CN110903326A - Discrete coordination molecule container, preparation method thereof and small molecule catalysis application - Google Patents
Discrete coordination molecule container, preparation method thereof and small molecule catalysis application Download PDFInfo
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- 238000006555 catalytic reaction Methods 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 150000003384 small molecules Chemical class 0.000 title description 3
- 239000003446 ligand Substances 0.000 claims abstract description 43
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- DGGZHROWZDIUAL-UHFFFAOYSA-N 1-[(4-carboxyphenyl)methyl]-2H-pyridine-4-carboxylic acid Chemical compound C(=O)(O)C1=CC=C(CN2CC=C(C(=O)O)C=C2)C=C1 DGGZHROWZDIUAL-UHFFFAOYSA-N 0.000 claims description 8
- YJLYANLCNIKXMG-UHFFFAOYSA-N N-Methyldioctylamine Chemical compound CCCCCCCCN(C)CCCCCCCC YJLYANLCNIKXMG-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- -1 hydrogen Chemical class 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 6
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 125000002950 monocyclic group Chemical group 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- AUNMUQMAYWGHIU-UHFFFAOYSA-N C(=O)(O)C1=CC=C(CC=2C=C(C(=C(C(=O)O)C2)N)C(=O)O)C=C1 Chemical compound C(=O)(O)C1=CC=C(CC=2C=C(C(=C(C(=O)O)C2)N)C(=O)O)C=C1 AUNMUQMAYWGHIU-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- GQPLZGRPYWLBPW-UHFFFAOYSA-N calix[4]arene Chemical compound C1C(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC2=CC=CC1=C2 GQPLZGRPYWLBPW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 3
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000009977 dual effect Effects 0.000 abstract description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 abstract description 3
- 238000006053 organic reaction Methods 0.000 abstract description 2
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 abstract 2
- 241000534944 Thia Species 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000007172 homogeneous catalysis Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical class C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/22—Magnesium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
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- C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
- C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
- C07C2603/50—Pyrenes; Hydrogenated pyrenes
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Abstract
The invention relates to a discrete coordination molecule container, a preparation method and application thereof, wherein the structure of the discrete coordination molecule container is as follows: [ M ] A4(μ4‑B)(X)]6Y6Z2. Wherein M is a metal element; b is H2O (water); x is thia cup [4]]An aromatic hydrocarbon ligand; y is an asymmetric tricarboxylic acid ligand; z is a symmetrical tricarboxylic acid ligand. The discrete coordination molecule container provided by the invention has a functionally modified inner cavity, the specific nano inner cavity structure realizes the enrichment of organic reaction substrates and enhances the contact with catalytic active sites, and meanwhile, the mu is4‑H2Of O
Of acidic active centres and imino groups
The alkaline active center forms an acid-base dual catalytic active center. The discrete coordination molecule container provided by the invention is used for homogeneous catalysis Knoevenagel condensation reaction, and has high catalytic activity.
Description
Technical Field
The invention belongs to the field of discrete coordination molecule container materials, and relates to a discrete coordination molecule container and a preparation method and application thereof. The coordination molecule container of the invention can be used in catalytic reactions.
Background
The molecular container has a cavity structure with a specific configuration, can selectively bind or contain guest molecules with specific size, configuration and functional groups, and provides a special chemical microenvironment for the contained guest molecules by utilizing the host-guest inclusion effect, so that the applications of the molecular container in the aspects of packaging unstable compounds, separating, storing and transmitting small molecular compounds, serving as a reaction container to realize small molecular catalysis, template synthesis of monodisperse nanoparticles and the like are realized, and the molecular container is always concerned by scientific researchers.
The controllable synthesis and application exploration of a highly controllable discrete coordination molecular container are realized by utilizing the rigid coordination bonding effect between metal and ligand, and the container is taken as an important research hotspot and is widely concerned by many researchers at home and abroad. The discrete coordination molecule container generally has the excellent characteristics of controllable and unique nano cavity, templatable synthesis, easy regulation of molecular structure and cavity size and the like. However, current research is more focused on the structural design of discrete coordination molecule vessels of simpler structural composition (e.g., binary components), and is less practical to implement as reaction vessels for organic catalysis. Therefore, the structural design of the multi-component structural component is utilized to develop and research the structural regulation and functionalization strategies of the coordination molecule container, and the application of the coordination molecule container in the fields of sensing, energy and the like is further realized, so that the method has very important significance.
Disclosure of Invention
The invention aims to provide a discrete coordination molecule container with a quaternary structure component, a preparation method thereof and small molecule catalysis application.
