Heteronuclear supramolecular coordination assembly as well as preparation method and application thereof

Abstract

The invention discloses a heteronuclear supramolecular coordination assembly and a preparation method and application thereof, and belongs to the technical field of synthesis of supramolecular metal organic complexes. Compared with an existing supramolecular coordination structure, the heteronuclear supramolecular coordination assembly has the advantages that the solvent condition is improved, and the heteronuclear supramolecular coordination assembly can be synthesized in a water solution under mild reaction conditions; the use of toxic and high-boiling-point organic solvents is avoided, the reaction post-treatment is convenient, and the green chemical development strategy is met. A flexible heteronuclear supramolecular coordination assembly with adaptive deformation characteristics is prepared by using a multi-coordination-site flexible ligand, and the application range of a rigid cavity structure is expanded. The heteronuclear supramolecular coordination assembly contains a metal active center, can be directly used as a nano-catalyst, and overcomes the defect that metal ions in most coordination structures lose activity due to coordination saturation. The structure can chelate active centers with different properties on the premise of keeping a skeleton stable and unchanged, and is beneficial to research on a mimic enzyme catalysis universality rule.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of synthesis of supramolecular metal-organic complexes, and particularly relates to a kind of heteronuclear supramolecular coordination assembly and a preparation method and application thereof. BACKGROUND

[0002] Supramolecular chemistry is a discipline that studies a complex but orderly and specific functional system formed by two or more chemical substances through intermolecular weak interaction forces. Chemists have made a series of research progress in the field of supramolecular metal-organic assembly. Not only have they synthesized coordination assemblies with beautiful structure, adjustable size and good stimulus responsiveness, but also have they studied selective recognition, wrapping and separation of specific substrates, stabilization of metastable species and acceleration of specific chemical reactions by using the cavities of the coordination assemblies. However, there are still aspects that can promote the research in this field. For example, compared with enzymes in organisms, the structures of the reported coordination assemblies are relatively simple, and most of them tend to be rigid structures; the metal ions are mostly saturated coordination, and the universality of catalytic application is poor. Therefore, there is still a great challenge to synthesize coordination assemblies with good stimulus responsiveness like enzymes and achieve unusual applications. SUMMARY

[0003] In order to solve the problems of rigidity of supramolecular coordination structure and deactivation of coordination metal ions, the application provides a kind of heteronuclear supramolecular coordination assembly and a preparation method and application thereof. It is an important metal-organic supramolecular coordination structure, which has a deformable skeleton and unsaturated coordination metal ions (active centers), and has important significance in enzyme-mimetic catalytic applications, and the synthesis method is simple and efficient, uses water as a solvent, and meets the concept of green chemistry.

[0004] In order to achieve the above application purposes, the application adopts the following technical solutions:

[0005] In a first aspect, the application provides a kind of heteronuclear supramolecular coordination assembly, which comprises a coordination cage and a coordination tube, the spatial structure of the coordination cage is shown as (I), and the spatial structure of the coordination tube is shown as (II):

[0006]

[0007] (I) (II)

[0008] Wherein, R is selected from ethylenediamine, N,N,N,N-tetramethylethylenediamine, bipyridine or cyclohexanediamine; M1 is Ag + ; M2 is Co 2 + , Ni 2+ , Cu 2+ or Zn2+ ; M3 is Pd 2+ .

[0009] In a second aspect, the present application provides a preparation method of the above-mentioned heteronuclear supramolecular coordination assembly, and the preparation method of the coordination cage comprises the following steps: dissolving the ligand L, the cis-terminated M3 metal node and the M1 metal salt in a solvent, and preparing the coordination cage through a coordination-directed self-assembly reaction.

[0010] The preparation method of the coordination tube comprises the following steps: dissolving the ligand L, the cis-terminated M3 metal node and the M2 metal salt in a solvent, and preparing the coordination tube through a coordination-directed self-assembly reaction.

[0011] Further, the chemical structural formula of the ligand L is as follows: .

[0012] Further, the cis-terminated M3 metal node is a cis-Pd 2+ complex with ethylenediamine, N,N,N,N-tetramethylethylenediamine, bipyridine or cyclohexanediamine as the terminal ligand; the M1 metal salt is a silver salt; and the M2 metal salt is selected from a cobalt salt, a nickel salt, a copper salt or a zinc salt.

[0013] The flexible ligand L chelates Ag + , and the cis-terminated Pd 2+ metal node is externally connected, so that the flexible heteronuclear coordination cage structure can be conveniently synthesized through one-pot reaction. + The flexible ligand L chelates transition metal ions Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , etc. 2+ , and the cis-terminated Pd - metal node is externally connected, so that the flexible heteronuclear coordination tube structure can be quickly prepared through one-pot reaction.

[0014] The outer coordination group of the heteronuclear supramolecular coordination assembly provided by the present application is diversified, and can be ethylenediamine, N,N,N,N-tetramethylethylenediamine, cyclohexanediamine, bipyridine, etc.

