CN112028819A

CN112028819A - Organic ligand compound of tetraphenyl ethylene terpyridine, coordination supermolecule, preparation and application thereof

Info

Publication number: CN112028819A
Application number: CN202010832834.4A
Authority: CN
Inventors: 王平山; 王峰; 王俊
Original assignee: Central South University
Current assignee: Central South University
Priority date: 2020-08-18
Filing date: 2020-08-18
Publication date: 2020-12-04
Anticipated expiration: 2040-08-18
Also published as: CN112028819B

Abstract

The invention belongs to the technical field of supramolecular materials, and particularly discloses a tetraphenyl ethylene terpyridine organic ligand compound, and preparation and application thereof. The supramolecule disclosed by the invention has good fluorescence performance.

Description

Organic ligand compound of tetraphenyl ethylene terpyridine, coordination supermolecule, preparation and application thereof

Technical Field

The invention relates to the technical field of organic synthesis and metal coordination, in particular to a preparation method of a rhombus metal organic fluorescent material for regulating and synthesizing a terpyridyl group by a precise structure.

Background

In the field of modern supramolecules, coordination driving has been developed as one of the most efficient methods for building supramolecular structures; terpyridine ligands are widely used in this field, and with the development of research, more and more attention is paid to a functional supramolecular structure which is highly complex in assembly and has artistic aesthetics. However, how to precisely regulate the supramolecular structure and make the supramolecular structure have good functionality remains a difficult problem to be faced at present. Most of the existing methods have the defects that when functional groups with better properties are introduced, precise control and coordination are difficult to form a preset organic metal complex, and the existing methods have the defects of high synthesis difficulty, high cost, difficult separation and purification, multiple reaction steps, low yield and the like.

Therefore, the development of a supramolecular organometallic complex with good properties and a simple and precise method for synthesizing a supramolecular structure is of great significance to the development of the supramolecular chemistry field and the application in industry.

Disclosure of Invention

In order to overcome the defects, the invention provides a tetraphenyl ethylene terpyridine organic ligand compound.

The second purpose of the invention is to provide a preparation method of the tetraphenyl ethylene terpyridine organic ligand compound.

The third purpose of the invention is to provide rhombic functional supramolecules (also called supramolecules in the invention) coordinately assembled by the tetraphenyl ethylene terpyridine organic ligand compound.

The fourth purpose of the invention is to provide a preparation method of the rhombic functional supramolecule.

The fifth purpose of the invention is to provide the application of the rhombic functional supermolecule as a fluorescent material.

A tetraphenyl ethylene terpyridine organic ligand compound having the structural formula 1:

the invention provides a ligand compound with a brand-new structure, and researches show that the intramolecular effect based on the structure is beneficial to obtaining supermolecules with diamond structures, and the supermolecules can be endowed with good fluorescence performance.

The preparation method of the tetraphenyl ethylene terpyridine organic ligand compound comprises the following steps:

step (1): carrying out cyclization reaction on a compound shown in a

formula

2, 3, 4-dibromoacetophenone, a nitrogen source and alkali to obtain a cyclization product shown in a formula 3:

step (2): carrying out coupling reaction on the cyclization product of the formula 3 and the compound of the formula 4 to obtain the compound;

the preparation method of the ligand provided by the invention can successfully obtain the ligand with a brand-new structure based on the synthesis thought of cyclization and Suzuki coupling.

The research of the invention finds that the ligand of the formula 1 can be successfully prepared based on the cyclization reaction and the coupling reaction, and the ligand is favorable for forming a supermolecule with a brand-new structure and fluorescence characteristic.

In the present invention, in the step (1), the reaction solvent is CH₃CH₂OH and toluene mixed solvent, preferably, the CH₃CH₂The volume ratio of OH to toluene is 5-15: 1; more preferably 9 to 11: 1. The research of the invention finds that the combined solvent is beneficial to the cyclization reaction and improves the cyclization yield and the selectivity of a target product.

Preferably, the dosage of the solvent is 40-100 mL/g based on the total substrate.

Preferably, the alkali metal hydroxide of the base is at least one of KOH and NaOH, and most preferably NaOH. The dosage of the alkali is 2 to 4 times of the molar weight of the compound shown in the formula 2, and the optimal equivalent is 3 times.

