CN107266506B - Cobalt nitrouracil supramolecular compound and preparation method thereof - Google Patents
Cobalt nitrouracil supramolecular compound and preparation method thereof Download PDFInfo
- Publication number
- CN107266506B CN107266506B CN201710439529.7A CN201710439529A CN107266506B CN 107266506 B CN107266506 B CN 107266506B CN 201710439529 A CN201710439529 A CN 201710439529A CN 107266506 B CN107266506 B CN 107266506B
- Authority
- CN
- China
- Prior art keywords
- cobalt
- nitrouracil
- bipyridine
- reaction
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- FJMGHHNXDDNEJN-UHFFFAOYSA-N [N+](=O)([O-])C=1C(NC(NC1)=O)=O.[Co] Chemical compound [N+](=O)([O-])C=1C(NC(NC1)=O)=O.[Co] FJMGHHNXDDNEJN-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000013078 crystal Substances 0.000 claims abstract description 19
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 15
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 7
- TUARVSWVPPVUGS-UHFFFAOYSA-N 5-nitrouracil Chemical compound [O-][N+](=O)C1=CNC(=O)NC1=O TUARVSWVPPVUGS-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- SMEGNDLCVNPDNK-UHFFFAOYSA-N 4-pyridin-4-ylpyridine;dihydrate Chemical group O.O.C1=NC=CC(C=2C=CN=CC=2)=C1 SMEGNDLCVNPDNK-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- GDUDPOLSCZNKMK-UHFFFAOYSA-L cobalt(2+);diacetate;hydrate Chemical compound O.[Co+2].CC([O-])=O.CC([O-])=O GDUDPOLSCZNKMK-UHFFFAOYSA-L 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- ZTGWXXOUUKHQLW-UHFFFAOYSA-N 1-nitropyrimidine-2,4-dione Chemical compound [O-][N+](=O)N1C=CC(=O)NC1=O ZTGWXXOUUKHQLW-UHFFFAOYSA-N 0.000 claims description 3
- WJFDCFHWFHCLIW-UHFFFAOYSA-N 2-(bromomethyl)-6-methylpyridine Chemical compound CC1=CC=CC(CBr)=N1 WJFDCFHWFHCLIW-UHFFFAOYSA-N 0.000 claims description 3
- 102000004190 Enzymes Human genes 0.000 claims description 3
- 108090000790 Enzymes Proteins 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical group O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims 1
- 238000001338 self-assembly Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 150000001869 cobalt compounds Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- 230000009878 intermolecular interaction Effects 0.000 description 4
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000002983 circular dichroism Methods 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229960003540 oxyquinoline Drugs 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- OPGJGRWULGFTOS-UHFFFAOYSA-N 5-nitro-2,4-dioxo-1h-pyrimidine-6-carboxylic acid Chemical compound OC(=O)C=1NC(=O)NC(=O)C=1[N+]([O-])=O OPGJGRWULGFTOS-UHFFFAOYSA-N 0.000 description 1
- VRWJFBJLEUPFNS-UHFFFAOYSA-N C1(=C2C(=CC=C1)B2)C21CC=C(N2)C=C2C=CC(C=C3C=CC(=CC=4C=CC(=C1)N4)N3)=N2 Chemical compound C1(=C2C(=CC=C1)B2)C21CC=C(N2)C=C2C=CC(C=C3C=CC(=CC=4C=CC(=C1)N4)N3)=N2 VRWJFBJLEUPFNS-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a cobalt nitrouracil supramolecular compound and a preparation method thereof, wherein the supramolecular compound is a cobalt compound with an accurate spatial structure and has a chemical formula of CoC18H32N8O18The structural unit is [ Co (bpy) ((H))2O)4]·2(C4H2N3O4)·6H2O (bpy ═ 4, 4' -bipyridine), the crystal system is a triclinic crystal system, the space group is P-1, and the unit cell parameters are
α -86.746 degrees, β -79.405 degrees, gamma-74.842 degrees, cobalt ion is six coordination octahedral geometric configuration, the preparation method of the cobalt nitro uracil supramolecular compound is that 5-nitro potassium orotate monohydrate, 4' -bipyridine ligand and cobalt ion with electrochemical activity are carried out self-assembly reaction, and the cobalt supramolecular compound is prepared.