[0015] Further, the anions in the M3 metal node, the M1 metal salt and the M2 metal salt are independently selected from NO3 - , BF4 - , SO4 2- or SbF6 - , the anion is a single anion when the coordination cage is prepared, and the anion is a single anion or a mixed anion when the coordination tube is prepared.

[0016] Further, when preparing the coordination cage, the molar ratio of ligand L, M3 metal node and M1 metal ion is 1:2:1; the dosage ratio of ligand L and solvent is 0.022 mmol:3 mL; when preparing the coordination tube, the molar ratio of ligand L, M3 metal node and M2 metal ion is 1:2:1; the dosage ratio of ligand L and solvent is 0.054 mmol:5 mL.

[0017] Further, the solvent is selected from water, an organic solvent or a mixed solution of the organic solvent and water, wherein the organic solvent is selected from dimethyl sulfoxide, CH3CN, CH3OH or CH3COCH3.

[0018] The reaction solvent used in the present application can be a pure water solution or a mixed solution of common organic reagents such as dimethyl sulfoxide (DMSO), acetonitrile, methanol, acetone and water, so as to realize green reaction process.

[0019] Further, when preparing the coordination cage and the coordination tube, the temperature of the coordination directed self-assembly reaction is 70℃.

[0020] By using the above technical solution, ligand L, cis-terminated Pd 2+ Metal node and various transition metal ions are added to water or other solvents for coordination directed self-assembly, and the clear solution after reaction is the expected product. The assembly contains a flexible cavity skeleton and a coordination unsaturated metal active site, can selectively wrap the corresponding matching substrate molecules, and utilizes the metal active site to perform corresponding catalytic reactions, which has important application value in matrix screening and enzyme-like catalysis. The present application is simple and easy to operate, and the raw materials are simple and easy to synthesize. The synthesis and performance research can be carried out in water, which conforms to the concept of green chemistry. At the same time, the structure has good acid-base stability and wide applicability, and has good compatibility with various transition metal ions.

[0021] In a third aspect, the present application provides the use of the above-mentioned heteronuclear supramolecular coordination assembly in enzyme-like catalysis or molecular recognition.

[0022] Biological enzyme structure analysis shows that the complex structure and excellent performance of biological enzymes are mainly derived from the flexible characteristics of their peptide chains and coordination unsaturated metal ions. The ligand L selected in the present application has a dual functional coordination site, which contains a nitrogen-containing macrocycle capable of chelating transition metals and a pyridine group capable of forming a strong coordination bond with a palladium node, and has good flexibility. The synthesis of heteronuclear supramolecular coordination assembly in solution by using coordination directed self-assembly strategy not only can enrich and expand the research field of supramolecular chemistry, but also provides a good strategy for the synthesis of artificial enzymes with comparable enzyme activity. It has important research significance and value for the synthesis and application exploration of flexible enzyme-like coordination assembly with multiple synergistic effects in the supramolecular level.

[0023] Compared with the prior art, the present application has the following advantages and technical effects:

[0024] Compared with the prior art, the present application has the following advantages and technical effects: BRIEF DESCRIPTION OF DRAWINGS

[0025] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments will be briefly introduced as follows. Obviously, the drawings in the following description only constitute some embodiments of the present application, and for those skilled in the art, other drawings can also be obtained from these drawings without creative labor.

[0026] Figure 1 A schematic diagram of the heteronuclear supramolecular coordination assembly of the present application;

[0027] Figure 2 A synthesis route diagram of the coordination cage Cage-Pd-Ag(BF4);

[0028] Figure 3 A hydrogen nuclear magnetic resonance spectrum diagram of the coordination cage Cage-Pd-Ag(BF4);

[0029] Figure 4 A carbon nuclear magnetic resonance spectrum diagram of the coordination cage Cage-Pd-Ag(BF4);

[0030] Figure 5 A hydrogen nuclear magnetic resonance spectrum diagram of the coordination cage Cage-Pd-Ag(SO4);

[0031] Figure 6 A carbon nuclear magnetic resonance spectrum diagram of the coordination cage Cage-Pd-Ag(SO4);

[0032] Figure 7 A stereoscopic structure diagram of the coordination cage Cage-Pd-Ag(SO4) prepared in Example 2;

[0033] Figure 8 A synthesis route diagram of the coordination tube Tube-Pd-Zn(NO3);

[0034] Figure 9 NMR hydrogen spectrum of coordination tube Tube-Pd-Zn(NO3)BF4;

[0035] Figure 10 NMR carbon spectrum of coordination tube Tube-Pd-Zn(NO3)BF4;

[0036] Figure 11 NMR hydrogen spectrum of coordination tube Tube-Pd-Zn(NO3)SO4;

[0037] Figure 12 NMR carbon spectrum of coordination tube Tube-Pd-Zn(NO3)SO4;

[0038] Figure 13 NMR hydrogen spectrum of coordination tube Tube-Pd-Zn(NO3)SbF6;

[0039] Figure 14 NMR carbon spectrum of coordination tube Tube-Pd-Zn(NO3)SbF6;

[0040] Figure 15 NMR hydrogen spectrum of coordination tube Tube-Pd-Co(NO3)SbF6;