Preferably, the molar ratio of the 3, 4-dibromoacetophenone to the compound shown in the formula 2 is 2-3: 1; preferably 2.1-2.5: 1.

Preferably, the nitrogen source is ammonia. The dosage of the nitrogen source is not less than the theoretical reaction amount, and preferably 1.1-10 times of the theoretical reaction amount.

In the step (2), the double-ortho modification characteristic and the large steric hindrance effect of the terpyridine multiply increase the synthesis difficulty, and in order to overcome the steric hindrance effect and improve the selectivity of the product subjected to double-ortho modification, the solvent, the catalyst dosage and the substrate proportion in the synthesis step are jointly controlled, so that the steric hindrance limitation is favorably broken through, the selectivity of the target product is favorably improved, and the yield and the purity of the target product are improved.

Preferably, in step (2), the solvent for the coupling reaction is a mixed solvent of THF/DMF. Preferably, in the mixed solvent, the volume ratio of THF/DMF is 4-8: 1; preferably 6: 1. The research finds that the adoption of the preferred mixed solvent is helpful to improve the selectivity of the target product and improve the yield and the purity of the product.

Preferably, the dosage of the solvent is 20-100 mL/g based on the total substrate.

Preferably, in the step (2), the catalyst for the coupling reaction is Pd (PPh)₃)₄And the amount of the catalyst is 0.16-0.36 times of the molar amount of the cyclization product of the formula 3 (the amount of the catalyst used in each reaction site is 0.06-0.09 eqv), and the optimal equivalent is 0.24 times. It has been found that the use of the catalyst and control of the preferred ratio helps to achieve double ortho coupling and to improve the yield and purity of the desired product, and that uncontrolled conditions will affect the conversion of the product and the selectivity of the desired product.

Preferably, in the step (2), the molar ratio of the compounds represented by the

formulas

3 and 4 is 1: 4.5-6. It was found that controlling the preferred ratio helps to improve the selectivity of the bis-ortho-tetra-coupled target product, and to improve the yield and purity of the target product.

Preferably, in the step (2), an acid-binding agent, preferably an alkali metal hydroxide, and more preferably at least one of KOH and NaOH, is further added to the coupling reaction system. The dosage of the acid-binding agent is not less than the theoretical reaction amount, and preferably 2-4 times of the theoretical reaction amount.

Preferably, the temperature of the coupling reaction is 70-90 ℃. The reaction time can be determined based on the control results such as TLC and HPLC.

The invention also provides a rhombus metal coordination supermolecule based on the terpyridyl group, which has a structural formula A:

wherein M is a hexacoordinate metal ion;

r is C₁～C₁₀Alkyl of (C)₁～C₁₀Alkoxy, nitro, trifluoromethyl, phenyl, benzyl or C₅～C₁₀A cycloalkyl group of (a).

The invention provides the supermolecule with the structure and the rhombic shape, and the supermolecule is found to improve the fluorescence property.

In the supermolecule of the invention, M is Ru²⁺、Co²⁺、Cu²⁺、Mg²⁺、Zn²⁺、Mn²⁺Or Ni²⁺At least one of them.

The invention also provides a preparation method of rhombus metal coordination supermolecule based on terpyridyl, which comprises the following steps of preparing the compound shown in the formula 1, the compound shown in the formula 5 and metal M²⁺Carrying out coordination reaction (self-assembly reaction);

wherein, the compound of formula 1, the compound of formula 5 and the metal M²⁺In a molar ratio of 2:2: 6.

The research of the invention finds that in order to successfully prepare the supermolecule, various technical problems such as unsatisfactory appearance uniformity, more impurity phases, unsatisfactory yield of target appearance products and the like need to be solved. In order to solve the problems, the invention innovatively researches and discovers that based on the combined control of the ligand structures shown in the

formulas

1 and 5 and further based on the ratio of the ligand structures to the ligand structures and the combined control of the metal ion types and the like, the supermolecules with the uniform rhombic structures can be obtained unexpectedly, and not only the yield of target products can be improved unexpectedly, the influence of heterogeneous phases can be avoided, the extinction of fluorescence can be avoided, and the fluorescence performance of the prepared products can be improved effectively.

In a preferred embodiment, M is mainly a divalent metal ion. Preferably M is Ru²⁺、Co²⁺、Cu²⁺、Mg²⁺、Zn²⁺、Mn²⁺Or Ni²⁺At least one of them. Most preferably Zn²⁺Its selectivity is high.