Description
Technical Field
The invention belongs to the field of supermolecule chemistry, and particularly relates to a cobalt nitrouracil supermolecule compound and a preparation method thereof.
Background
Supramolecules are composed of two or more secondary units, and form a molecular aggregate with a certain structure and function through intermolecular forces. Intermolecular forces within supramolecules are non-covalent, typically electrostatic, hydrogen bonding, van der waals forces, and the like. Supramolecules are ubiquitous, as are enzymes and their substrates, hormones and their receptors, and clathrates of crown ethers with certain metals. The concept of "supramolecular chemistry" was first proposed by french scientist j.m. lehn in 1978 and won the nobel prize in 1987. He pointed out that "there is a field of molecular chemistry based on covalent bonds, and supramolecular chemistry based on molecular assemblies and intermolecular bonds". Supramolecular chemistry is the chemistry of molecular aggregates formed based on non-covalent intermolecular interactions, in other words the intermolecular interactions are the core of supramolecular chemistry. In supramolecular chemistry, different types of intermolecular interactions are distinguishable, and can be classified according to their different degrees of strength, orientation, and dependence on distance and angle: coordination bonds, hydrogen bonds, pi-pi stacking interactions, electrostatic interactions, hydrophobic interactions, and the like of metal ions. Their intensity distribution ranges from weak to moderate in pi-pi stacking and hydrogen bonding to strong or very strong in metal ion coordination bonds, and these forces become the fundamental method for driving the self-assembly of supramolecules. One can assemble components or building blocks with specific structures and functions into new supramolecular compounds in a certain way, using intermolecular interaction forces as tools, according to the principle of supramolecular self-assembly. These novel compounds not only exhibit unique properties not possessed by a single molecule, but also greatly increase the number and variety of compounds. If one can control the supramolecular self-assembly process very well, compounds with specific structures and functions can be obtained more simply and reliably according to the intended target.
Researches show that 4, 4-dimethyl bipyridyl can be well matched with a cavity formed by porphyrin and crown ether, and porphyrin excited-state molecules generated under the illumination condition can well perform electron transfer to form a good optical switch model, so that the optical switch model has potential application in photochemistry. The host-guest adaptation principle of supramolecular chemistry is widely applied to piezoelectric chemical sensors. The supermolecule is used as a sensitive coating of a piezoelectric chemical sensor, and the special spatial structure of the supermolecule is utilized to carry out molecular recognition on target molecules through the synergistic effect among molecules. Analytes conforming to the spatial structure are selectively adsorbed, which can significantly improve the selectivity of the piezo-chemical sensor. The process by which a supramolecular host (or receptor) selectively binds to a guest (or substrate) and performs a specific function, allows specific recognition of its supramolecular compounds. The [ Cu ] can be synthesized by using benzene tricarboxylic acid (TMA) as a ligand3(TMA)(H2O)3]nThe coordination of supermolecule crystals makes it possible to manufacture nano-scale porous materials by means of ligand supermolecule and realize a nano-reactor. Many metal complexes of 8-hydroxyquinoline and phenanthroline have fluorescence, and 8-hydroxyquinoline or phenanthroline is introduced into a large ring, and both have independent coordination functions, so that a stable supramolecular compound can be formed and further developed into a photochemical device. The aggregate formed by accumulating the tetra (4-boranophenyl) porphyrin (TBPP) in aqueous solution and in the presence of sugar molecules by pi-pi, the Exciton Coupling Band (ECB) symbol of the Circular Dichroism (CD) has specificity to the absolute configuration of the sugar molecules, the absolute configuration of the sugar molecules can be detected, and the supramolecule has wide application in analytical chemistry. The common synthesis methods for supramolecules include the following: hydrothermal, solvothermal, microwave, ultrasonic synthesis and other synthetic methods. Different synthetic methods often yield products of different structures. In addition, the hydrothermal or solvothermal synthesis tends to give low yields and contains various impurities or by-products.
The invention discloses a cobalt nitrouracil supramolecular compound, which contains free guest molecules of 5-nitrouracil in the structure, wherein the nitrouracil has a receptor and a donor of a hydrogen bond and can form a specific hydrogen bond with certain molecules, so that the compound has potential application in the aspects of molecular recognition, host-guest molecule exchange, sensing and the like. In addition, the compound contains divalent Co2+Ion, divalent Co2+The ion having d7The valence electron structure, which has empty or unfilled electron empty orbitals, can form d-d transition, so that the valence electron structure has rich electrochemical activity, and the valence electron structure has potential application in electrocatalysis or simulated enzyme catalysis.