[0041] Figure 16 NMR carbon spectrum of coordination tube Tube-Pd-Co(NO3)SbF6;

[0042] Figure 17 NMR hydrogen spectrum of coordination tube Tube-Pd-Ni(NO3)SbF6;

[0043] Figure 18 NMR carbon spectrum of coordination tube Tube-Pd-Ni(NO3)SbF6;

[0044] Figure 19 NMR hydrogen spectrum of coordination tube Tube-Pd-Cu(NO3)SbF6;

[0045] Figure 20 NMR carbon spectrum of coordination tube Tube-Pd-Cu(NO3)SbF6;

[0046] Figure 21 NMR hydrogen spectrum of coordination tube Tube-Pd-Cu(NO3)SbF6;

[0047] Figure 22 NMR carbon spectrum of coordination tube Tube-Pd-Cu(NO3)SbF6;

[0048] Figure 23 Single crystal structure of coordination tube Tube-Pd-Zn(NO3)-

[0049] Figure 24 Single crystal structure of coordination cage Cage-Pd-Ag(BF4)-

[0050] Figure 25 Single crystal structure of coordination cage Cage-Pd-Ag(SO4)-

[0051] Figure 26 Stereoscopic structure of coordination body prepared in Examples 4-9;

[0052] Figure 27 pH stability range of coordination tube Tube-Pd-Zn(NO3) prepared in Example 3;

[0053] Figure 28 Host-guest simulation structure of coordination tube Tube-Pd-Zn(NO3) and CO3 2- ;

[0054] Figure 29 A) Schematic diagram of coordination tube Tube-Pd-Zn(NO3) promoting CO2 to CO3 2- ; B) Nuclear magnetic carbon spectrum, where a is the nuclear magnetic carbon spectrum of CO2, b is the nuclear magnetic carbon spectrum of the blank test, c is the nuclear magnetic carbon spectrum of coordination tube Tube-Pd-Zn(NO3), d is the nuclear magnetic carbon spectrum of the catalytic reaction, e is the nuclear magnetic carbon spectrum of CO3 2- precipitated, and f is the nuclear magnetic carbon spectrum of the cyclic catalytic experiment; C) Infrared spectrum of coordination tube Tube-Pd-Zn(NO3), CO3 2- @ Tube-Pd-Zn(NO3) and Na2CO3; D) Host-guest single crystal structure of coordination tube Tube-Pd-Zn(NO3) encapsulating CO3 2- .

[0055] Figure 30 Nuclear magnetic carbon spectrum of coordination tube Tube-Pd-Co(NO3 SbF6) and Tube-Pd-Ni(NO3 SbF6) catalyzing CO2 to CO3 2- , where A) is the catalytic reaction carbon spectrum of Tube-Pd-Co(NO3 SbF6), and B) is the catalytic reaction carbon spectrum of Tube-Pd-Ni(NO3 SbF6). DETAILED DESCRIPTION

[0056] The detailed description set forth below of various example embodiments of the application describes and discloses only the specific methods and materials in accordance with the embodiments of the application as described in this application. There is no intention that the application be limited to the methods and materials described or illustrated herein, except as set forth in the claims. However, as this application is only illustrative of the application, the scope of the application is indicated by the appended claims rather than by the foregoing description, and all changes that come within the meaning and range of equivalency of the claims are intended to be embraced therein.

[0057] It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. Additionally, the use of "including", "comprising", "having" and "with" are not intended to be limiting of the application. It is intended that the specification and examples be considered as exemplary only, with the true scope of the application being indicated by the appended claims.

[0058] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice of the present application, the preferred methods and materials are described herein. All patents, patent applications, publications, and descriptions mentioned herein are incorporated by reference in their entirety for the disclosure and

[0059] Many modifications and variations of this application can be made in the light of the above teachings without departing from the spirit and scope thereof, and it is to be understood that all such modifications and variations warrant the patentable subject matter under the patent laws. Other embodiments of the application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. For example, the specification and examples are illustrative only, and do not limit the scope of the application.

[0060] As used herein, the terms "comprise", "comprising", "include", "including", "have", "having" and the like are open-ended and do not exclude additional elements or steps.

[0061] The ligand L in the embodiments of the application is purchased from Tianjin Dadi Kanghe Pharmaceutical Technology Co., Ltd.; cis-capped Pd 2+ The preparation method of the metal node is prepared according to Tae Hwan Noh, Sung Min Kim, Kyung Hwan Park and Ok-Sang Jung, Bonding modes of nitrite and nitrate in palladium(II) and platinum(II) complexes [J]. Transition Met Chem, 2012, 37, 535-540; unless otherwise specified, the remaining materials in the application are commercially available products.

[0062] The embodiment of the present application provides a preparation method of a heteronuclear supramolecular coordination assembly, comprising the following steps: dissolving a ligand L, a cis-terminated M3 metal node and an M1 metal salt or an M2 metal salt in a solvent, obtaining a reaction solution containing coordination cage and coordination tube structures through a coordination-directed self-assembly reaction, without additional treatment, and after cooling to room temperature, the obtained clear solution is the heteronuclear supramolecular coordination assembly, which can be directly used for detection and performance test without purification.