The research of the invention also finds that controlling the solvent and the temperature in the coordination reaction process is beneficial to further improving the product morphology selectivity and is beneficial to obtaining the rhombic morphology material with better uniformity.

Preferably, the solvent of the coordination reaction process is CH₃OH/CH₃CN mixed solution, more preferably CH₃OH/CH₃CN/CHCl₃The mixed solution of (1). It has been found that in the preferred solvent, it helps to obtain the material with diamond morphology.

Preferably, the amount of the solvent used in the coordination reaction is 0.1 to 10L/g.

Preferably, in the solvent of the coordination reaction process, CH₃1-3 parts of OH by volume; CH (CH)₃CN accounts for 1-2 parts by volume; CHCl₃The amount of (c) is 0 to 2 parts by volume (preferably 1 to 2 parts by volume).

Preferably, the temperature during the coordination reaction is 25-80 ℃; more preferably 50 to 65 ℃. Researches show that the ligand, the ligand ratio and the solvent system are matched, and the optimal temperature is further controlled, so that the selectivity of the rhombohedral product is further improved, and the supermolecule with uniform rhombohedral morphology is obtained.

The time of the coordination reaction can be determined based on the control result of HPLC, and preferably, the time of the coordination reaction is 8 to 12 hours.

The invention discloses a preferable supermolecule synthesis method, which has a synthesis reaction formula shown in a reaction formula 1:

the synthesis steps are as follows: firstly, preparing [1- (4-formaldehyde phenyl) -1,2, 2-triphenyl)]And closing the ring of ethylene under the alkaline condition to obtain the compound L. And reacting the compound L with 4-phenylboronic acid-2, 2': the ligand R was obtained by Suzuki coupling of 6, 2 "-terpyridine. Secondly, o-xylene 2 in liquid bromine CH₂Cl₂In the solution, brominating to obtain 4, 5-dibromo-1, 2-xylene 3, and reacting with 4-phenylboronic acid-2, 2': 6, 2 "-terpyridine in Pd (Ph)₃)₄To generate ligand V through coupling. Finally, Zn (NO) is added into a methanol/trichloromethane mixed solution system of the ligand R and the ligand V₃)₂And (3) forming a metal organic complex C by coordination. And (3) comparing the luminescence properties of the metal organic complex C in different solvents.

A more preferable preparation method of the terpyridyl rhombus metal organic fluorescent material specifically comprises the following steps:

step (a): preparation of compound L:

[1- (4-Methylphenyl) -1,2, 2-triphenyl ] ethylene and 3, 4-dibromoacetophenone were added to a 250mL round-bottomed flask containing 100mL/10mL absolute ethanol/toluene, NaOH was added, and the mixture was stirred at room temperature overnight. And adding 20mL of ammonia water into the mixed reaction solution, refluxing for 10h, cooling the reaction solution to room temperature, performing suction filtration to obtain a solid, and washing with isopropanol to obtain a white solid L.

Step (b): preparation of ligand R:

in a 250mL round bottom flask was added the compound L, 4-phenylboronic acid-2, 2': 6, 2 "-terpyridine, NaOH and 120mL/20mL solvent THF/DMF, and additional Pd (Ph)₃)₄Reflux at 80 ℃ overnight under nitrogen. After the reaction is finished, cooling the reaction liquid to room temperature, spin-drying the solvent, adding methanol for reflux, performing suction filtration to obtain a white solid, and finally using CH₂Cl₂/CH₃Recrystallization of OH gave a white powder R.

Step (c): preparation of compound 3:

to contain 60mLCH₂Cl₂Adding o-xylene into a 100mL round-bottom flask, and completely dissolving the o-xyleneUnder stirring, 10mL of a solution of liquid bromine in methylene chloride was added through a constant pressure dropping funnel, and the mixture was reacted at room temperature for 2 hours. After the reaction is finished, adding a saturated aqueous solution of sodium bisulfite to quench unreacted liquid bromine, extracting with water and saturated experimental water for three times respectively, collecting the lower organic solvent, and spin-drying to obtain a white solid 3

Step (d): preparation of ligand V:

in a 250mL round bottom flask was added the compound 3, 4-phenylboronic acid-2, 2': 6, 2 "-terpyridine, NaOH and 80mL of solvent THF, followed by Pd (Ph)₃)₄Reflux at 80 ℃ overnight under nitrogen. After the reaction is finished, cooling the reaction liquid to room temperature, spin-drying the solvent, adding methanol for reflux, performing suction filtration to obtain a white solid, and finally using CH₂Cl₂/CH₃Recrystallization of OH gave white powder V.