Disclosure of Invention
The invention aims to solve the technical problem of providing a supermolecule compound which has mild reaction conditions, simple preparation process, low cost and good structural stability and contains divalent cobalt ions, 4' -bipyridine and 5-nitrouracil building units and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: a cobalt nitrouracil supramolecular compound which has a certain spatial structure and has a chemical formula of CoC18H32N8O18The structural unit is [ Co (bpy) ((H))2O)4]·2(C4H2N3O4)·6H2O (bpy ═ 4, 4' -bipyridine), the crystal system is a triclinic crystal system, the space group is P-1, and the unit cell parameters are
α -86.746 degrees, β -79.405 degrees, gamma-74.842 degrees, cobalt ions are in a six-coordination octahedral geometrical configuration, and the nitrouracil is 5-nitrouracil.
The preparation method of the cobalt nitrouracil supramolecular compound comprises the following steps:
(1) weighing a certain amount of cobalt acetate hydrate and 5-nitro potassium orotate monohydrate, placing the cobalt acetate hydrate and the 5-nitro potassium orotate monohydrate into a beaker, adding 8-15 mL of water according to the mass ratio of Co (II) ions to the 5-nitro potassium orotate monohydrate of 1:1, heating and stirring to dissolve the mixture to obtain a reaction mixture solution;
(2) transferring the reaction mixture solution into a stainless steel reaction kettle containing 25mL of polytetrafluoroethylene lining, adding a proper amount of hydrated 4, 4' -bipyridine and 1-2 mL of ethanol, sealing the reaction kettle, placing the reaction kettle in a forced air drying oven, heating to react at 90-100 ℃ for 36-48 hours, cooling to room temperature after the reaction is finished, filtering out precipitates, standing the filtrate for 2-4 days, and slowly volatilizing part of the solvent to obtain red flaky crystals;
(3) taking out the red flaky crystal, and naturally drying to obtain the supramolecular compound;
preferably, the substances participating in the reaction are all chemically pure, the hydrated cobalt acetate is cobalt acetate tetrahydrate, and the hydrated 4,4 '-bipyridine is 4, 4' -bipyridine dihydrate;
preferably, the amount ratio of the substances participating in the reaction is: cobalt ion, 5-nitro potassium orotate monohydrate, hydrated 4, 4' -bipyridine 1: 1.
Compared with the prior art, the invention has the advantages that:
carrying out supermolecule self-assembly reaction on nitroorotic acid with rigid plane conjugation, a 4,4 '-bipyridine ligand and cobalt ions with electrochemical activity, wherein in the reaction, the 4, 4' -bipyridine is used as a bridging ligand to connect adjacent cobalt ions to form a one-dimensional chain structure with positive charges; 5-nitroorotic acid is decarboxylated in the reaction to form 5-nitrouracil, which loses a proton present in the crystal lattice as a monovalent anion. The coordinated water molecules, the object water molecules and the object 5-nitrouracil form a supermolecular network structure through various hydrogen bonds. The characteristics lead the supermolecule compound to have potential application prospect in the aspects of cation and anion recognition, host-guest molecule (ion) exchange, electrochemical sensing and the like.
Drawings
FIG. 1 is a diagram of the structural units of the supramolecular compounds of the present invention (for clarity of illustration, hydrogen atoms, carbon atoms, and symmetrically manipulated atoms are not labeled);
figure 2 is a diagram of the formation of a two-dimensional network within an ac of a supramolecular compound of the invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1:
weighing Co (Ac)2·4H2Placing O (0.25mmol, 0.0623g) and 5-nitro potassium orotate monohydrate (0.25mmol, 0.0643g) in a beaker, adding 8mL of water, heating and stirring to dissolve the O and the 5-nitro potassium orotate monohydrate to obtain a reaction mixture solution; transferring the reaction mixture solution into a stainless steel reaction kettle containing 25mL of polytetrafluoroethylene lining, adding 4, 4' -bipyridine dihydrate (0.25mmol, 0.0481g), adding 1mL of ethanol, sealing the reaction kettle, placing the reaction kettle in an air-blowing drying oven, heating at 90 ℃ for reaction for 48 hours, cooling to room temperature after the reaction is finished, filtering out precipitates, standing the filtrate for 4 days, and slowly volatilizing part of the solvent to obtain red flaky crystals; and taking out the red flaky crystal, and naturally drying to obtain the supramolecular compound.
