15min, the organic phase was removed under reduced pressure, the residue was dissolved with ethyl acetate and sodium bicarbonate solution (8mL +2mL), the organic phases were combined and the solvent was spin-dried, the residue was added with aqueous methanol, pH 1 was adjusted with 5% concentrated sulfuric acid, stirred for 2 hours, pH 9 was adjusted with sodium hydroxide, extracted again with ethyl acetate, the organic phases were combined and passed through a silica gel column with mobile phase (petroleum ether: ethyl acetate 10:1) to give compound D as a colorless oil in 91% yield.1H NMR(400MHz,CDCl3)δ8.56(d,J＝8Hz,1H),8.43(s,1H),8.33(s,1H),7.98(s,1H),7.16(d,J＝8Hz,1H),4.04(s,3H,OCH3),2.68-2.77(m,4H),1.71-1.79(m,4H),0.96-1.00(m,6H)ppm；13C NMR(101MHz,CDCl3)δ166.19,156.61,155.29,153.88,152.84,148.96,147.43,125.29,124.61,124.37,121.93,52.81,37.47,37.43,23.57,23.50,13.85,13.74ppm.ESI-MS:m/z 299.17[M+1]+.
(5) Synthesis of Compound E
Product D (3.25mmol) from the previous step was added to a methanol/tetrahydrofuran (20/5mL) solution, sodium borohydride (0.756g,20mmol) was added in portions, stirred at room temperature for 2 hours, saturated potassium bicarbonate solution was added, stirred for 30min, extracted with ethyl acetate, the organic phases were combined and removed under reduced pressure, and the white solid obtained without further purification, compound E, was obtained in 87% yield.1H NMR(400MHz,CDCl3)δ8.56(d,J＝8Hz,1H),8.56(d,J＝8Hz,1H),8.23(s,1H),8.14(s,1H),7.14(d,J＝8Hz,1H),7.06(s,1H),4.81(s,2H,CH2O),4.23(br,1H,OH),2.66-2.70(m,4H),1.67-1.75(m,4H),0.94-1.00ppm；13C NMR(101MHz,CDCl3)δ158.06,155.67,154.80,153.52,152.63,149.02,124.10,121.39,120.44,120.20,63.94,37.54,37.51,23.64,23.58,13.80,13.79ppm.ESI-MS:m/z 271.17[M+1]+.
(6) Synthesis of Compound F
Selenium dioxide (0.145g,1.3mmol) is taken, 6mL of 1, 4-dioxane solvent is added, the temperature is raised to 65 ℃ and stirring is carried out for 30min, the obtained compound E (0.7g, 2.6mmol) is dissolved in 9mL of 1, 4-dioxane and slowly dripped into the turbid liquid, the temperature is raised to 110 ℃ and reflux is carried out for 2 hours, the temperature is reduced to room temperature, gray precipitate is filtered, filter residue is washed by ethyl acetate, organic phases are combined, the solvent is removed under reduced pressure, and a mobile phase (petroleum ether: ethyl acetate ═ 4:1) is used for passing through a silica gel column to obtain white solid, namely the compound F (ligand precursor containing aldehyde group) with the yield of 91%.1H NMR(400MHz,CDCl3)δ10.19(s,1H,CHO),8.58(d,J＝8Hz,1H),8.48(s,1H),8.37(s,1H),7.81(s,1H),7.19(d,J＝8Hz,1H),2.70-2.780(m,4H),1.70-1.77(m,4H),0.96-1.02(m,6H)ppm；13C NMR(101MHz,CDCl3)δ194.16,156.79,155.10,153.97,152.88,152.41,149.12,125.48,124.54,121.58,121.55,37.54,37.43,23.62,23.49,13.81,13.74ppm.ESI-MS:m/z 269.17[M+1]+.
(7) Synthesis of Compound G
Adding the obtained compound F (1mmol) and 2-bromothiophene (10mmol) into 5mL of glacial acetic acid, stirring for 10min, adding boron trifluoride diethyl etherate complex 1mL, heating to 50 ℃, detecting a point plate until no compound F exists, adding 20mL of water to quench the reaction, adding 100mL of mixed solution of petroleum ether and ethyl acetate of 1:1 in 3 times for extraction, combining organic phases, washing the organic phases by saturated sodium carbonate solution and saturated saline solution, drying the organic phases by anhydrous sodium sulfate, removing the solvent under reduced pressure, and passing through a silica gel column by using a mobile phase (petroleum ether: ethyl acetate ═ 10:1) to obtain a yellow oily substance, namely compound G (ligand containing thiophene units), with the yield of 93%.1H NMR(400MHz,CDCl3)δ8.55(d,J＝4Hz,1H),8.47(s,1H),8.19(s,1H),7.12-7.14(m,2H),6.86(d,J＝4Hz,2H,T-H),6.70(d,J＝4Hz,2H,T-H),5.80(s,1H,CH),2.73(t,J＝8Hz,2H),2.65(t,J＝8Hz,2H),1.68-1.83(m,4H),1.03(t,J＝8Hz,3H),0.95(t,J＝8Hz,3H)ppm；13C NMR(101MHz,CDCl3)δ158.54,156.02,155.67,153.98,152.62,148.87,147.36,128.88,125.87,124.34,122.63,122.06,119.93,112.44,50.92,37.59,37.52,23.65,23.35,13.86ppm.ESI-MS:m/z 576.97[M+1]+.
