CN113416204A - Coordination polymer crystal material containing 2, 6-diimidazole pyridine and preparation method thereof - Google Patents

Coordination polymer crystal material containing 2, 6-diimidazole pyridine and preparation method thereof Download PDF

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CN113416204A
CN113416204A CN202110582490.0A CN202110582490A CN113416204A CN 113416204 A CN113416204 A CN 113416204A CN 202110582490 A CN202110582490 A CN 202110582490A CN 113416204 A CN113416204 A CN 113416204A
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pyridine
diimidazole
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钱军
段华建
彭诗祺
张轶丰
冯世嘉
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    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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Abstract

The invention belongs to the field of catalysis and drug transportation, and discloses a coordination polymer crystal material containing 2, 6-diimidazole pyridine, and a preparation method and application thereof. Mixing CuSCN and NH4Adding SCN into a DMF solvent in proportion, and violently stirring under the protection of nitrogen atmosphere to obtain a colorless clear solution; then adding bridging ligand 2, 6-diimidazole pyridine, changing the color of the solution from colorless to blue-green, and continuously stirring until the solution is clear and transparent; filtering, sequentially adding DMF solvent as buffer solution and acetonitrile or isopropanol solvent as diffusion layer to the upper layer of the filtrate, and performing diffusion culture. After a certain time, [ Cu (2,6-BIP) is obtained2(NCS)2}]nCrystal, i.e. aA coordination polymer crystal material containing 2, 6-diimidazole pyridine. The obtained copper coordination polymer crystal material of the 2, 6-diimidazole pyridine can be used as a photocatalysis or drug transport material.