Example 2:
weighing Co (Ac)2·4H2Placing O (0.5mmol, 0.1245g) and 5-nitro potassium orotate monohydrate (0.5mmol, 0.1286g) in a beaker, adding 10mL of water, heating and stirring to dissolve the O and the 5-nitro potassium orotate monohydrate to obtain a reaction mixture solution; transferring the reaction mixture solution into a stainless steel reaction kettle containing 25mL of polytetrafluoroethylene lining, adding 4, 4' -bipyridine dihydrate (0.5mmol, 0.0961g), adding 2mL of ethanol, sealing the reaction kettle, placing the reaction kettle in an air-blast drying oven, heating at 95 ℃ for reaction for 40 hours, cooling to room temperature after the reaction is finished, filtering out precipitates, standing the filtrate for 3 days, and slowly volatilizing part of the solvent to obtain red flaky crystals; and taking out the red flaky crystal, and naturally drying to obtain the supramolecular compound.
Example 3:
weighing Co (Ac)2·4H2Placing O (0.5mmol, 0.1245g) and 5-nitro potassium orotate monohydrate (0.5mmol, 0.1286g) in a beaker, adding 15mL of water, heating and stirring to dissolve the O and the 5-nitro potassium orotate monohydrate to obtain a reaction mixture solution; transferring the reaction mixture solution into a stainless steel reaction kettle containing 25mL of polytetrafluoroethylene lining, adding 4, 4' -bipyridine dihydrate (0.5mmol, 0.0961g), adding 2mL of ethanol, sealing the reaction kettle, placing the reaction kettle in an air-blast drying oven, heating at 100 ℃ for reaction for 36 hours, cooling to room temperature after the reaction is finished, filtering out precipitates, standing the filtrate for 2 days, and slowly volatilizing part of the solvent to obtain red flaky crystals; and taking out the red flaky crystal, and naturally drying to obtain the supramolecular compound.
The supramolecular compound obtained in example 1-3 was subjected to structural tests, and the results showed that the cobalt nitrouracil supramolecular compound has the structural units shown in fig. 1 (for clarity of illustration, hydrogen atoms, carbon atoms and symmetrically manipulated atoms are not labeled), and the cobalt nitrouracil supramolecular compound forms a two-dimensional network structure in ac as shown in fig. 2. The chemical formula of the supermolecular compound prepared by the invention is CoC18H32N8O18The structural unit is [ Co (bpy) ((H))2O)4]·2(C4H2N3O4)·6H2O (bpy ═ 4, 4' -bipyridine), crystalIs a triclinic system, space group is P-1, and cell parameters are
α -86.746 degrees, β -79.405 degrees, gamma-74.842 degrees and cobalt ions are in a six-coordination octahedral geometrical configuration, in the supermolecule compound, 4, 4' -bipyridine is used as a bridging ligand to connect adjacent cobalt ions to form a one-dimensional chain structure with positive charges, 5-nitroorotic acid is decarboxylated in a reaction to form 5-nitrouracil, 5-nitrouracil loses a proton to exist in a crystal lattice as a monovalent negative ion, and coordinated water molecules, guest water molecules and guest 5-nitrouracil form a supermolecule network structure through various hydrogen bonds.
Claims (2)
1. The supermolecular compound of cobalt nitro uracil has certain spatial structure and its structural unit is [ Co (bpy) (H)2O)4]·2(C4H2N3O4)·6H2O, wherein bpy is 4, 4' -bipyridine and the chemical formula is CoC18H32N8O18The crystal system is triclinic, the space group is P-1, and the cell parameters are
α -86.746 degrees, β -79.405 degrees, gamma-74.842 degrees, cobalt ions are in a six-coordination octahedral geometrical configuration, 4' -bipyridine is used as a bridging ligand to connect adjacent cobalt ions to form a one-dimensional chain structure with positive charges, 5-nitroorotic acid is decarboxylated in the reaction to form 5-nitrouracil, 5-nitrouracil loses a proton and exists in a crystal lattice as a univalent negative ion, and coordinated water molecules, guest water molecules and guest 5-nitrouracil form a supermolecular network structure through multiple hydrogen bonds(ii) a Divalent Co2+The ion having d7The valence electron structure has empty or empty orbitals which are not filled with electrons, and can form d-d transition, and the characteristics enable the supermolecular compound to have specific performance in the aspects of electrocatalysis or simulated enzyme catalysis, cation and anion recognition, ion exchange and electrochemical sensing; the nitrouracil is 5-nitrouracil.
