CN109232616B - (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex and preparation method thereof - Google Patents

(-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex and preparation method thereof Download PDF

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CN109232616B
CN109232616B CN201811266246.8A CN201811266246A CN109232616B CN 109232616 B CN109232616 B CN 109232616B CN 201811266246 A CN201811266246 A CN 201811266246A CN 109232616 B CN109232616 B CN 109232616B
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李郤里
朱灿灿
刘应凡
李凤彩
李俊锋
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Zhengzhou University of Light Industry
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Abstract

The invention discloses a (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex, the molecular formula of which is [ Ag (L) ClO4]∞The invention uses chiral monodentate N-containing organic ligand L [ (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine]With AgClO4The preparation method of the (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex obtained by the reaction has the advantages of simple process, normal temperature and pressure reaction, good safety, low cost, easy post-treatment and high yield up to 86%; the complex not only has chiral optical activity, but also has the capability of absorbing ultraviolet light and generating visible light emission, is a bifunctional material simultaneously having chiral optical activity and light conversion capability, and is expected to have wide commercial application prospect as a novel luminescent material in the aspects of circular polarization luminescence, fluorescence immunoassay, nonlinear optical materials, light conversion molecular devices and the like.

Description

(-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex and preparation method thereof
Technical Field
The invention belongs to the technical field of inorganic-organic hybrid chiral functional materials and preparation and application thereof, and particularly relates to a chiral silver complex with visible light luminescent property and a preparation method thereof.
Background
Chirality is a fundamental property of matter that plays an important role in biology, medicinal chemistry, and material science. The design and synthesis of chiral structures has long been an interesting topic, attracting the attention of researchers in many research areas, not only because they have important structures related to biology, but also because chiral materials have broad commercial application prospects in nonlinear optics, asymmetric catalysis, enantioselective adsorption and separation, etc.
In the transition metal complexes, d10The silver complex with electronic configuration has unique luminescent property, is an important molecular-based luminescent material, and becomes a popular research subject in the fields of coordination chemistry and material science. Especially the introduction of chirality in luminescent silver complexes, it is also possible to impart to such luminescent materials some chirally related and interesting physical properties such as: chiral circular polarization luminescence, chiral fluorescent probes, chiral induction and the like are potential multifunctional materials. The design and preparation of such materials are even more of an interesting and challenging research topic for synthetic chemists and material scientists.
Disclosure of Invention
The invention aims to provide a (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex luminescent material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
(-) -2- (4 '-pyridyl) -4, 5-pinene-pyridine chiral silver complex, wherein the (-) -2- (4' -pyridyl) -4, 5-pineneThe molecular formula of the chiral silver-pyridine complex is [ Ag (L) ClO4] ∞Wherein L is a chiral monodentate N-containing organic ligand: (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine with the structural formula
Figure DEST_PATH_IMAGE002
。
The preparation method of (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex comprises the following steps:
(1) will dissolve silver perchlorate AgClO4The methanol solution is put into a test tube to be used as a bottom layer, wherein the concentration of the silver perchlorate is 0.01-0.02 mol/L;
(2) adding 6-8 mL of mixed solution of methanol and dichloromethane as an intermediate buffer layer on the bottom layer;
(3) dissolving a chiral monodentate N-containing organic ligand L: slowly adding dichloromethane solution of (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine into a test tube to serve as the uppermost layer, wherein the concentration of the chiral monodentate N-containing organic ligand L is 0.01-0.02 mol/L; standing the tube at room temperature for 4-5 days to obtain colorless crystal, filtering, washing with methanol and water, and drying at room temperature to obtain (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO4] ∞；
The volume ratio of the bottom layer, the middle buffer layer and the uppermost layer is (4-7) to (6-9) to (4-7).
The volume ratio of the methanol to the dichloromethane in the mixed solution of the methanol and the dichloromethane in the step (2) is 1: 2.
The two reactants AgClO4The ratio of the amount of the substance to the chiral monodentate N-containing organic ligand L is 1: 1.
In the step (3), the chiral monodentate N-containing organic ligand L: the preparation method of (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine comprises the following steps:
a. preparation of 4- (pyridylacetyl) pyridine iodide salt intermediate: adding 5.3 g of 4-acetylpyridine into a 250mL round-bottom flask, dissolving with 25-30 mL of pyridine, adding 20-25 mL of pyridine solution dissolved with 18-21 g of iodine into the round-bottom flask, heating the mixture to 100-110 ℃, reacting for 4-4.5 hours, cooling to room temperature, filtering, washing twice with a small amount of pyridine, and drying in vacuum to obtain a gray solid which is the required intermediate;