Description

Coordination polymer crystal material containing 2, 6-diimidazole pyridine and preparation method thereof
Technical Field
The invention belongs to the field of catalysis and drug transportation, and particularly relates to a coordination polymer crystal material containing 2, 6-diimidazole pyridine, and a preparation method and application thereof.
Background
Coordination polymers (Coordination polymers) or Metal Organic frameworks (Metal Organic frameworks) have potential application values in the aspects of gas absorption, separation, catalysis, drug delivery, nanoparticle embedding and the like due to the characteristics of diversified Framework structures, porosity, multi-cavity and the like. During synthesis, various bridging ligands such as rigid 4, 4' -bipyridyl and terephthalic acid or flexible thiocyanate are mostly introduced into the coordination polymer with the porous structure. Through modification of the bridged ligand, such as changing the length and flexibility of the ligand or modifying a group, the shape, the volume, the active site and the like of a polymer pore or a cavity can be adjusted, and the application performance of the polymer pore or the cavity is further influenced. Therefore, different types of bridging ligands are introduced to synthesize the coordination polymer with a novel structure, a simple and convenient method is explored by utilizing a molecular engineering technology to prepare the crystal material, the performances of adsorption, catalysis and the like of the crystal material are researched, and the method is finally applied to the fields of catalysis, drug transportation and the like and has very important significance.
Disclosure of Invention
The main content of the invention is as follows: a coordination polymer [ Cu (2,6-BIP) with a helical structure is synthesized by introducing a bridging ligand with a specific spatial configuration by a self-assembly method2(NCS)2}]nWherein the 2,6-BIP (2,6-bis (1-iMidazoly) pyridine) is 2, 6-diimidazole pyridine. 2, 6-diimidazole pyridine is a hinge-like molecule, and the C-N bond between three aromatic rings can rotate to some extent. Thus, such semi-rigid ligands allow a certain degree of structural adjustment in the construction of polymer structures, while avoiding the disadvantage of poor support of flexible ligands.
The invention firstly provides a coordination polymer crystal material containing 2, 6-diimidazole pyridine, wherein Cu atoms in the crystal material are respectively linked with two terminal groups NCS in a hexa-coordination mode-The N atom is coordinated with N atoms on imidazole rings of four bridging organic ligands to form an octahedral space configuration, and N is more than 1. The crystal structure of the asymmetric unit is as followsShown in a chemical formula.
Figure BDA0003086547930000021
The invention also provides a preparation method of the coordination polymer containing 2, 6-diimidazole pyridine, which comprises the following steps:
step 1:
mixing CuSCN and NH4Adding SCN into a Dimethylformamide (DMF) solvent according to a certain molar ratio, and violently stirring under the protection of nitrogen atmosphere to obtain a colorless clear solution.
Step 2:
adding the bridging ligand 2, 6-diimidazole pyridine into the solution obtained in the step 1, changing the color of the solution from colorless to blue-green, and continuously stirring until the solution is clear and transparent.
And step 3:
and (3) filtering the solution obtained in the step (2), and sequentially adding a DMF solvent as a buffer solution and an acetonitrile or isopropanol solvent as a diffusion layer to the upper layer of the filtrate for diffusion culture. After a certain time, [ Cu (2,6-BIP) is obtained2(NCS)2}]nThe crystal is a coordination polymer crystal material containing 2, 6-diimidazole pyridine.
Further, in step 1, the CuSCN and NH4The molar ratio of SCN is 1: 1-1: 2.
Further, in the step 2, the molar ratio of the added ligand 2, 6-diimidazole pyridine to CuSCN is 1:1, and the stirring time is 3-6 h.
Further, in step 2, the color change that occurs with the addition of the ligand 2, 6-diimidazole pyridine is due to Cu in CuSCN+Is oxidized into Cu2+。
Further, in the step 3, the volume ratio of the buffer solution to the diffusion layer is 1: 1-1: 3.
Further, in step 3, the time of the decentralized culture is three to five days.
Further, the [ Cu (2,6-BIP)2(NCS)2}]nThe crystal belongs to monoclinic systemSpace group is P21/c。
[Cu(2,6-BIP)2(NCS)2}]nUsing Rigaku Satum 724+X-ray diffractometer, MoK alpha radiation monochromated by a graphite monochromator
Figure BDA0003086547930000031
T293K, diffraction data corrected for Lp factor and Multi-scan absorption. Using SHELXTL-97 program package to complete structure analysis, using direct method and round difference Fourier synthesis method to determine coordinates of all non-hydrogen atoms, finally using full matrix least square method to give F2The structure is modified. All non-hydrogen atoms are corrected anisotropically, hydrogen atoms are added by a theoretical method, and an isotropic displacement parameter (U) is giveniso＝1.2，UeqThe equivalent isotropic displacement parameter of the parent atom).
The copper coordination polymer crystal material containing 2, 6-diimidazole pyridine can be used as a photocatalysis or drug transport material, and the research on the field of reaction catalysis or drug carriers is realized.
The principle of the invention is as follows:
the patent designs and synthesizes a copper coordination polymer containing 2, 6-diimidazole pyridine with a two-dimensional spiral structure by using a hinge-like molecular structure of a 2, 6-diimidazole pyridine ligand from the structure of the polymer. The corresponding crystal material is obtained by a normal temperature solvent diffusion method by applying the principle of crystal engineering.