2. A method for the preparation of cobalt nitrouracil supramolecular compounds as claimed in claim 1, comprising the steps of:
(1) weighing a certain amount of cobalt acetate hydrate and 5-nitro potassium orotate monohydrate, placing the cobalt acetate hydrate and the 5-nitro potassium orotate monohydrate into a beaker, adding 8-15 mL of water according to the mass ratio of Co (II) ions to the 5-nitro potassium orotate monohydrate of 1:1, heating and stirring to dissolve the mixture to obtain a reaction mixture solution;
(2) transferring the reaction mixture solution into a stainless steel reaction kettle containing 25mL of polytetrafluoroethylene lining, adding a proper amount of hydrated 4, 4' -bipyridine and 1-2 mL of ethanol, sealing the reaction kettle, placing the reaction kettle in a forced air drying oven, heating to react at 90-100 ℃ for 36-48 hours, cooling to room temperature after the reaction is finished, filtering out precipitates, standing the filtrate for 2-4 days, and slowly volatilizing part of the solvent to obtain red flaky crystals;
(3) taking out the red flaky crystal, and naturally drying to obtain the supramolecular compound;
the substances participating in the reaction are all chemically pure, the hydrated cobalt acetate is cobalt acetate tetrahydrate, and the hydrated 4,4 '-bipyridine is dihydrate 4, 4' -bipyridine; the mass ratio of the substances participating in the reaction is as follows: cobalt ion, 5-nitro potassium orotate monohydrate, hydrated 4, 4' -bipyridine 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710439529.7A CN107266506B (en) | 2017-06-12 | 2017-06-12 | Cobalt nitrouracil supramolecular compound and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710439529.7A CN107266506B (en) | 2017-06-12 | 2017-06-12 | Cobalt nitrouracil supramolecular compound and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107266506A CN107266506A (en) | 2017-10-20 |
| CN107266506B true CN107266506B (en) | 2020-05-15 |
Family
ID=60067081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710439529.7A Active CN107266506B (en) | 2017-06-12 | 2017-06-12 | Cobalt nitrouracil supramolecular compound and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107266506B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108676020A (en) * | 2018-05-08 | 2018-10-19 | 宁波大学 | A kind of nitrouracil copper super molecular compound and preparation method thereof |
| CN110818746A (en) * | 2019-11-27 | 2020-02-21 | 宁波大学 | 5-nitro orotic acid cobalt complex and preparation method and application thereof |
| CN115403781B (en) * | 2022-10-06 | 2024-03-19 | 北京师范大学 | Room temperature phosphorescence metal halide crystalline material with reverse excitation wavelength dependence and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396458A (en) * | 2013-08-12 | 2013-11-20 | 宁波大学 | Compound with electrochemical response to formaldehyde and preparation method thereof |
| CN103435659A (en) * | 2013-08-12 | 2013-12-11 | 宁波大学 | Cobalt complex with electrochemical catalytic activity |
| CN103467367A (en) * | 2013-09-13 | 2013-12-25 | 宁波大学 | Cobalt complex having electrocatalytic activity on hydrogen peroxide |
-
2017
- 2017-06-12 CN CN201710439529.7A patent/CN107266506B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103396458A (en) * | 2013-08-12 | 2013-11-20 | 宁波大学 | Compound with electrochemical response to formaldehyde and preparation method thereof |
| CN103435659A (en) * | 2013-08-12 | 2013-12-11 | 宁波大学 | Cobalt complex with electrochemical catalytic activity |
| CN103467367A (en) * | 2013-09-13 | 2013-12-25 | 宁波大学 | Cobalt complex having electrocatalytic activity on hydrogen peroxide |
Non-Patent Citations (2)
| Title |
|---|
| "巴比妥酸及其衍生物超分子组装与性能研究";闫营;《中国优秀硕士学位论文全文数据库·工程科技I辑》;20150315;全文 * |
| "氮杂环类金属超分子组装与性能研究";邴月;《中国优秀硕士学位论文全文数据库·工程科技I辑》;20130315;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107266506A (en) | 2017-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107266506B (en) | Cobalt nitrouracil supramolecular compound and preparation method thereof | |