The object of the invention is achieved by:
in a first aspect, the present invention provides a discrete coordination molecule container having the general structural formula:
[M4(μ4-B)(X)]6Y6Z2；
wherein the content of the first and second substances,
m is a metal element selected from magnesium, zinc, manganese, cobalt, nickel, copper, iron and ruthenium;
b is H2O (water); mu.s4Represents that 4M forms a bridging coordination with the 4-coordinated O atom.
X is a thiacalix [4] arene ligand, and the molecular structure of the ligand is as follows:
R1hydrogen, alkyl, aryl; a is S, SO2；
Y is an asymmetric tricarboxylic acid ligand, and the molecular structure of the asymmetric tricarboxylic acid ligand is as follows:
R2、R3independently selected from nitrogen or carbon;
z is a symmetrical tricarboxylic acid ligand, and the molecular structure of the ligand is as follows:
according to the present invention, the single crystal structure of the discrete coordination molecule container is shown in FIG. 1:
in the present invention, the alkyl group means a straight chain or branched alkyl group having 1 to 10 carbon atoms, preferably a branched alkyl group having 4 to 8 carbon atoms, for example, a tert-butyl group, a tert-pentyl group, a tert-octyl group and the like.
The aryl group means a monocyclic, polycyclic aromatic group having 6 to 20 carbon atoms, and representative aryl groups include: phenyl, naphthyl, and the like.
According to the invention, R is1Preferably tert-butyl, tert-octyl, phenyl; a is preferably SO2。
According to the invention, X is preferably a 5,11,17, 23-tetra-tert-butyl-sulfonyl bridged calix [4] arene ligand and Y is preferably a 5- (4-carboxybenzyl) amino isophthalic acid ligand.
Specifically, the complex of the invention can be:
[Co4(μ4-H2O)(TBSC)]6(TC1)6(TC2)2、[Zn4(μ4-H2O)(TBSC)]6(TC1)6(TC2)2、[Mg4(μ4-H2O)(TBSC)]6(TC1)6(TC2)2wherein TBSC represents 5,11,17, 23-tetra-tert-butyl-sulfonyl bridged cup [4]]Arene ligands, TC1 for 1- (4-carboxybenzyl) isonicotinic acid ligand, TC2 for 1,3, 5-cyclohexanetricarboxylic acid ligand.
In a second aspect, the present invention provides a method of making the discrete coordination molecule container, comprising the steps of: h is to be4X、H3Y、H3The self-assembly reaction of the Z and M metal salts in an organic solvent results in a container of discrete coordination molecules, wherein X, Y, Z, M is as described above.
According to the invention, the metal salt of M is preferably a nitrate or a halide.
According to the present invention, the organic solvent is preferably an amide solvent or a mixed solvent of an amide and an alcohol, such as N, N '-Dimethylformamide (DMF), a mixed solvent of N, N' -dimethylformamide and methanol; a mixed solvent of N, N '-dimethylformamide and methanol is preferable, and a mixed solvent of N, N' -dimethylformamide and methanol at a volume ratio of 5:3 is further preferable.
According to the invention, in the method, the molar ratio of X, Y, Z and M is 0.9-1.1: 1.2-2.5: 0.2-1.0: 4.0-7.0, and the preferred molar ratio is 1:1.5:0.33: 5.
According to the invention, the reaction is carried out at a temperature of 25 to 140 ℃. Preferably, the crystallization product of the discrete coordination molecule container is obtained at the reaction temperature of 100-110 ℃.
In a third aspect, the invention provides the use of the discrete coordination molecule container as a molecular reaction container for catalysis of Knoevenagel condensation reactions in homogeneous phase, by the following method: the discrete coordination molecule container is used as a catalyst and is mixed with an aldehyde substrate and malononitrile, the molar ratio of the aldehyde substrate to the malononitrile is 1:1, the dosage of the discrete coordination molecule container catalyst is 2 mol%, the reaction temperature is 20-40 ℃, the solvent is chloroform, and the reaction time is 48 hours.
Preferably, the aldehyde substrate is an aryl aldehyde, which refers to a monocyclic, polycyclic aromatic group having 6 to 20 carbon atoms, representative aryl groups including: phenyl, naphthyl, anthracenyl, pyrenyl, and the like.
Preferably, the aldehyde substrate is selected from: benzaldehyde, 2-aldehyde naphthalene, 2-aldehyde anthracene and 1-aldehyde pyrene.
Compared with the prior art, the invention has the following advantages:
1) the preparation method of the discrete coordination molecule container can be carried out at normal temperature or lower temperature (such as 100 ℃), is simple, quick, energy-saving and efficient, has wide sources of raw materials and reagents and low price, and is beneficial to large-scale application;
2) the invention is realized by
Acidic mu4-H2O center and
the alkaline imino group is combined and constructed in the inner cavity of the coordination molecule container, so that a double acid-base catalysis mechanism is realized; the method realizes the local concentration enrichment of the reaction substrate and the high-efficiency catalytic reaction activity by utilizing the cavity confinement effect, and has great application prospect.
Drawings
FIG. 1 is a schematic representation of the crystal structure of the discrete coordination molecule container made in example 1.
FIG. 2 is a schematic representation of the reaction of the synthesized discrete coordination molecule container of the present invention for catalyzing Knoevenagel condensation.
Detailed Description
In order to make the objects, technical solutions and technical effects of the present invention more clear, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the embodiments described in this specification are only for the purpose of illustrating the present invention and are not to be construed as limiting the present invention. The appended claims outline the scope of the invention, but some changes to the embodiments of the invention, guided by the idea of the invention, are intended to be covered by the spirit and scope of the claims.
Example 1
Preparation of discrete coordination molecule Container [ Co4(μ4-H2O)(TBSC)]6(TC1)6(TC2)2(wherein TBSC represents 5,11,17, 23-tetra-tert-butyl-sulfonyl bridged cup [4]]Arene ligands, TC1 for 1- (4-carboxybenzyl) isonicotinic acid ligand, TC2 for 1,3, 5-cyclohexanetricarboxylic acid ligand.
CoCl2·6H2O(59.50mg,0.25mmol),H3TC1(23.00mg,0.073mmol)，H3TC2(3.60mg,0.0167mmol) and H4TBSC (42.15mg,0.05mmol) was dissolved in a mixed solvent of 5mL of N, N' -Dimethylformamide (DMF) and 3mL of methanol, heated to 100 ℃ at a heating rate of 0.5 ℃/min, and the temperature was maintained at 100 ℃ for 24 hours, and then slowly cooled to obtain pink crystals. Yield: 62.5 percent.
The product is characterized by X-ray single crystal diffraction and the like, and the specific results are as follows:
TABLE 1 Co4(μ4-H2O)(TBSC)]6(TC1)6(TC2)2Crystallographic parameters of
The above data indicate that the target product [ Co ] is obtained in this example4(μ4-H2O)(TBSC)]6(TC1)6(TC2)2(wherein TBSC represents 5,11,17, 23-tetra-tert-butyl-sulfonyl bridged cup [4]]Arene ligands, TC1 for 1- (4-carboxybenzyl) isonicotinic acid ligand, TC2 for 1,3, 5-cyclohexanetricarboxylic acid ligand).
FIG. 1 is a schematic diagram of the crystal structure of the discrete coordination molecule container prepared in preparation example 1. As can be seen from FIG. 1, a discrete coordination molecule container molecule is formed by six 1- (4-carboxybenzyl) isonicotinic acid ligands and two 1,3, 5-cyclohexanetricarboxylic acid ligands bridging six tetranuclear metal cups [4]]The supermolecule polyhedral structure with an inverse triangular prism configuration is obtained by the aromatic hydrocarbon structural unit. Wherein, six four-core metal cups [4]]The aromatic hydrocarbon structural unit is positioned at the vertex of the polyhedron, six 1- (4-carboxyl benzyl) isonicotinic acid ligands occupy six triangular side surfaces of the anti-triangular prism, and two 1,3, 5-cyclohexanetricarboxylic acid ligands are positioned at two bottom surfaces of the anti-triangular prism. The discrete coordination molecule container molecule comprises an inner cavity consisting of a triacid bridging ligand and tetranuclear metal calixarene, can be used for effectively combining and containing a guest molecule, and utilizes the mu of the guest molecule4-H2Of O
Acidic active center and imino group
The alkaline active center realizes dual catalytic activity of acid and alkali.
Example 2
Preparation of discrete coordination molecule Container [ Mg4(μ4-H2O)(TBSC)]6(TC1)6(TC2)2(wherein TBSC represents 5,11,17, 23-tetra-tert-butyl-sulfonyl bridged cup [4]]Arene ligands, TC1 for 1- (4-carboxybenzyl) isonicotinic acid ligand, TC2 for 1,3, 5-cyclohexanetricarboxylic acid ligand.
MgCl2·6H2O(50.75mg,0.25mmol),H3TC1(23.00mg,0.073mmol)，H3TC2(3.60mg,0.0167mmol) and H4TBSC (42.15mg,0.05mmol) was dissolved in a mixed solvent of 5mL of N, N' -Dimethylformamide (DMF) and 1mL of methanol, and heated at a heating rate of 0.5 ℃/min toThe temperature is kept at 100 ℃ for 24h, and the reaction is slowly cooled to obtain colorless crystals. Yield: 50.9 percent.