The invention has the beneficial effects that:
(1) the invention prepares the copper coordination polymer crystal containing 2, 6-diimidazole pyridine, and determines the crystal structure through single crystal diffraction characterization, wherein the crystal system is monoclinic, and the space group is P21/c。
(2) The invention selects 2, 6-diimidazole pyridine ligand and CuSCN and NH4And (3) carrying out coordination on copper-containing complex ions formed after the SCN reaction to obtain the copper coordination polymer with a two-dimensional spiral structure. Wherein the 2, 6-diimidazole pyridine ligand is a hinge-like molecule, and C-N bonds among three aromatic rings can rotate to a certain degree, so that the polymer is constructedThe structure can be adjusted to a certain extent during structure, the defect of poor supporting property of the flexible ligand is avoided, and a design thought is provided for synthesis of the polymer.
Drawings
FIG. 1[ Cu (2,6-BIP)2(NCS)2}]nCrystal structure of asymmetric unit, 30% probability ellipsoid (hydrogen atom omitted in figure);
FIG. 2[ Cu (2,6-BIP)2(NCS)2}]nThe coordination environment of the Cu atom in (a);
FIG. 3[ Cu (2,6-BIP)2(NCS)2}]nThe two-dimensional helical structure of (1), hydrogen atoms are omitted in the figure.
Detailed Description
The present invention will be described or further illustrated below with reference to specific examples, which show detailed embodiments and specific operations for better understanding the technical spirit of the present invention, but the scope of the present invention is not limited to the following.
Example 1:
0.0126g of CuSCN (0.1mmol) and 0.0076g of NH were weighed4SCN (0.1mmol) is added into 3mL of DMF solution, and a colorless solution is obtained after vigorous stirring for 1 hour; then 0.0213mg of 2,6-BIP (0.1mmol) is added, stirring is continued for 6 hours to obtain a blue-green solution, and filtering is carried out; then, 1mL of DMF solution was added as a buffer solution and 1mL of acetonitrile solution was added as a diffusion layer to the upper layer of the filtrate. After standing for two days, green crystals were obtained in a yield of 0.038g and a yield of 64% (based on Cu). Elemental analysis: c24H18CuN12S2Theoretical value: c, 47.87; h, 3.01; n, 27.91 (%). Measured value: c, 48.12; h, 3.19; n, 28.17 (%). IR (KBr pellet, v/cm)-1): 2083(s), 2054(s), 1654(m), 1605(s), 1585(m), 1491(s), 1458(s), 1319(w), 1286(w), 1233(m), 1176(w), 1061(m), 1004(w) (C ═ N on the pyridine ring), 849(w), 792(m), 743(w), 653 (m).
To determine its structure, we measured the crystal structure of the coordination polymer by single crystal X-ray diffraction. The coordination polymer crystallography data, the main bond length and bond angle data are shown in tables 1 and 2.
TABLE 1 crystallographic data for coordination polymers
Figure BDA0003086547930000041
Figure BDA0003086547930000051
TABLE 2 major bond lengths of coordination polymers
Figure BDA0003086547930000052
Key angle (°)
Figure BDA0003086547930000053
Example 2:
0.0146g of CuSCN (0.12mmol) and 0.0182g of NH were weighed out4SCN (0.24mmol) is added into 5mL of DMF solution, and a colorless solution is obtained after vigorous stirring for 1 hour; then adding 0.0255mg of 2,6-BIP (0.12mmol), continuously stirring for 6 hours to obtain a blue-green solution, and filtering; then 1mL of DMF as a buffer solution and 2mL of isopropanol solution as a diffusion layer were added to the upper layer of the filtrate in this order. After standing for four days, green crystals were obtained in a yield of 0.045g and a yield of 63.2% (in terms of Cu).
Example 3:
0.0170g of CuSCN (0.14mmol) and 0.0152g of NH were weighed out4SCN (0.2mmol) is added into 5mL of DMF solution, and colorless solution is obtained after vigorous stirring for 1 hour; then 0.0298mg of 2,6-BIP (0.14mmol) is added, stirring is continued for 6 hours to obtain a blue-green solution, and filtering is carried out; then 1.5 mL of DMF as a buffer solution and 3mL of acetonitrile solution as a diffusion layer were added to the upper layer of the filtrate in this order. After standing for three days, green crystals were obtained in a yield of 0.048g and a yield of 57.7% (in terms of Cu).
FIG. 1 shows [ Cu (2,6-BIP)2(NCS)2}]nAsymmetric sheetMeta-crystal structure, [ Cu (2,6-BIP)2(NCS)2}]nThe asymmetric cell structure of (1) comprises a Cu2+Ion, two fragments of 2,6-BIP organic ligand, an NCS-Ions.
FIG. 2 shows [ Cu (2,6-BIP)2(NCS)2}]nThe coordination environment of Cu atom in the coordination polymer is that the Cu atom in the coordination polymer is in a six-coordination octahedral space configuration and is respectively connected with two terminal groups NCS-The N atom is coordinated with the N atoms on imidazole rings of four bridging organic ligands, the complex obtains a two-dimensional crystal structure through the bridging action of the 2,6-BIP ligand, and the average bond length of the Cu atom and the Cu-N on the 2,6-BIP ligand is
Figure BDA0003086547930000061
Cu and terminal ligand NCS-Coordinated Cu-N bond length of
Figure BDA0003086547930000062
FIG. 3 shows [ Cu (2,6-BIP)2(NCS)2}]nThe coordination polymer has a two-dimensional helical structure. In the complex, three rings, namely a pyridine ring in the middle of the ligand 2,6-BIP and two imidazole rings on two sides, are not positioned on the same plane, the dihedral angles of the pyridine ring and the two imidazole rings are 3.383 degrees and 35.584 degrees respectively, and certain distortion exists, so that the structure of the polymer is a spiral two-dimensional structure.

Claims (7)

1. A coordination polymer crystal material containing 2, 6-diimidazole pyridine, which is characterized in that the molecular formula is [ Cu (2,6-BIP)2(NCS)2}]nCu atom is respectively linked with two terminal groups NCS in a hexacoordination mode-The N atom on the N-substituted imidazole complex is coordinated with the N atoms on four bridged organic ligands to form an octahedral space configuration; n is greater than 1; belonging to monoclinic system, space group is P21/c。
2. The method for preparing a coordination polymer crystalline material containing 2, 6-diimidazole pyridine according to claim 1, comprising the steps of:
step 1:
mixing CuSCN and NH4Adding SCN into a dimethyl formamide DMF solvent according to a certain molar ratio, and violently stirring under the protection of nitrogen atmosphere to obtain a colorless clear solution;
step 2:
adding a bridging ligand 2, 6-diimidazole pyridine into the solution obtained in the step 1, changing the color of the solution from colorless to blue-green, and continuously stirring until the solution is clear and transparent;
and step 3:
filtering the solution obtained in the step 2, sequentially adding a DMF solvent as a buffer solution and an acetonitrile or isopropanol solvent as a diffusion layer on the upper layer of the filtrate, and performing diffusion culture; after a certain time, [ Cu (2,6-BIP) is obtained2(NCS)2}]nThe crystal is a coordination polymer crystal material containing 2, 6-diimidazole pyridine.
3. The method of claim 2, wherein in step 1, the CuSCN and NH are present4The molar ratio of SCN is 1: 1-1: 2.
4. The preparation method according to claim 2, wherein in the step 2, the ligand 2, 6-diimidazole pyridine and CuSCN are added in a molar ratio of 1:1, and the stirring time is 3-6 h.
5. The method according to claim 2, wherein in the step 3, the volume ratio of the buffer solution to the diffusion layer is 1:1 to 1: 3.
6. The method according to claim 2, wherein the time for the dispersion culture in step 3 is three days to five days.
7. Use of the 2, 6-diimidazole pyridine-containing coordination polymer crystalline material according to claim 1 as a photocatalytic or drug transport material.
CN202110582490.0A 2021-05-27 2021-05-27 Coordination polymer crystal material containing 2, 6-diimidazole pyridine and preparation method thereof Pending CN113416204A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116120576A (en) * 2023-01-31 2023-05-16 四川轻化工大学 Preparation method and application of copper transition metal organic framework material

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHRISTOPHER W. GLYNN ET AL: "Synthesis and metal complexes of 2,6-bis(1-triazolo)pyridine: X-ray structure of 2,6-bis(1-triazolo)pyridine dihydrochloride", 《INORGANICA CHIMICA ACTA》 *
CUI, GUANG HUA ET AL: "catena-Poly[[bis(isothiocyanato-.kappa.N)copper(II)]bis(μ-1,1"-methylenedi-1H-imidazole-.kappa.N3:.kappa.N3")]", 《ACTA CRYSTALLOGRAPHICA, SECTION E: STRUCTURE REPORTS ONLINE》 *
YALI HU ET AL: "Crystal structure, thin film preparation, theoretical and experimental study the nonlinear optical properties of a novel copper complex", 《YALI HU ET AL》 *
周莉莉: "硫系杂双过渡金属W／S／Cu原子簇化合物的合成及结构表征", 《江苏大学硕士学位论文》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116120576A (en) * 2023-01-31 2023-05-16 四川轻化工大学 Preparation method and application of copper transition metal organic framework material
CN116120576B (en) * 2023-01-31 2024-03-12 四川轻化工大学 Preparation method and application of copper transition metal organic framework material

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