| Cui et al. | Hydrothermal synthesis, crystal structures and luminescent properties of two new Ln (III)–succinate (Ln= Eu, Tb) complexes exhibiting three dimensional networks | |
| CN102491987B (en) | 1,10-phenanthroline hydrate functionalized N-heterocyclic carbene and tetranuclear copper compound and preparation method for same | |
| Cheng et al. | Substituted groups-directed assembly of Cd (II) coordination polymers based on 5-R-1, 3-benzenedicarboxylate and 4, 4'-bis (1-imidazolyl) bibenzene: syntheses, structures and photoluminescent properties | |
| CN111875642A (en) | Poly-terpyridyl metal organic ligand compound, five-membered flower ring-shaped supramolecule assembled by same and preparation method of five-membered flower ring-shaped supramolecule | |
| Wang et al. | Rational Synthesis and Characterization of Two Three‐Dimensional Metal‐Organic Frameworks Incorporating Silver Chains and 1, 2, 3, 4, 5, 6‐Cyclohexanehexacarboxylate | |
| Çolak et al. | Synthesis, structural characterisation of zinc (II)-pyridine-2, 5-dicarboxylate complexes and self-assembled 1D water cluster in a supramolecular architecture | |
| Zhu et al. | Syntheses, structures, molecular and cationic recognitions and catalytic properties of two lanthanide coordination polymers based on a flexible tricarboxylate | |
| Rana et al. | 1D coordination polymers formed by tetranuclear lead (II) building blocks with carboxylate ligands: In situ isomerization of itaconic acid | |
| Adhikary et al. | Heterogenization of three homogeneous catalysts: a comparative study as epoxidation catalyst | |
| Nie et al. | Synthesis and structure of a polymeric 1, 3-benzenedicarboxylato complex of Mn (II) with phenanthroline | |
| Zhang et al. | Vanadium (V) complexes with bromo-substituted hydrazones: Synthesis, characterization, X-ray crystal structures and antimicrobial activity | |
| CN107417928A (en) | A kind of metallic silver coordination polymer containing mixed ligand and preparation method thereof | |
| Zhang et al. | Three silver complexes constructed from organic carboxylic acid and 1, 2-bis (4-pyridyl) ethane ligands: syntheses, crystal structures, and luminescent properties | |
| Bao et al. | Hydrothermal synthesis and crystal structure of four lead (II) coordination polymers with a carboxylate functionalized imidazophenanthroline derivative ligand | |
| Gu et al. | Self-assembly of γ-octamolybdate-based frameworks decorated by 1, 3-bis (4-pyridyl) propane through covalent bond | |
| Han et al. | The first polyoxometalate polymer constructed by assembly of the heptamolybdic anion and copper coordination groups | |
| CN106995467B (en) | A kind of method of microwave catalysis synthesis bicycloplatin | |
| Sun et al. | Solvothermal syntheses, crystal structures, and optical and thermal properties of transition metal selenidostannates | |
| Cheng et al. | Syntheses, structures, and characterizations of two new lead (II) supramolecular complexes containing 4-aminobenzenesulfonate ligand | |
| Suenaga et al. | Three-dimensional silver (I) co-ordination polymer with pocket structures | |
| CN109956981A (en) | A kind of isopolyacid precursor assembling manganese and copper are heteroatomic polyacid material | |
| Knight et al. | A new coordination mode for tris (2-carboxyethyl) phosphine: Synthesis, crystal structure and characterization of the mixed-valence Co (III)/Co (II)/Co (III) complex [Co {P (CH2CH2COO) 2 (CH2CH2COOH)} 2] 2 [Co (H2O) 4][Na2 (H2O) 4] Cl2· 6H2O | |
| Wei et al. | Post-coordination functionalisation of pyrazolyl-based ligands as a route to polynuclear complexes based on an inert Ru II N 6 core | |
| Cho et al. | Synthesis and crystal structure of nickel (II) complexes with bis (5-methyl-2-thiophenemethyl)(2-pyridylmethyl) amine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |