CN105693637B - Luminescent material [Cu(tibc)2]n and its synthesis method - Google Patents

Abstract

The invention discloses a fluorescent material [Cu(tibc) ₂ ] _n and a synthesis method. The molecular formula of the monomer is: C ₁₈ H ₁₀ CuBr ₄ N ₈ O ₂ , the molecular weight is: 797.70g/mol, Htibc is 3,5-dichlorosalicylaldehyde acetal 4-amino-1,2,4 triazole Schiff alkali. Dissolve analytically pure 3,5-dibromosalicylaldehyde and analytically pure 4-amino-1,2,4-triazole in analytically pure ethanol, heat to reflux, and dry to obtain the ligand Htibc. The dried Htibc and analytically pure copper acetate were dissolved in analytically pure N,N'-dimethylformamide, and then distilled water was added, and left to stand in an oven at 80°C for three days. [Cu(tibc) ₂ ] _n produces 520nm fluorescence with 193.7au intensity under 450nm incident light irradiation; in 800V photomultiplier tube, under 3 times amplification factor, in 1mol/L potassium persulfate solution, produced 2750a.u. Intensive and stable luminescence. The invention has the advantages of simple process, low cost, easy control of chemical components, good repeatability and high output.

Description

Luminescent material [Cu(tibc)2]n and its synthesis method

technical field

The present invention relates to a stable luminescent material [Cu(tibc) ₂ ] _n , (Htibc is 2,4-dibromo-6-(1,2,4)-triazole-4-iminomethylphenol) and synthesis methods.

Background technique

After decades of development, modern luminescent materials have become supporting materials in information display, lighting sources, optoelectronic devices and other fields, playing an increasingly important role in social development and technological progress. Especially now that energy is scarce, the development of luminescent materials with high conversion efficiency is one of the methods to solve the problem of energy shortage.

Contents of the invention

The purpose of the present invention is to synthesize [Cu(tibc) ₂ ] _n by means of a micro-vial reaction method in order to design and synthesize functional materials with excellent luminescent properties.

The monomer molecular formula of [Cu(tibc) ₂ ] _n involved in the present invention is: C ₁₈ H ₁₀ CuBr ₄ N ₈ O ₂ , the relative molecular weight is: 753.5, and Htibc is 2,4-dibromo-6-(1,2 , 4)-triazole-4-iminomethylphenol, the crystal structure data is shown in Table 1, and the bond length and bond angle data are shown in Table 2.

Table 1: Crystallographic parameters of [Cu(tibc) ₂ ] _n

^a R ₁ ＝Σ||F _o |–|F _c ||/Σ|F _o |. ^b wR ₂ ＝[Σw(|F _o ² |–|F _c ² |) ² /Σw(|F _o ² |) ² ] ^1/2

Table 2: Bond lengths of [Cu(tibc) ₂ ] _n and bond angle°

Br4—C12 1.894(9) N9—C0AA 1.288(11) Br8—C6 1.898(10) N11—C2 1.297(11) Cu9—O3 1.939(5) N19—Cu9iv 2.385(7) Cu9—O3i 1.939(5) N19—C21 1.253(12) Cu9—N11i 2.048(7) C21—C2AAv 1.469(12) Cu9—N11 2.048(7) C2AA—C21ii 1.469(12) Cu9—N19ii 2.385(7) C2AA—C1AA 1.396(13) Cu9—N19iii 2.385(7) C2AA—C18 1.421(13) O3—C18 1.284(10) C6—C1AA 1.379(14) N7—N19 1.415(9) C6—C20 1.369(15) N7—C2 1.335(11) C12—C18 1.422(11) N7—C0AA 1.350(11) C12—C20 1.351(13) N9—N11 1.368(10) O3—Cu9—O3i 180.0 C2—N11—N9 108.1(7) O3i—Cu9—N11i 89.3(3) N7—N19—Cu9iv 122.4(5) O3i—Cu9—N11 90.7(3) C21—N19—Cu9iv 119.3(6) O3—Cu9—N11i 90.7(3) C21—N19—N7 112.5(7) O3—Cu9—N11 89.3(3) N19-C21-C2AAv 125.3(8) O3—Cu9—N19iii 99.3(2) N11—C2—N7 109.5(8) O3i—Cu9—N19ii 99.3(2) N9—C0AA—N7 110.6(8) O3i—Cu9—N19iii 80.7(2) C1AA—C2AA—C21ii 115.7(8) O3—Cu9—N19ii 80.7(2) C1AA—C2AA—C18 122.3(8) N11i—Cu9—N11 180.0(2) C18—C2AA—C21ii 122.1(8) N11—Cu9—N19ii 85.6(3) C1AA—C6—Br8 119.9(8) N11—Cu9—N19iii 94.4(3) C20—C6—Br8 119.2(8) N11i—Cu9—N19iii 85.6(3) C20—C6—C1AA 120.6(9) N11i—Cu9—N19ii 94.4(3) C6—C1AA—C2AA 119.2(9) N19iii—Cu9—N19ii 180.0 C18—C12—Br4 116.9(6) C18—O3—Cu9 126.0(5) C20—C12—Br4 119.0(7) C2—N7—N19 127.5(7) C20—C12—C18 124.1(8) C2—N7—C0AA 105.3(7) O3—C18—C2AA 125.5(7) C0AA—N7—N19 126.8(7) O3—C18—C12 120.7(8) C0AA—N9—N11 106.4(7) C2AA—C18—C12 113.8(8) N9—N11—Cu9 123.2(5) C12—C20—C6 119.8(9) C2—N11—Cu9 128.5(6)