A step (e): preparation of Complex C:

ligand V, ligand R and CH are added into a 100mL round-bottom flask₃OH/CH₃CN/CHCl₃(20mL/20mL/20mL), performing ultrasonic treatment for 10min, and after the two ligands are completely dissolved, dropwise adding Zn (NO) into the solution₃)₂The solution was heated to reflux overnight. After the reaction is finished, cooling the reaction liquid to room temperature, and carrying out suction filtration to obtain a yellow solid C.

The invention has the advantages of

(1) The invention provides a brand new tripyridyl ligand;

(2) the invention provides a brand new synthesis idea of the terpyridyl ligand, and finds that the synthesis difficulty is small, reaction raw materials are cheap and easy to obtain, the reaction conditions are mild, and the selectivity and yield of each reaction are high. Research also finds that controlling the conditions of the cyclization and coupling reaction processes is helpful for improving the selectivity of target products and improving the yield and purity of the products.

(3) The invention provides a supermolecule with a brand-new diamond structure.

(4) The coordination reaction of the invention controls the coordination ions, the proportion, the solvent, the temperature and other conditions, is favorable for further improving the shape selectivity and is favorable for further having supermolecules with uniform rhombic shapes,

(5) the supramolecule can show excellent fluorescence performance. In addition, the fluorescent property of the fluorescent material synthesized by the invention can be regulated and controlled by solubility, so that the fluorescent material has great potential value, plays a role in promoting the development of supramolecular functional materials, and has great application prospect in industry.

Drawings

[ FIG. 1 ] A preparation of Compound L prepared in example 1¹H NMR spectrum;

FIG. 2 is a drawing of ligand R prepared in example 1¹H NMR spectrum;

FIG. 3 is a drawing of Compound 3 prepared in example 2¹H NMR spectrum;

FIG. 4 is a drawing of ligand V prepared in example 2¹H NMR spectrum;

FIG. 5 shows Complex C prepared in example 3₁Is/are as follows¹H NMR spectrum;

FIG. 6 shows Complex C prepared in example 3₁ESI-MS spectrum of

FIG. 7 shows Complex C prepared in comparative example 3(Fe)₂Is/are as follows¹H NMR spectrum

FIG. 8 shows Complex C prepared in example 4₄The ESI-MS spectrum of (E), wherein the peaks of the target product (rhombohedral product) are 757, 886, 1058, 1299; peaks for triangular by-products 685, 963, 1299, 1517;

FIG. 9 is a fluorescence performance diagram of example 5;

FIG. 10 is a graph of the fluorescence properties of example 5 (after dissolution of vial No. 3);

FIG. 11 shows a formula of A (R is-OCH)₃That is, example 3 yellow solid C₁) A plot of fluorescence intensity data under different conditions;

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1

Step (1) is to mix [1- (4-formaldehyde phenyl) -1,2, 2-triphenyl)]Ethylene (500mg, 1.39mmol) and 3, 4-dibromoacetophenone (930mg,3.32mmol) were added to a 250mL round-bottomed flask containing 100mL/10mL absolute ethanol/toluene, NaOH (166mg,4.17mmol) was added, and the mixture was stirred at room temperature overnight. And adding 20mL of ammonia water into the mixed reaction solution, refluxing for 10h, cooling the reaction solution to room temperature, performing suction filtration to obtain a solid, and washing with isopropanol to obtain a white solid L (1060mg) with the yield of 80%.¹H NMR(500MHz,CDCl₃)8.41(s,2H,H^a),7.98-7.97(d,2H,H^b),7.83(s,2H,H^c),7.78-7.76(d,2H,H^d),7.52-7.50(d,2H,tpy-H^g),7.23-7.21(d,2H,tpy-H^h),7.17-7.07(m,19H,^B _, ^C,D,E-Ph-H).