[0063] A specific synthesis route is as follows:

[0064] ;

[0065] The synthesis route of the coordination cage is as follows:

[0066] ;

[0067] The synthesis route of the coordination tube is as follows:

[0068] .

[0069] In some preferred embodiments, the cis-terminated M3 metal node is a cis-Pd 2+ complex with ethylenediamine, N,N,N,N-tetramethylethylenediamine, bipyridine or cyclohexanediamine as the terminal ligand; the M1 metal salt is a silver salt; and the M2 metal salt is selected from a cobalt salt, a nickel salt, a copper salt or a zinc salt. The anions in the M3 metal node, the M1 metal salt and the M2 metal salt are independently selected from NO3 - , BF4 - , SO4 2- , SbF6 - . The anion is a single anion when the coordination cage is prepared, and the anion is a single anion or a mixed anion when the coordination tube is prepared. For example, the cis-terminated M3 metal node is a cis-Pd 2+ complex with N,N,N,N-tetramethylethylenediamine as the terminal ligand, the prepared coordination cage Cage-Pd-Ag(BF4) and Cage-Pd-Ag(SO4) are sandwich structures, and the prepared coordination tube Tube-Pd-Zn(NO3), Tube-Pd-Zn(NO3BF4), Tube-Pd-Zn(NO3SO4), Tube-Pd-Co(NO3SbF6), Tube-Pd-Ni(NO3SbF6), Tube-Pd-Cu(NO3SbF6) and Tube-Pd-Zn(NO3SbF6) are three-prism structures.

[0070] Figure 1 A schematic diagram of the heteronuclear supramolecular coordination assembly of the present application.

[0071] In some preferred embodiments, when the coordination cage is prepared, the molar ratio of ligand L, M3 metal node and M1 metal ion is 1:2:1; the ratio of the amount of ligand L and solvent is 0.022 mmol:3 mL; when the coordination tube is prepared, the molar ratio of ligand L, M3 metal node and M2 metal ion is 1:2:1; the ratio of the amount of ligand L and solvent is 0.054 mmol:5 mL.

[0072] In some preferred embodiments, the solvent is selected from water, an organic solvent or a mixed solution of the organic solvent and water, wherein the organic solvent is selected from dimethyl sulfoxide, CH3CN, CH3OH or CH3COCH3.

[0073] In some preferred embodiments, when water is used as the solvent in the synthesis process, the temperature is adjusted to 70 DEG C, and the reaction time is maintained for 6 hours; different anions have certain influence on the solubility of the supramolecular assembly, if the solubility in water is poor, the solution can be replaced by DMSO, CH3CN, CH3OH, CH3COCH3 solvent, or a mixed solution of one of DMSO, CH3CN, CH3OH, CH3COCH3 and water, the volume ratio is H2O / organic solvent = 1 / 1~1 / 5 or 5 / 1~1 / 1 (volume ratio).

[0074] The present application relates to a synthesis technology of supramolecular metal organic complexes, and describes a convenient synthesis scheme of a kind of heteronuclear flexible supramolecular coordination assembly. The structure can not only be directly synthesized in aqueous solution, has good water solubility. Moreover, it can be conveniently obtained in conventional single organic solvent such as DMSO (dimethyl sulfoxide), acetonitrile, methanol, acetone or mixed solution thereof and water. In addition, the supramolecular coordination structure contains unsaturated coordination metal ion, which can specifically recognize substrate molecules and enzyme catalytic application by using its flexible cavity.

[0075] The heteronuclear supramolecular coordination assembly structure prepared in the embodiments of the present application is simple and efficient in characterization means, has high structural symmetry, and can be conveniently tracked and confirmed by nuclear magnetic resonance; furthermore, the structure can obtain single crystal structure of target structure by using volatilization or solvent diffusion method, which is convenient for further determining the real structure.

[0076] The room temperature of the present application refers to 25±2 DEG C.

[0077] Example 1 Preparation method of heteronuclear supramolecular coordination assembly coordination cage

[0078] The synthesis method of the coordination cage Cage-Pd-Ag(BF4) is as follows: the ligand L (12.10 mg, 0.022 mmol), Me4en-Pd(BF4)2 (17.43 mg, 0.04 mmol) and AgBF4 (4.29 mg, 0.022 mmol) are weighed and added to a 5 mL reaction bottle, then 3 mL of water is added, and heating is carried out at 70 ℃ for 6 hours. After the reaction is completed, a yellow transparent solution is obtained, and a nuclear magnetic spectrum is tested to obtain the coordination cage Cage-Pd-Ag(BF4). By using the solvent diffusion method, the acetone solution is diffused into the reaction solution, and after standing for 3 weeks, blocky light yellow transparent crystals are obtained.

[0079] The synthesis reaction temperature and time of the coordination cage Cage-Pd-Ag(BF4) provided by the application can be adjusted, the temperature range can be 50 ℃-130 ℃, and the reaction time range can be 0.5 hours-8 hours.

[0080] Figure 24 It is a single crystal graph of the coordination cage Cage-Pd-Ag(BF4).

[0081] The synthesis route of the coordination cage Cage-Pd-Ag(BF4) is as shown in Figure 2 .

[0082] Figure 3 It is a nuclear magnetic resonance hydrogen spectrum graph of Cage-Pd-Ag(BF4).

[0083] Figure 4 It is a nuclear magnetic resonance carbon spectrum graph of Cage-Pd-Ag(BF4).

[0084] The nuclear magnetic resonance data of the coordination cage Cage-Pd-Ag(BF4) is as follows: 1 H NMR (400 MHz, 298 K, D2O): δ9.02 (d, J = 5.9 Hz, 8H), 8.87 (d, J = 5.8 Hz, 8H), 7.59 (d, J = 5.9 Hz, 8H),7.31 (d, J = 7.3 Hz, 8H), 4.28 (d, J = 14.3 Hz, 8H), 4.02 (d, J = 14.4 Hz,8H), 3.26 (d, J = 12.7 Hz, 8H), 3.14 (s, 16H), 2.78 (s, 48H), 1.51 (dd, J =25.1, 12.8 Hz, 16H), 1.05 (d, J = 13.4 Hz, 8H). 13C NMR (101 MHz, 298 K, D2O): δ 150.62 (s), 143.54 (s), 130.19 (s), 129.19 (s), 63.01 (s), 62.65 (s), 55.17(s), 50.21 (d, J = 12.8 Hz), 43.32 (s).

[0085] Example 2 Preparation method of heteronuclear supramolecular coordination assembly coordination cage

[0086] The preparation method of the heteronuclear supramolecular coordination assembly coordination cage Cage-Pd-Ag(S04) is the same as that in Example 1, except that Me4en-Pd(BF4)2 is replaced by Me4en-PdSO4 in equimolar amount, and AgBF4 is replaced by 0.5 molar equivalent of Ag2SO4.

[0087] Figure 25 The single crystal diagram of the coordination cage Cage-Pd-Ag(S04).

[0088] Figure 5 The nuclear magnetic resonance hydrogen spectrum of the coordination cage Cage-Pd-Ag(S04), Figure 6 The nuclear magnetic resonance carbon spectrum of the coordination cage Cage-Pd-Ag(S04).

[0089] The coordination cage Cage-Pd-Ag(S04) prepared in this example is in a solution state, and its nuclear magnetic resonance data are as follows: 1 H NMR (400 MHz, 298 K, D2O): δ 9.02 (d, J = 5.9 Hz, 8H), 8.87 (d, J = 5.8 Hz, 8H), 7.59 (d, J = 5.9 Hz, 8H), 7.31 (d, J = 7.3 Hz, 8H), 4.28 (d, J = 14.3 Hz, 8H), 4.02 (d, J = 14.4 Hz, 8H), 3.26 (d, J = 12.7 Hz, 8H), 3.14 (s, 16H), 2.78 (s, 48H), 1.51 (dd, J = 25.1, 12.8 Hz, 16H), 1.05 (d, J = 13.4 Hz, 8H). 13C NMR (101 MHz, 298 K, D2O): δ 150.62 (s), 143.54 (s), 130.19 (s), 129.19(s), 63.01 (s), 62.65 (s), 55.17 (s), 50.21 (d, J = 12.8 Hz), 43.32 (s).

[0090] Figure 7 A perspective view of the coordination cage Cage-Pd-Ag(SO4) prepared in Example 2.

[0091] Example 3 Preparation method of heteronuclear supramolecular coordination assembly coordination tube

[0092] The synthesis method of the coordination tube Tube-Pd-Zn(NO3) is as follows: the ligand L (29.4 mg, 0.054 mmol), Zn(NO3)2·6H2O (16.30 mg, 0.054 mmol) and Me4en-Pd(NO3)2 (37.44 mg, 0.108 mmol) are added into a 5 mL reaction bottle, and 5 mL of water is added, and the reaction is heated at 70 ℃ for 6 hours to obtain a light yellow clear solution. By using the solvent diffusion method, 2 mL of a tetrahydrofuran solution (THF) is diffused into the reaction solution, and the block-shaped colorless transparent crystal is obtained after standing for 4 weeks.

[0093] The synthesis reaction temperature and time of the coordination tube Tube-Pd-Zn(NO3) provided by the application can be adjusted, the temperature range can be 50 ℃-130 ℃, and the reaction time range can be 0.5 hours-8 hours.

[0094] The single crystal graph of the coordination tube Tube-Pd-Zn(NO3) is as shown in Figure 23 .

[0095] The synthesis route of the coordination tube Tube-Pd-Zn(NO3) is as shown in Figure 8 .

[0096] Figure 9 The coordination tube Tube-Pd-Zn(NO3) is a nuclear magnetic resonance hydrogen spectrum.

[0097] Figure 10 The coordination tube Tube-Pd-Zn(NO3) is a nuclear magnetic resonance carbon spectrum.