b. chiral monodentate N-containing organic ligand L: synthesis of (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine: weighing 4.2 g of the 4- (pyridine acetyl) pyridine iodide salt intermediate prepared in the step a and 2.5-3.2 g of ammonium acetate (NH)4Ac) is placed in a three-neck flask, and then 45-50 mL of formamide (CH) is added3CONH2). 2.8 g of myrtenal (-) -myrtenoal (produced by carbofuran corporation) is added under continuous stirring, the mixture is heated to 75-85 ℃, the reaction is carried out for 12-12.5 hours under nitrogen, the product is filtered to obtain milk white solid, the milk white solid is washed by water and recrystallized by ethanol, and then the solid is dried in vacuum to obtain the chiral monodentate N-containing organic ligand L.
The invention has the beneficial effects that: (1) the invention relates to a chiral monodentate N-containing organic ligand L [ (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine]With AgClO4The preparation method of the (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex obtained by the reaction has the advantages of simple process, normal temperature and pressure reaction, good safety, low cost, easy post-treatment and high yield up to 86%; (2) the (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex prepared by the invention not only has chiral optical activity, but also has the capability of absorbing ultraviolet light and generating visible light emission, and is a rare bifunctional material with chiral optical activity and light conversion capability. (3) The chiral luminescent material has the advantages of mild synthesis conditions, high yield, strong stability, good reproducibility and easy separation and purification, and is expected to have wide commercial application prospect in the aspects of circular polarization luminescence, fluorescence immunoassay, nonlinear optical materials, light conversion molecular devices and the like as a novel luminescent material.
Drawings
FIG. 1 shows example 1 (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO4]nThe coordination environment of Ag (I) ion of (1), H atom has been omitted for clarity.
FIG. 2 shows example 1 (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complexThe compound [ Ag (L) ClO4]nThe two-dimensional layered molecular structure of (a) has been omitted for clarity.
FIG. 3 shows example 1 (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO4]nEmission spectrum of the luminescent material.
FIG. 4 shows example 1 (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO4]nExcitation spectrum of luminescent material.
FIG. 5 shows example 1 (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO4]nChiral circular dichroism spectra of luminescent materials.
Detailed Description
Example 1
This example (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO4]nThe preparation method comprises the following steps:
(1) will dissolve AgClO4A solution of (0.08 mmol, 16.6 mg) in methanol (4 mL) was placed in the bottom layer of the tube;
(2) then 6 mL of a mixed solution of methanol and methylene chloride (volume ratio CH) was added3OH : CH2Cl2= 1: 2) as an intermediate buffer layer;
(3) dichloromethane (4 mL) dissolved with chiral monodentate N-containing organic ligand L (0.08 mmol, 20 mg) is slowly added into a test tube as the uppermost layer, the test tube stands for 4-5 days at room temperature to generate massive colorless crystals, the crystals are filtered, washed with methanol and water respectively, and dried at room temperature to obtain (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO4]nThe calculated yield was 86% (calculated as silver).
(-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO is measured by Bruker SMART APEX CCD diffractometer single crystal diffractometer at normal temperature4]nThe molecular structure of (1) (see fig. 1 and 2). As shown in FIG. 2, the molecular structure of the chiral silver complex luminescent material is composed of a repeating unit [ Ag (L) ClO4]Two-dimensional of compositionA layered structure. (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO) was measured by using a Biologic MS-500 chiral polarimeter4]nThe complex shows negative Cotton effect at the wavelength λ = 253 and 320 nm, confirming the chiral optical activity of the silver complex luminescent material (see fig. 5).
(-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO4]nThe luminescence property test of (1):
(-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO) was tested at room temperature using FLS980P fluoroscope spectrometer4]nEmission and excitation spectra of (corresponding to fig. 3 and 4, respectively). The test shows that: (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO4]nUnder the irradiation of 370 nm ultraviolet light, 600 nm orange red fluorescence can be emitted. This result indicates that: the prepared (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO4]nThe chiral silver complex has large Stokes displacement, can effectively absorb ultraviolet light and generate visible light emission, and therefore, the chiral silver complex has high-efficiency light conversion capability and has potential application prospects in the aspects of selection and development of light conversion devices.
This example shows chiral monodentate N-containing organic ligands L: the preparation method of (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine comprises the following steps:
a. preparation of 4- (pyridylacetyl) pyridine iodide salt intermediate: adding 5.3 g of 4-acetylpyridine into a 250mL round-bottom flask, dissolving with 25mL of pyridine, adding 20 mL of pyridine solution dissolved with 18 g of iodine into the round-bottom flask, heating the mixture to 100 ℃, reacting for 4.5 hours, then cooling to room temperature, filtering, washing twice with a small amount of pyridine, and drying in vacuum to obtain a gray solid which is the required intermediate;
b. chiral monodentate N-containing organic ligand L: synthesis of (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine: weighing 4.2 g of the 4- (pyridylacetyl) pyridinium iodide intermediate prepared in step a and 2.5 g of ammonium acetate (NH)4Ac) was placed in a three-neck flaskTo the flask, 45 mL of formamide (CH) was added3CONH2) 2.8 g of myrtenal (-) -myrtenoal (from carbofuran) are added with continuous stirring, heated to 75 ℃ and reacted under nitrogen for 12.5 hours, the product is filtered to give a milky white solid, washed with water, recrystallized from ethanol and then dried to give the chiral monodentate N-containing organic ligand L: (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine.
The yield was 87% (based on intermediate). Elemental analysis: according to the formula C17H18N2(molecular weight 250.33): c, 81.56, H, 7.25, N, 11.19, C, 81.51, H, 7.34 and N, 11.13. Infrared spectrum IR (KBr) 2947(s), 2991(m), 2864(v), 1584(m), 1450(s), 1383(m), 782(m), 756(s).
Example 2
This example (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO4]nThe preparation method comprises the following steps:
(1) will dissolve AgClO4A solution of (0.04 mmol, 8.3 mg) in methanol (4 mL) was placed in the bottom layer of the tube;
(2) then 8mL of a mixed solution of methanol and methylene chloride (volume ratio CH) was added3OH : CH2Cl2= 1: 2) as an intermediate buffer layer;
(3) dichloromethane (4 mL) dissolved with chiral monodentate N-containing organic ligand L (0.04 mmol, 10 mg) is slowly added into a test tube as the uppermost layer, the test tube stands for 4-5 days at room temperature to generate massive colorless crystals, the crystals are filtered, washed with methanol and water respectively, and dried at room temperature to obtain (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO4]n。
This example shows chiral monodentate N-containing organic ligands L: the preparation method of (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine comprises the following steps:
a. preparation of 4- (pyridylacetyl) pyridine iodide salt intermediate: adding 5.3 g of 4-acetylpyridine into a 250mL round-bottom flask, dissolving with 30mL of pyridine, adding 25mL of pyridine solution dissolved with 21 g of iodine into the round-bottom flask, heating the mixture to 110 ℃, reacting for 4.5 hours, then cooling to room temperature, filtering, washing twice with a small amount of pyridine, and drying in vacuum to obtain a gray solid which is the required intermediate;
b. chiral monodentate N-containing organic ligand L: synthesis of (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine: weighing 4.2 g of the 4- (pyridylacetyl) pyridinium iodide intermediate prepared in step a and 3.2 g of ammonium acetate (NH)4Ac) was placed in a three-necked flask, and 50mL of formamide (CH) was added3CONH2) Adding 2.8 g of myrtenal (-) -myrtenoal (produced by carbofuran corporation) under continuous stirring, heating to 85 ℃, reacting for 12 hours under nitrogen, filtering the product to obtain a milky white solid, washing with water, recrystallizing with ethanol, and drying the solid to obtain the chiral monodentate N-containing organic ligand L: (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine.
Example 3
This example (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO4]nThe preparation method comprises the following steps:
(1) will dissolve AgClO4(0.08 mmol, 16.6 mg) in methanol (7 mL) was placed in the bottom layer of the tube;
(2) then, 9 mL of a mixed solution of methanol and methylene chloride (volume ratio: CH) was added3OH : CH2Cl2= 1: 2) as an intermediate buffer layer;
(3) dichloromethane (6 mL) dissolved with chiral monodentate N-containing organic ligand L (0.08 mmol, 20 mg) is slowly added into a test tube as the uppermost layer, the test tube stands for 4-5 days at room temperature to generate massive colorless crystals, the crystals are filtered, washed with methanol and water respectively, and dried at room temperature to obtain (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO4]n。
This example shows chiral monodentate N-containing organic ligands L: the preparation method of (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine comprises the following steps:
a. preparation of 4- (pyridylacetyl) pyridine iodide salt intermediate: adding 5.3 g of 4-acetylpyridine into a 250mL round-bottom flask, dissolving with 28 mL of pyridine, adding 24 mL of pyridine solution dissolved with 20 g of iodine into the round-bottom flask, heating the mixture to 105 ℃, reacting for 4.5 hours, then cooling to room temperature, filtering, washing twice with a small amount of pyridine, and drying in vacuum to obtain a gray solid which is the required intermediate;
b. chiral monodentate N-containing organic ligand L: synthesis of (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine: weighing 4.2 g of the 4- (pyridylacetyl) pyridinium iodide intermediate prepared in step a and 3.0 g of ammonium acetate (NH)4Ac) was placed in a three-necked flask, and 48 mL of formamide (CH) was added3CONH2) 2.8 g of myrtenal (-) -myrtenoal (from carbofuran) are added with continuous stirring, heated to 80 ℃ and reacted under nitrogen for 12.5 hours, the product is filtered to obtain a milky white solid, washed with water, recrystallized from ethanol and then dried to obtain the chiral monodentate N-containing organic ligand L: (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine.