(8) Synthesis of Compound H
Taking Pt (DMSO)2Cl2(0.3mmol) is added into methanol solution (15mL), stirring is carried out for 10min, suspension is obtained, compound G (0.3mmol) is added into 5mL of methanol solution, a small amount of dichloromethane is added to increase the dissolution of compound G, the dissolved solution is dripped into the suspension, stirring is carried out for 5 hours at room temperature, yellow solid precipitates, and the compound H (complex monomer) is obtained after suction filtration, washing by methanol and drying in a vacuum drying oven.1H NMR(400MHz,CDCl3)δ9.45(d,J＝4Hz,1H),7.77(s,1H),7.71(s,1H),7.58(s,1H,T-H),7.42-7.43(m,1H),6.79(d,J＝4Hz,1H,T-H),6.71(d,J＝4Hz,1H,T-H),5.87(s,1H,CH),2.67-2.75(m,4H),1.57-1.79(m,4H),0.99-1.03(m,6H)ppm.ESI-MS:m/z 803.90[M+1]+.
(9) Synthesis of Compound I
Adding complex H (0.081g, 0.1mmol) into 20mL of N, N-dimethylformamide solution, adding 0.5mL of triethylamine, stirring for 12-14 hours, filtering, washing the obtained filter residue with methanol, and drying in a vacuum drying oven to obtain brown powder, namely the compound I (complex dimer).
Example (b): the synthesis steps of each compound will be described in detail using 2, 6-pyridinedicarboxylic acid as the starting material.
(1) Synthesis of Compound J
300mL of absolute ethyl alcohol and 33.4g of 2, 6-dipicolinic acid are added into a 500mL three-necked flask, 10mL of concentrated sulfuric acid is added after uniform stirring, the mixture is refluxed for 5 hours at 90 ℃, ethanol is removed by spinning under reduced pressure, 200mL of water is added into the residue, the pH value is adjusted to be neutral by sodium carbonate, 150mL of mixed organic phase (petroleum ether: ethyl acetate ═ 2:1) is added for extraction, the organic phases are combined, dried by anhydrous sodium sulfate, the solvent is removed under reduced pressure, and the mixture is purified by a silica gel column to obtain white crystal 2, 6-dihydroxymethylpyridine, namely a compound J, wherein the yield is 95%.
(2) Synthesis of Compound K
Adding 300mL of anhydrous methanol into a 500mL single-neck bottle, adding 17.8g of 2, 6-ethyl-dicarboxylate pyridine, uniformly stirring, adding 3.6g of sodium borohydride in batches, stirring for 3 hours, adding 10.7g of anhydrous calcium chloride in batches, stirring for 4 hours at room temperature, removing the solvent under reduced pressure, adding 100mL of saturated potassium carbonate solution, stirring for 4 hours, removing solvent water, drying under reduced pressure, and quickly passing through a silica gel column to obtain 9.88g of white solid, namely compound K, with the yield of 94.5%.
(3) Synthesis of Compound L
Dissolving 2.8g of 2, 6-dihydroxymethylpyridine in a 250mL three-necked flask, adding 80mL of 1.4-dioxane, stirring to dissolve, adding 2.66g of selenium dioxide powder, refluxing at 105 ℃ for 2 hours, cooling to room temperature in the flask, filtering out solids, removing liquid by rotary evaporation under reduced pressure, and passing through a silica gel column by using a mixed organic phase (petroleum ether: ethyl acetate: 8:1) to obtain off-white crystals, namely the compound L, with the yield of 80%.
(4) Synthesis of Compound M
Taking 0.54g of 2, 6-dialdehyde pyridine, adding 0.95g of 2-chlorothiophene into 10mL of glacial acetic acid solvent together, uniformly stirring, adding 5mL of boron trifluoride diethyl etherate complex to obtain 0.33g of red sticky matter, namely a compound M (a ligand precursor containing aldehyde group); the yield was 23.3%.