[0098] The nuclear magnetic resonance data of Tube-Pd-Zn(NO3) is as follows: 1H NMR (400 MHz, 298 K, D2O): δ 9.10 (d, J = 4.5 Hz, 12H), 9.02 (d, J = 6.4 Hz, 12H), 7.77 (d, J = 4.7 Hz, 12H), 7.69 (d, J = 5.8 Hz, 12H), 4.33 (d, J = 14.7 Hz, d, J = 4.5 Hz, 12H), 4.19 (d, J = 13.0 Hz, d, J = 4.5 Hz, 12H), 3.02 (s, 24H), 2.67 (d, J = 16.5 Hz, 72H), 2.96 (d, J = 43.9 Hz, 12H), 1.88 (m, 12H). 13 C NMR (101 MHz, 298 K,D2O): δ 151.32 (d, J = 11.5 Hz), δ 150.58 (m), δ 143.66 (m), δ 131.09 (m), δ 128.82 (m), δ 62.97 (s), δ 54.06 (m), δ 50.30 (s), δ 48.07 (m).

[0099] Example 4

[0100] The coordination tube Tube-Pd-Zn(NO3BF4) was synthesized according to the method of Example 3, except that Me4en-Pd(NO3)2was replaced by Me4en-Pd(BF4)2in equimolar amount.

[0101] Figure 11 The NMR hydrogen spectrum of the coordination tube Tube-Pd-Zn(NO3BF4).

[0102] Figure 12 The NMR carbon spectrum of the coordination tube Tube-Pd-Zn(NO3BF4).

[0103] The NMR data of the coordination tube Tube-Pd-Zn(NO3BF4) in solution are: 1H-NMR (400MHz, D20, 298 K) δ = 9.10 (d, J = 5.3 Hz, 12H), 8.99 (d, J = 5.6 Hz, 12H), 7.76 (d, J = 3.9 Hz, 12H), 7.67 (d, J = 5.8 Hz, 12H), 4.34 (d, J = 14.2 Hz, 12H), 4.20 (d, J = 13.3 Hz, 12H), 3.10 (s, 27H), 2.71-2.67 (m, 101H), 1.89-1.78 (m, 18H). 13 C NMR (101MHz, D20, 298 K): δ = 151.99, 151.86, 150.35, 150.04, 143.76, 143.56, 134.71, 134.57, 131.21, 131.09, 128.73, 128.61, 62.59, 62.47, 54.06, 53.96, 53.80, 50.26, 50.16, 48.20, 47.90, 47.56, 47.26.

[0104] Example 5

[0105] The coordination tube Tube-Pd-Zn(N03SO4) was synthesized according to the method of Example 3, except that Me4en-Pd(N03)2was replaced by Me4en-PdSO4in equimolar amount.

[0106] Figure 13 The H-NMR spectrum of the coordination tube Tube-Pd-Zn(N03SO4).

[0107] Figure 14 The C-NMR spectrum of the coordination tube Tube-Pd-Zn(N03SO4).

[0108] The coordination tube Tube-Pd-Zn(N03SO4) was in solution state, and its NMR data were as follows: 1H-NMR (400MHz, D20, 298 K) δ = 9.18 (d, J = 5.6 Hz, 12H), 9.09 (d, J = 5.7 Hz, 12H), 7.81 (d, J = 4.6 Hz, 12H), 7.74 (d, J = 5.3 Hz, 12H), 4.43 (d, J = 12.2 Hz, 12H), 4.30 (d, J = 12.3 Hz, 12H), 3.05 (s, 27H), 2.82-2.57 (m, 111H), 2.32-2.28 (m, 10H). 13 CNMR (101MHz, D20, 298 K): δ = 151.71, 151.56, 150.16, 150.02, 130.87, 130.70, 128.76, 128.63, 128.50, 62.92, 62,62, 53.75, 53.61, 53.48, 50.18, 49.75, 48.59, 48.45, 46.83, 46.69, 46.58.

[0109] Example 6

[0110] The coordination tube Tube-Pd-Zn(NO3SbF6) was synthesized according to the method of Example 3, except that Me4en-Pd(NO3)2was replaced by Me4en-Pd(SbF6)2in equimolar amount.

[0111] Figure 15 The H-NMR spectrum of the coordination tube Tube-Pd-Zn(NO3SbF6).

[0112] Figure 16 The C-NMR spectrum of the coordination tube Tube-Pd-Zn(NO3SbF6).

[0113] The coordination tube Tube-Pd-Zn(NO3SbF6) was in solution state, and its NMR data were as follows: 1H-NMR (400MHz, D20, 298 K) δ = 9.10 (d, J = 5.2 Hz, 12H), 9.02 (d, J = 5.3 Hz, 12H), 7.76 (d, J = 4.1 Hz, 12H), 7.69 (d, J = 5.3 Hz, 12H), 4.33 (d, J = 2.2 Hz, 12H), 4.19 (d, J = 2.5 Hz, 12H), 3.07-2.96 (m, 36H), 2.68-2.65 (m, 80H), 2.30-1.88 (m, 15H). 13 C NMR (101MHz, D20, 298 K): δ = 151.72, 151.58, 150.54, 150.34, 131.18, 129.52, 129.11, 128.94, 128.47, 62.83, 62.40, 62.32, 53.38, 53.27, 52.99, 50.05, 49.81, 48.16, 47.95, 47.73.