Step (2) in a 250mL round-bottom flask, compound L (1000mg,1.05mmol), 4-phenylboronic acid-2, 2': 6, 2 "-terpyridine (1780mg,5.04mmol), NaOH (504mg,12.60mmol) and the solvent THF/DMF (120:20mL), and Pd (Ph) added₃)₄(290mg,0.25mmol, under nitrogen, 80 ℃ C.)RefluxingOvernight. After the reaction is finished, cooling the reaction liquid to room temperature, spin-drying the solvent, adding methanol for reflux, performing suction filtration to obtain a white solid, and finally using CH₂Cl₂/CH₃Recrystallization of OH gave R (1550mg) as a white powder in 80% yield.¹H NMR(400MHz,CDCl₃)8.78(s,8H,^1,2-tpy-H^3′,5′),8.72(d,4H,^1-tpy-H^6,6″),8.71-8.64(m,10H,^1,2-tpy-H^3,3″,^1-tpy-H^6,6″),8.43-8.41,(m,2H,H^b),8.35(s,2H,H^c),8.03(s,2H,H^a),7.92-7.78(m,16H,^1-tpy-H^4,4″,^1-tpy-H^g,^2-tpy-H^4,4″,²tpy-H^g),7.76-7.63(d,2H,H^d),7.54-7.48(d,2H,^1-Tpy-H^h),7.46-7.43(d,2H,^2-Tpy-H^h),7.36-7.22(m,8H,^1-tpy-H^5,5″,²-tpy-H^5,5″),7.18-7.08(m,23H,^A,B,C,D,E-H^Ph),7.02(s,2H,^A-H^ph).

Comparative example 1

Compared with the example 1, the difference is mainly that in the step (1), a single ethanol is used as a solvent, and specifically:

[1- (4-Methylphenyl) -1,2, 2-triphenyl ] ethylene (500mg, 1.39mmol) and 3, 4-dibromoacetophenone (930mg,3.32mmol) were added to a 250mL round-bottomed flask containing 100mL absolute ethanol, NaOH (166mg,4.17mmol) was added, and the mixture was stirred at room temperature overnight. And continuously adding 20mL of ammonia water into the mixed reaction liquid, refluxing for 10h, cooling the reaction liquid to room temperature, and performing suction filtration to obtain a solid, wherein the polarity is the reaction polarity before the ammonia water is added. Showing that the target cyclization product L was not obtained.

Comparative example 2

Compared with example 1, the difference is mainly that in step (2), a single THF is used as a solvent, specifically:

in a 250mL round bottom flask was added compound L (1000mg,1.05mmol), 4-phenylboronic acid-2, 2': 6, 2 "-terpyridine (1780mg,5.04mmol), NaOH (504mg,12.60mmol) and solvent 120mL THF, followed by Pd (Ph)₃)₄(290mg,0.25mmol) and refluxed at 80 ℃ overnight under nitrogen. After the reaction is finished, cooling the reaction liquid to room temperature, spin-drying the solvent, adding methanol for reflux, performing suction filtration to obtain a white solid, and finally using CH₂Cl₂/CH₃Recrystallization of OH gave R (580mg) as a white powder in 30% yield.

Example 2

To contain 60mLCH₂Cl₂After o-dimethoxybenzene (2g,14.47mmol) was completely dissolved in a 100mL round-bottom flask, 10mL of a solution of liquid bromine (5.1g,31.84mmol) in methylene chloride was added through an isopiestic dropping funnel under stirring, and the mixture was reacted at room temperature for 2 hours. After the reaction was completed, a saturated aqueous solution of sodium bisulfite was added to quench the unreacted liquid bromine, which was extracted three times with water and saturated experimental water, respectively, and the lower organic solvent was collected and spin-dried to give 3(4.2g, 98% yield) as a white solid.¹H NMR(500MHz,CDCl₃)7.08(s,2H,ph-H),3.88(s,6H,-OCH₃).

In a 250mL round bottom flask was added compound 3(3g,10.14mmol), 4-phenylboronic acid-2, 2': 6, 2 "-terpyridine (8.5g,24.33mmol), NaOH (2.4g,60.82mmol) and the solvent THF (80mL), and additional Pd (Ph)₃)₄(1.4g,1.22mmol) at 80 ℃ under nitrogen protectionRefluxingOvernight. After the reaction is finished, cooling the reaction liquid to room temperature, spin-drying the solvent, adding methanol for reflux, performing suction filtration to obtain a white solid, and finally using CH₂Cl₂/CH₃Recrystallization of OH gave white powder V (6.2g) in 80% yield.¹H NMR(500MHz,CDCl₃):8.76(s,4H,H^3',5'),8.71-8.70(d,J＝5Hz,4H,H^6,6”),8.67-8.66(d,J＝5Hz,4H,H^3,3”),7.89-7.86(m,4H,H^4',4”),7.86-7.84(d,J＝10Hz,4H,H^g),7.36-7.34(d,J＝10Hz,4H,H^h),7.35-7.32(m,4H,H^5',5”),7.05(s,2H,Hⁱ),4.03(s,6H,-OCH₃)

Example 3

A100 mL round-bottomed flask was charged with ligand V (10mg, 0.013mmol), ligand R (23.8mg, 0.013mmol), and CH₃OH/CH₃CN/CHCl₃(20mL/20mL/20mL), performing ultrasonic treatment for 10min, and after the two ligands are completely dissolved, dropwise adding Zn (NO) into the solution₃)₂Methanol solution (2mL,49mg/8mL) was reacted at 55 ℃ overnight. After the reaction is finished, cooling the reaction liquid to room temperature, adding ammonium hexafluorophosphate, stirring for 30min, and respectively carrying out suction filtration to obtain yellow solid C₁The yield was 92%.¹The H NMR spectrum is shown in FIG. 5, and the ESI-MS spectrum is shown in FIG. 6. The purity is shown in nuclear magnetism, the complex is mainly used for proving whether the complex is formed or not, the nuclear magnetism can represent whether the complex is formed or not and the purity to a certain degree, and the ESI-MS can prove the existence and the structural characteristics of the complex.

¹H NMR(500MHz,CD₃CN):9.10-9.05(m,12H,^1,2,3-tpy-H³'_, ⁵'),8.83-8.81(m,20H,^2,3-tpy-H⁴'_, ⁴”,H^b,c),8.64-8.63(m,20H,^1-tpy-H⁴'_, ⁴”),8.24-8.11(m,44H,^1,2-tpy-H^g,¹ _, ^3-tpy-H⁵'_, ⁵”,^1,2-tpy-H^g,H^a),7.84-7.66(m,60H,^1,2,3-tpy-H⁶'_, ⁶”,H^d,^1-tpy-H^5',5”,^2,3-tpy-H^h,^1-tpy-H^g),7.37-7.15(m,39H,^2,3-tpy-H^5',5”,^A,B,C,D,E-H^Ph),6.78(m,4H,H^m),4.03(s,6H,-OCH₃).

Comparative example 3

The difference compared to example 3 is mainly that an equimolar concentration of an equivalent amount of Cd (NO) is used₃)₂Solution and FeCl₂Solution replacement of said Zn (NO)₃)₂And (3) solution. Respectively obtaining light yellow solid C₂And a purple solid C₃In which C is₂And C₃Is unable to distinguish the absence of the target product, and C₁Nuclear magnetic distribution peaks belonging to the target product appear.¹The H NMR spectrum is shown in FIG. 7.

Example 4

Compared with the example 3, the difference is that the temperature of the coordination reaction is 80 ℃, and specifically:

ligand V (10mg), ligand R (23.8mg), and CH were added to a 100mL round-bottomed flask₃OH/CH₃CN/CHCl₃(20mL/20mL/20mL), performing ultrasonic treatment for 10min, and after the two ligands are completely dissolved, dropwise adding Zn (NO) into the solution₃)₂The solution was reacted at 80 ℃ overnight. After the reaction is finished, cooling the reaction liquid to room temperature, adding ammonium hexafluorophosphate, stirring for 30min, and respectively carrying out suction filtration to obtain yellow solid C₄However, the ESI-MS spectrum of the product is mainly the peak forming the triangular structure, and less signal peaks with the diamond target product exist, so that the yield of the target product is low.

Example 5

Taking 3 small bottles with numbers of 1,2 and 3; 2mg of complex C are weighed out separately₁Prepared in example 3) and 0.5mL CH was added₃CN, heating to completely dissolve. 1mLCH is added into bottles No. 1,2 and 3 respectively₃CN；1mLCH₃OH；0.5CH₃OH is kept stand and observed, and 0.5mL of the solution is addedCHCl₃And then comparing the fluorescence properties. And observing the fluorescence property under an ultraviolet fluorescent lamp. The experimental result is obtained, and no fluorescence exists in the No. 1 bottle; the No. 2 bottle shows fluorescence along with the addition of the methanol; the fluorescence property appeared first in bottle No. 3, but disappeared as the solution mixed complex was completely dissolved again. The fluorescence is caused by unique aggregation state luminescence of the tetraphenyl vinylbenzene, and under the condition of dissolution, in a benign solvent, the complex molecules are well dissolved and dispersed, and only weak fluorescence exists at the moment; however, with the addition of the poor solvent, the complex molecules are changed from dispersion to stacking and are gathered together, so that the circulation and the density of electrons are enhanced, and the fluorescence performance is enhanced. The fluorescence image is shown in FIG. 9. The fluorescence intensity data are shown in FIG. 11. Showing excellent fluorescence intensity in aqueous solution.

Claims

1. A tetraphenyl ethylene terpyridine organic ligand compound is characterized in that the compound has a structural formula 1:

2. a method for preparing the tetraphenyl ethylene terpyridine organic ligand compound of claim 1, comprising the steps of:

step (1): carrying out cyclization reaction on a compound shown in a formula 2, 3, 4-dibromoacetophenone, a nitrogen source and alkali to obtain a cyclization product shown in a formula 3:

3. the process for preparing the organic ligand compound of tetraphenyl ethylene terpyridine according to claim 2,

in the step (1), the reaction solvent is CH₃CH₂OH and toluene mixed solvent;

preferably, said CH₃CH₂The volume ratio of OH to toluene is 5-15: 1;

preferably, the alkali metal hydroxide of the alkali is at least one of KOH and NaOH;

preferably, the amount of the base used is 2 to 4 times the molar amount of the compound of formula 2;

preferably, the nitrogen source is ammonia; the dosage of the nitrogen source is not less than the theoretical reaction amount;

the temperature of the cyclization reaction is reflux.

4. The method for preparing the organic ligand compound of tetraphenyl ethylene terpyridine as claimed in claim 2, wherein in the step (2), the solvent for the coupling reaction is a mixed solvent of THF/DMF; preferably, in the mixed solvent, the volume ratio of THF/DMF is 4-8: 1;

preferably, the catalyst for the coupling reaction is Pd (PPh)₃)₄And the dosage of the catalyst is 0.16 to 0.36 time of the molar weight of the cyclization product of the formula 3;

preferably, the molar ratio of the compounds in the formula 3 to the compounds in the formula 4 is 1: 4.5-6;

preferably, an acid-binding agent, preferably an alkali metal hydroxide, is further added to the coupling reaction system;

preferably, the temperature of the coupling reaction is 70-90 ℃.

5. A rhombohedral metal coordinating supramolecule based on terpyridyl groups having the formula A:

wherein M is a hexacoordinate metal ion;

6. Rhombohedral metal-coordinating supramolecules based on terpyridyl groups as claimed in claim 1, wherein M is Ru²⁺、Co²⁺、Cu²⁺、Mg²⁺、Zn²⁺、Mn²⁺Or Ni²⁺At least one of them.

7. A method for preparing rhomboidal metal-coordinated supramolecules based on terpyridyl groups as claimed in claim 5 or 6, characterized in that compounds of formula 1, compounds of formula 5 and metal M as claimed in claim 1 are used²⁺Carrying out coordination reaction to obtain;

8. Method for the preparation of rhomboidal metal-coordinated supramolecules based on terpyridyl groups as claimed in claim 7, wherein the solvent of the coordination reaction process is CH₃OH/CH₃CN mixed solution, more preferably CH₃OH/CH₃CN/CHCl₃The mixed solution of (1);

preferably, in the solvent of the coordination reaction process, CH₃1-2 parts by volume of OH; CH (CH)₃CN accounts for 1-2 parts by volume; CHCl₃The amount of (A) is 0-2 parts by volume.

9. The method for the preparation of rhomboidal metal-coordinated supramolecules based on terpyridyl groups according to claim 7, wherein the temperature during the coordination reaction is 25-80 ℃ C; more preferably 50 to 65 ℃.

10. Use of rhombohedral metal-coordinated supramolecules based on terpyridyl groups as claimed in claim 5 or 6 or as prepared by the preparation method as claimed in any one of claims 7 to 9 as fluorescent materials.