The product is characterized by X-ray single crystal diffraction and the like, and the specific results are as follows:
TABLE 2 Mg4(μ4-H2O)(TBSC)]6(TC1)6(TC2)2Crystallographic parameters of
The above data indicate that the target product [ Mg ] is obtained in this example4(μ4-H2O)(TBSC)]6(TC1)6(TC2)2(wherein TBSC represents 5,11,17, 23-tetra-tert-butyl-sulfonyl bridged cup [4]]Arene ligands, TC1 for 1- (4-carboxybenzyl) isonicotinic acid ligand, TC2 for 1,3, 5-cyclohexanetricarboxylic acid ligand).
Example 3
The use of the discrete coordination molecule container prepared in example 1 as a catalyst in homogeneously catalyzed Knoevenagel condensation reactions was examined. 0.1mmol of the aldehyde substrate, 0.1mmol of malononitrile and 2 mol% of the catalyst were weighed out and dissolved in 1mL of chloroform, and the reaction was stirred at room temperature for 48 hours. The separation was carried out by flash column chromatography on silica gel using petroleum ether/ethyl acetate (volume ratio: 5:1) as eluent. And (4) carrying out rotary evaporation to obtain a corresponding condensation product, analyzing by using a nuclear magnetic resonance spectrum, and quantitatively calculating the reaction yield by adopting an internal standard method. The catalytic results were as follows:
the above data indicate that the discrete coordination molecule container prepared by the present invention realizes enrichment of organic reaction substrates and enhances contact with catalytic active sites by using the inner cavity structure, and realizes efficient catalytic activity by using the acid-base dual catalytic active centers.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (5)
1. A discrete coordination molecule container having the general structural formula:
[M4(μ4-B)(X)]6Y6Z2；
wherein the content of the first and second substances,
m is a metal element selected from magnesium, zinc, manganese, cobalt, nickel, copper, iron and ruthenium;
b is H2O (water);
μ4represents that 4M forms a bridging coordination with the 4-coordinated O atom;
x is a thiacalix [4] arene ligand, and the molecular structure of the ligand is as follows:
R1hydrogen, alkyl, aryl; a is S, SO2；
Y is an asymmetric tricarboxylic acid ligand, and the molecular structure of the asymmetric tricarboxylic acid ligand is as follows:
R2、R3independently selected from nitrogen or carbon;
z is a symmetrical tricarboxylic acid ligand, and the molecular structure of the ligand is as follows:
the alkyl group means a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, preferably a branched-chain alkyl group having 4 to 8 carbon atoms, and the aryl group means a monocyclic or polycyclic aromatic group having 6 to 20 carbon atoms.
2. The discrete coordination molecule container of claim 1 or 2, the R1Preferably tert-butyl, tert-octyl, phenyl; a is preferably SO2(ii) a B is preferably OH;
the X is preferably a 5,11,17, 23-tetra-tert-butyl-sulfonyl bridged calix [4] arene ligand, and the Y is preferably a 5- (4-carboxybenzyl) amino isophthalic acid ligand;
specifically, the complex of the invention can be:
[Co4(μ4-H2O)(TBSC)]6(TC1)6(TC2)2、[Zn4(μ4-H2O)(TBSC)]6(TC1)6(TC2)2、[Mg4(μ4-H2O)(TBSC)]6(TC1)6(TC2)2wherein TBSC represents 5,11,17, 23-tetra-tert-butyl-sulfonyl bridged cup [4]]Arene ligands, TC1 for 1- (4-carboxybenzyl) isonicotinic acid ligand, TC2 for 1,3, 5-cyclohexanetricarboxylic acid ligand.
3. A method of making the discrete coordination molecule container of any of claims 1-2, comprising the steps of:
h is to be4X、H3Y、H3(ii) self-assembly of the Z and M metal salts in an organic solvent to give discrete coordination molecule containers, wherein X, Y, Z, M is as defined in any one of claims 1 to 3;
the solvent is preferably a mixed solvent of N, N' -dimethylformamide and methanol; preferably, the molar ratio of X to Y to Z to M is 1:1.5:0.33: 5;
the reaction temperature is 25-140 ℃; preferably, the reaction is carried out at a reaction temperature of 100-110 ℃.
4. The method for catalyzing Knoevenagel condensation reaction in homogeneous phase by using the discrete coordination molecule container as claimed in any one of claims 1 to 2, which is characterized in that the discrete coordination molecule container as claimed in any one of claims 1 to 3 is used as a catalyst and is mixed with an aldehyde substrate and malononitrile, the molar ratio of the aldehyde substrate to the malononitrile is 1:1, the amount of the catalyst used in the discrete coordination molecule container is 2 mol%, the reaction temperature is 20-40 ℃, the solvent is chloroform, and the reaction time is 48 hours.
5. The method of using a discrete coordination molecule container of claim 4 for heterogeneous phase catalysis of Knoevenagel condensation reactions, wherein the aldehyde substrate is an aryl aldehyde.
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