[0114] Example 7

[0115] The synthesis of Tube-Pd-Co(N03SbF6) was the same as Example 3, except that Me4en-Pd(N03)2was replaced by Me4en-Pd(SbF6)2in equimolar amount, and Zn(N03)2was replaced by Co(N03)2in equimolar amount.

[0116] Figure 17 The H-NMR spectrum of Tube-Pd-Co(N03SbF6).

[0117] Figure 18 The C-NMR spectrum of Tube-Pd-Co(N03SbF6).

[0118] Tube-Pd-Co(N03SbF6) was in solution state, and its NMR data were as follows: 1H-NMR (400MHz, D20, 298 K) δ = 9.05 (d, J = 5.6 Hz, 12H), 8.99 (d, J = 5.9 Hz, 12H), 7.69 (d, J = 3.6 Hz, 12H), 7.65 (d, J = 5.9 Hz, 12H), 4.34 (d, J = 14.8 Hz, 12H), 4.23 (d, J = 13.6 Hz, 12H), 2.98 (s, 24H), 2.91 (s, 18H), 2.53 (d, J = 17.9 Hz, 72H), 2.43-1.97 (m, 30H). 13 C NMR (101MHz, D20, 298 K): δ = 151.57, 151.41, 151.06, 150.93, 131.05, 130.96, 129.29, 129.22, 62.49, 62.19, 53.28, 53.01, 50.07, 48.06, 47.79, 47.54.

[0119] Example 8

[0120] The synthesis method of coordination tube Tube-Pd-Ni(NO3SbF6) is the same as Example 3, except that Me4en-Pd(NO3)2is replaced by Me4en-Pd(SbF6)2in equimolar amount, and Zn(NO3)2is replaced by Ni(NO3)2in equimolar amount.

[0121] Figure 19 The coordination tube Tube-Pd-Ni(NO3SbF6) prepared in this example is in solution state, and its nuclear magnetic resonance data are as follows:

[0122] Figure 20 The coordination tube Tube-Pd-Ni(NO3SbF6) prepared in this example is in solution state, and its nuclear magnetic resonance data are as follows:

[0123] The coordination tube Tube-Pd-Ni(NO3SbF6) prepared in this example is in solution state, and its nuclear magnetic resonance data are as follows: 1H-NMR (400MHz, D20, 298 K) δ = 9.12 (d, J = 5.2 Hz, 12H), 9.06 (d, J = 5.7 Hz, 12H), 7.76 (d, J = 3.3 Hz, 12H), 7.72 (d, J = 5.4 Hz, 12H), 4.43 (d, J = 13.8 Hz, 12H), 4.31 (d, J = 13.4 Hz, 12H), 3.06 (s, 24H), 2.99 (s, 18H), 2.59 (d, J = 17.5 Hz, 72H), 2.36-2.29 (m, 30H). 13 C NMR (101MHz, D20, 298 K): δ = 151.50, 151.37, 151.02, 150.93, 144.11, 143.68, 141.74, 141.56, 131.13, 130.91, 129.34, 129.16, 62.70, 62.57, 53.56, 50.218, 48.08, 47.87, 47.75, 46.30, 45.47.

[0124] Example 9

[0125] The synthesis method of coordination tube Tube-Pd-Cu(NO3SbF6) is the same as Example 3, except that Me4en-Pd(NO3)2is replaced by Me4en-Pd(SbF6)2in equimolar amount, and Zn(NO3)2is replaced by Cu(NO3)2in equimolar amount.

[0126] Figure 21 The hydrogen nuclear magnetic resonance spectrum of coordination tube Tube-Pd-Cu(NO3SbF6).

[0127] Figure 22 The carbon nuclear magnetic resonance spectrum of coordination tube Tube-Pd-Cu(NO3SbF6).

[0128] Coordination tube Tube-Pd-Cu(NO3SbF6) is in solution state, and its nuclear magnetic signal splitting is poor due to paramagnetic effect of Cu ions in coordination tube system, and wide peaks are presented, and the approximate nuclear magnetic signal peaks are as follows: 1 H-NMR (400MHz, D20, 298 K) δ = 9.12 (d, J = 5.2 Hz, 12H), 9.06 (d, J = 5.7 Hz, 12H), 7.76 (d, J = 3.3 Hz, 12H), 7.72 (d, J = 5.4 Hz, 12H), 4.43 (d, J = 13.8 Hz, 12H), 4.31 (d, J = 13.4 Hz, 12H), 3.06 (s, 24H), 2.99 (s, 18H), 2.59 (d, J = 17.5 Hz, 72H), 2.36-2.29 (m, 30H).13 C NMR (101MHz, D2O, 298 K): δ = 159.63, 157.14, 153.77,62.50, 50.02, 43.31.