(5) Synthesis of Compound N
Dissolving the product 71mg obtained in the previous step in an absolute ethyl alcohol solvent, adding 76mg of tetraphenylethenylamino, heating at 50 ℃ for 2 hours to obtain a Schiff base-containing ligand, namely a compound N, directly spin-drying the solvent, and directly carrying out the next reaction without purification.
(6) Synthesis of Compound O
66mg of Pd (DMSO)2Cl2Dissolving in methanol to obtain suspension, dissolving the product in methanol (with small amount of dichloromethane as adjuvant), dripping into the suspension, stirring for 2 hr, and filtering to obtain precipitate as complex monomer, i.e. compound O.
(7) Synthesis of Compound P
Dissolving 82.5mg of the obtained complex monomer in 20mL of N, N-dimethylformamide solution, adding 0.5mL of triethylamine, stirring for 12-14 hours, filtering, washing the obtained filter residue with methanol, and drying in a vacuum drying oven to obtain a complex dimer, namely a compound P.

Claims (6)

1. A metal organic complex with near infrared absorption and emission performance is characterized in that: the general structural formula of the metal organic complex is as follows,
Figure FDA0003195721440000011
preparing ligand by condensation reaction of aldehyde group-containing ligand precursor and thiophene or furan or pyrrole or selenophene, and reacting the ligand and Pd (DMSO)2Cl2Or Pt (DMSO)2Cl2Preparing a complex monomer through coordination reaction, and performing condensation dimerization reaction on the complex monomer to obtain the metal organic complex;
wherein R is1Is H, CH3、C2H5、C3H7、C4H9、C5H11、C6H13、C7H15、C8H17、CH(C5H11)2、OH、OCH3、OC2H5、OC3H7、OC4H9、OC8H17Any of nitro, cyano, or phenyl substituents;
R2is any one of H, F, Cl, Br and I;
X1、X2、X3、X4each independently is any one of N, O, S, Se;
m is any one of Pd and Pt.
2. A method for preparing the metal organic complex with near infrared absorption and emission performance according to claim 1, which is characterized in that: the method mainly comprises the following steps:
(1) adding a ligand precursor containing aldehyde group as a raw material and thiophene or furan or pyrrole or selenophene into a glacial acetic acid solvent, adding a catalyst, and performing condensation reaction to obtain a ligand containing thiophene or furan or pyrrole or selenophene units;
(2) the ligand obtained in the step (1) is mixed with Pd (DMSO)2Cl2Or Pt (DMSO)2Cl2Adding the mixture into a methanol solution according to an equal molar ratio to obtain a precipitate, namely a complex monomer;
(3) dissolving the complex monomer obtained in the step (2) in a solvent D, stirring for 12-14 hours, filtering the stirred solvent D in which the complex monomer is dissolved, washing the obtained filter residue with methanol, and drying to obtain a complex dimer, wherein the complex dimer is a metal organic complex with near-infrared absorption and emission performances.
3. The method for preparing metal organic complexes with near infrared absorption and emission properties according to claim 2, wherein the method comprises the following steps: and (3) dissolving the complex monomer obtained in the step (2) in a solvent D, adding a proper amount of an inducer to make the solution alkaline, stirring for 12-14 hours, filtering the stirred solvent D in which the complex monomer is dissolved, adding the inducer, washing the obtained filter residue with methanol, and drying to obtain a complex dimer, wherein the complex dimer is a metal organic complex with near infrared absorption and emission properties.
4. A process for preparing a class of organometallic complexes having near infrared absorption and emission properties according to claim 3, wherein: the inducer is any one of triethylamine and ethylenediamine.
5. The method for preparing metal organic complexes with near infrared absorption and emission properties according to claim 2, wherein the method comprises the following steps: in the step (1), the catalyst is any one of boron trifluoride diethyl etherate, hydrofluoric acid and trifluoroacetic acid.
6. The method for preparing metal organic complexes with near infrared absorption and emission properties according to claim 2, wherein the method comprises the following steps: in the step (3), the solvent D is any one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, pyridine and aniline.
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Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Dinuclear palladium–azido complexes containing thiophene derivatives:reactivity toward organic isocyanides and isothiocyanates;Xiaohong Chang et al.;《Dalton Trans.》;20070118;792-801页 *
Stable π Radical from a Contracted Doubly N-Confused Hexaphyrin by Double Palladium Metalation;Yutaka Hisamune et al.;《Angew. Chem. Int. Ed.》;20150507;7323-7327页 *
Synthesis of Metal-Containing Poly(thiophene methines) via Solid-and Melt-State Polymerization and Their Related Applications as Highly Sensitive Ni2+ Chemosensors;Qi Luo et al.;《Organometallics》;20190131;647-653页 *

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