Claims (4)

1. The (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex has the molecular formula of [ Ag (L) ClO4]∞Wherein L is a chiral monodentate N-containing organic ligand: (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine with the structural formula
Figure FDA0002556200820000011
2. The preparation method of (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex according to claim 1, wherein the preparation method comprises the following steps: the method comprises the following steps:
(1) will dissolve AgClO4The methanol solution is put into a test tube to be used as a bottom layer, wherein the concentration of the silver perchlorate is 0.01-0.02 mol/L;
(2) adding a mixed solution of methanol and dichloromethane on the bottom layer as an intermediate buffer layer;
(3) dissolving a chiral monodentate N-containing organic ligand L: (-) -2- (4' -pyridyl)) Slowly adding a dichloromethane solution of 4, 5-pinene-pyridine into the test tube to serve as the uppermost layer, wherein the concentration of the chiral monodentate N-containing organic ligand L is 0.01-0.02 mol/L; standing the tube at room temperature for 4-5 days to obtain colorless crystal, filtering, washing with methanol and water, and drying at room temperature to obtain (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex [ Ag (L) ClO4]∞；
The liquid volume ratio of the bottom layer, the middle buffer layer and the uppermost layer is (4-7) to (6-9) to (4-7);
in the step (3), the chiral monodentate N-containing organic ligand L: the preparation method of (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine comprises the following steps:
preparation of 4- (pyridylacetyl) pyridine iodide salt intermediate: adding 5.3 g of 4-acetylpyridine into a 250mL round-bottom flask, dissolving with 25-30 mL of pyridine, adding 20-25 mL of pyridine solution dissolved with 18-21 g of iodine into the round-bottom flask, heating the mixture to 100-110 ℃, reacting for 4-4.5 hours, cooling to room temperature, filtering, washing twice with a small amount of pyridine, and drying in vacuum to obtain a gray solid which is the required intermediate;
b. chiral monodentate N-containing organic ligand L: synthesis of (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine: weighing 4.2 g of the 4- (pyridine acetyl) pyridine iodonium salt intermediate prepared in the step a and 2.5-3.2 g of ammonium acetate, placing the intermediate and the ammonium acetate in a three-neck flask, adding 45-50 mL of formamide, adding 2.8 g of myrtenal (-) -myrtenal under continuous stirring, heating to 75-85 ℃, reacting for 12-12.5 hours under nitrogen, filtering the product to obtain a milky white solid, washing with water, recrystallizing with ethanol, and then drying the solid in vacuum to obtain the chiral monodentate N-containing organic ligand L.
3. The preparation method of (-) -2- (4' -pyridyl) -4, 5-pinene-pyridine chiral silver complex according to claim 2, wherein the preparation method comprises the following steps: the volume ratio of the methanol to the dichloromethane in the mixed solution of the methanol and the dichloromethane in the step (2) is 1: 2.
4. (-) -2- (4' -pyridyl) according to claim 2The preparation method of the (E) -4, 5-pinene-pyridine chiral silver complex is characterized by comprising the following steps: the AgClO4The ratio of the amount of the substance to the chiral monodentate N-containing organic ligand L is 1: 1.
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Title
"Helical Silver(I) 2,4′-Bipyridine Chains Organized into 2-D Networks by Metal-Counterion or Metal-Metal Bonding. Structures of [Ag(2,4′-bipyridine)]X(X-=NO3- or ClO4-)";Ming-Liang Tong等;《Inorg.Chem.》;19980915;第37卷(第20期);摘要、第5279页左栏第3-4段，第5280页左栏第1段 *
"具有光、磁和铁电性质的手性分子基稀土功能材料的构筑与研究";和来福;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20120615(第06期);正文第9页第2段、第15页、第三章 *

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