Operate on this: (i) -x, -y+1, -z; (ii) x, -y+1/2, z - 1/2; (iii) -x, y+1/2, -z +1/2; (iv)-x,y-1/2,-z+1/2; (v)x,-y+1/2,z+1/2.

The specific steps of the synthetic method of [Cu(tibc) ₂ ] _n are:

(1) 2.79g of analytically pure 3,5-dibromosalicylaldehyde and 0.841g of analytically pure 4-amino-1,2,4-triazole were dissolved in 30mL of analytically pure ethanol solution, heated to reflux and After stirring for two hours, a solid precipitated, filtered, washed three times with 10 mL of analytically pure ethanol, and dried at 50° C. to obtain the ligand Htibc. Dissolve 0.069-0.138g of dried Htibc and 0.040-0.080g of analytically pure copper acetate in 5mL of analytically pure N,N'-dimethylformamide, place in a micro-reaction flask, add 5mL of distilled water, and After standing in the oven for three days, red crystals [Cu(tibc) ₂ ] _n formed. The structure of [Cu(tibc) ₂ ] _n was determined by a single crystal diffractometer. The crystal structure data is shown in Table 1, and the bond length and angle data are shown in Table 2.

(2) Dissolve [Cu(tibc) ₂ ] _n obtained in step (1) in analytically pure N,N'-dimethylformamide solvent to prepare a solution with a concentration of 5.0×10 ^-6 mol/L, and perform fluorescence Test, -[Cu(tibc) ₂ ] _n -under the incident light of 450nm produces 520nm fluorescence of 193.7au intensity; in the 800V photomultiplier tube, under the magnification factor of 3 times, take 100μL of the above prepared solution In 1mol/L potassium persulfate solution (conductive medium), 2750a.u. intensity luminescence is produced, and under this condition, it can continue and stably luminescence.

The invention has the advantages of simple process, low cost, easy control of chemical components, good repeatability and high output.

Description of drawings

Fig. 1 is a structure diagram of [Cu(tibc) ₂ ] _n in the present invention.

Fig. 2 is a two-dimensional plan view of [Cu(tibc) ₂ ] _n in the present invention.

Fig. 3 is a three-dimensional structure diagram of [Cu(tibc) ₂ ] _n in the present invention.

Fig. 4 is a fluorescence spectrum diagram of [Cu(tibc) ₂ ] _n in the present invention.

Fig. 5 is an electrochemiluminescence spectrum diagram of [Cu(tibc) ₂ ] _n in the present invention.

Detailed ways

Example 1:

The molecular formula of [Cu(tibc) ₂ ] _n involved in the present invention is: C ₁₈ H ₁₀ CuBr ₄ N ₈ O ₂ , the relative molecular weight is: 753.5, and Htibc is 2,4-dibromo-6-(1,2,4 )-triazole-4-iminomethylphenol, the crystal structure data is shown in Table 1, and the bond length and bond angle data are shown in Table 2.

[Cu(tibc) ₂ ] The specific steps of the synthetic method of _n are:

(1) 2.79g of analytically pure 3,5-dibromosalicylaldehyde and 0.841g of analytically pure 4-amino-1,2,4-triazole were dissolved in 30mL of analytically pure ethanol solution, heated to reflux and After stirring for two hours, a solid precipitated, filtered, washed three times with 10 mL of analytically pure ethanol, and dried at 50° C. to obtain the ligand Htibc. Yield: 3.214 g, 94% yield. Dissolve 0.069g of dried Htibc and 0.040g of analytically pure copper acetate in 5mL of analytically pure N,N'-dimethylformamide, place in a micro-reaction flask, add 5mL of distilled water, and place in an oven at 80°C Three days later, red crystals [Cu(tibc) ₂ ] _n formed. Yield: 0.039 g, 43% yield. The structure of [Cu(tibc) ₂ ] _n was determined by a single crystal diffractometer. The crystal structure data is shown in Table 1, and the bond length and angle data are shown in Table 2.

(2) Dissolve [Cu(tibc) ₂ ] _n obtained in step (1) in analytically pure N,N'-dimethylformamide solvent to prepare a solution with a concentration of 5.0×10 ^-5 mol/L, and perform fluorescence Test, [Cu(tibc) ₂ ] _n produces 520nm fluorescence with 193.7au intensity under the irradiation of 450nm incident light; in the 800V photomultiplier tube, under the magnification factor of 3 times, take 100μL of the above prepared solution and place it in 1mol In /L potassium persulfate solution (conductive medium), the intensity of luminescence of 2750a.u. is produced, and under this condition, the luminescence can be sustained and stable.

Example 2:

The molecular formula of [Cu(tibc) ₂ ] _n involved in the present invention is: C ₁₈ H ₁₀ CuBr ₄ N ₈ O ₂ , the relative molecular weight is: 753.5, and Htibc is 2,4-dibromo-6-(1,2,4 )-triazole-4-iminomethylphenol, the crystal structure data is shown in Table 1, and the bond length and bond angle data are shown in Table 2.

[Cu(tibc) ₂ ] The specific steps of the synthetic method of _n are:

(1) 2.79g of analytically pure 3,5-dibromosalicylaldehyde and 0.841g of analytically pure 4-amino-1,2,4-triazole were dissolved in 30mL of analytically pure ethanol solution, heated to reflux and After stirring for two hours, a solid precipitated, filtered, washed three times with 10 mL of analytically pure ethanol, and dried at 50° C. to obtain the ligand Htibc. Yield: 3.214 g, 94% yield. Dissolve 0.138g of dried Htibc and 0.080g of analytically pure copper acetate in 5mL of analytically pure N,N'-dimethylformamide, place in a micro-reaction flask, add 5mL of distilled water, and place in an oven at 80°C Three days later, red crystals [Cu(tibc) ₂ ] _n formed. Yield: 0.078 g, 43% yield. The structure of -[Cu(tibc) ₂ ] _n - was determined by a single crystal diffractometer, the crystal structure data is shown in Table 1, and the bond length and bond angle data are shown in Table 2.

(2) Dissolve [Cu(tibc) ₂ ] _n obtained in step (1) in analytically pure N,N'-dimethylformamide solvent to prepare a solution with a concentration of 5.0×10 ^-5 mol/L, and perform fluorescence Test, [Cu(tibc) ₂ ] _n produces 520nm fluorescence with 193.7au intensity under the irradiation of 450nm incident light; in the 800V photomultiplier tube, under the magnification factor of 3 times, take 100μL of the above prepared solution and place it in 1mol In /L potassium persulfate solution (conductive medium), the intensity of luminescence of 2750a.u. is produced, and under this condition, the luminescence can be sustained and stable.

Claims (1)

1. a kind of luminescent material [Cu (tibc)₂]_n, it is characterised in that [Cu (tibc)₂]_nMonomer molecule formula be： C₁₈H₁₀CuBr₄N₈O₂, relative molecular weight is：753.5, Htibc be bis- bromo- 6- (1,2,4) of 2,4--triazole -4- formaminos Phenol, crystal structural data are shown in Table one, and bond distance's bond angle data are shown in Table two；193.7a.u. is generated under the incident light irradiation of 450nm The fluorescence of the 520nm of intensity；Under the photomultiplier of 800V, 3 times of amplification coefficient, in conducting medium 1mol/L potassium peroxydisulfates In solution, shining for 2750a.u. intensity and stabilization is generated；

Table one:[Cu(tibc)₂]_nCrystallographic parameter

^aR₁=Σ | | F_o|–|F_c||/Σ|F_o|；^bwR₂=[Σ w (| F_o ²|–|F_c ²|)²/Σw(|F_o ²|)²]^1/2

Table two:The bond distance of [Cu (tibc) 2] nWith bond angle °

Symmetry operation:(i)-x,-y+1,-z；(ii)x,-y+1/2,z-1/2；(iii)-x,y+1/2,-z+1/2；(iv)-x,y- 1/2,-z+1/2；(v)x,-y+1/2,z+1/2；

[the Cu (tibc)₂]_nSynthetic method the specific steps are：

By analytically pure 3, the 5- Dibromosalicylaldehydes of 2.79g and the analytically pure 4- amino -1,2 of 0.841g, 4- triazoles are dissolved in 30mL It analyzes in straight alcohol solution, is heated to reflux and has solid precipitation after stirring two hours, filter, washed with 10mL analysis straight alcohols Three times, drying at 50 DEG C is placed, ligand Htibc is obtained；Htibc and 0.040-0.080g points after 0.069-0.138g is dried It analyses pure copper acetate and is dissolved in 5mL and analyze pure N, in N '-dimethyl formamide, be placed in micro- reaction bulb, add 5mL distilled water, Three days are stood in 80 DEG C of baking ovens, there are red crystals to generate i.e. [Cu (tibc)₂]_n。