[0129] The preparation method used in the preparation of ligand tube in Examples 4-9 is the same as the feeding ratio of the ligand tube Tube-Pd-Zn(NO3) in Example 3, and the metal node and metal salt used are replaced with the corresponding raw materials. By using the solvent diffusion method, acetone or tetrahydrofuran solution (THF) is diffused into the corresponding reaction solution, and after standing for 3-5 weeks, transparent crystals with different colors and shapes can be obtained. Among them, the crystal color of Zn 2+ chelated is colorless, the crystal color of Cu 2+ chelated is blue, the crystal color of Co 2+ chelated is purple or purple red, the crystal color of Ni 2+ chelated is blue, and the crystal color of Ag + captured is light yellow. Figure 26 The spatial structure of the ligand prepared in Examples 4-9. It should be emphasized that the heteronuclear supramolecular complex of the present application is not limited to the content represented by Figure 7 and Figure 26 R is the assembly structure of ethylenediamine, cyclohexanediamine, and bipyridine, and the corresponding structure shown in Figure 7 and Figure 26 .

[0130] Performance test test one

[0131] The significant feature of the heteronuclear supramolecular coordination assembly prepared by the present application is that the coordination center part can bind different metal ions in a coordination unsaturated mode, providing various catalytically active centers for the structure cavity. Such structure has good water solubility (water stability) and can carry out green enzyme-like catalytic performance research with water as the medium. In addition, the ligand center of such structure chelates metal ions with coordination unsaturation, has Lewis acidity, and its axial orientation can bind Lewis bases such as OH - , and has good acid and alkali resistance.

[0132] By testing the stability of the coordination tube (Tube-Pd-Zn(NO3)) prepared in Example 3 (Example 3) in the pH=1-12 range, it is found that it can be stable for several months, and its acid and alkali resistance range is better than that of most known Pd-based supramolecular coordination structures. Such structure has potential research value in catalytic performance research, and chelating different metal ions can specifically catalyze certain reactions, such as the ligand L center part binding metal Cu 2+ ion, which can catalyze the aryl cyclopropane 1,3-amination lactonization reaction; binding metal Ru 2+ , Ir3+ The ions can carry out photocatalytic CO2 reduction, and hydrogen production by water splitting; and can realize enzyme-like catalytic conversion of CO2 in combination with metal Zn 2+ The ions can realize enzyme-like catalytic conversion of CO2. Figure 27 The acid-base stability interval diagram of the coordination tube Tube-Pd-Zn(NO3) prepared in Example 3 (Example 3) is shown in the figure. Figure 27 As can be seen from the figure, the coordination tube Tube-Pd-Zn(NO3) (Example 3) can well maintain the stability of the structure in the interval of pH = 1 and 12, which provides a basic guarantee for realizing enzyme-like catalytic reactions of the structure in different acid-base environments.

[0133] Performance test test two

[0134] In order to realize the enzyme-like catalytic reaction of the heteronuclear supramolecular coordination assembly prepared in the application, the application preferentially studies the catalytic CO2 conversion reaction. The carbonic anhydrase in the organism can efficiently and specifically realize the conversion of CO2 into carbonate ions, which is due to the synergistic effect of the active center Zn 2+ of the enzyme and the flexible cavity. Inspired by this biological phenomenon, the coordination tube structure synthesized in the application has an active center and an adaptable internal cavity, so the coordination tube structure may have the characteristics of carbonic anhydrase. The application uses the Materials Studio software to perform molecular simulation, and finds that the shape and size of the carbonate ion can perfectly match the coordination tube structure. Figure 28 The host-guest simulation structure diagram of Tube-Pd-Zn(NO3) (Example 3) and CO3 2- As can be seen from the figure, Figure 28 the size and shape of the internal cavity of Tube-Pd-Zn(NO3) (Example 3) perfectly match the shape and size of CO3 2- , the Zn 2- chelated by CO3 2+ in the cavity maintains a reasonable distance. In addition, the entire skeleton cavity maintains a positive charge, has a good electrostatic effect with the negatively charged CO3 2- , and the H atom in the cavity can form multiple C-O---H with CO3 2- , thereby enhancing the stability of the host-guest complex formed by the cavity and CO3 2- .

[0135] The catalytic CO2 conversion reaction conditions are as follows: the coordination tube Tube-Pd-Zn(NO3) (Example 3) (63.87 mg, 0.015 mmol) is added to a 20 mL reaction test tube, 4 mL of a mixed solvent containing 0.03 mmol NaOH and H2O / DMSO = 2 / 1 is added, CO2 is continuously introduced into the reaction test tube for 3 hours, and nuclear magnetic resonance 13C spectrum. CO2 conversion experiment conditions of coordination tube Tube-Pd-Co(NO3 SbF6) (Example 7), Tube-Pd-Ni(NO3 SbF6) (Example 8), Tube-Pd-Cu(NO3 SbF6) (Example 9) are the same as Tube-Pd-Zn(NO3) (Example 3). Analyze the reaction results by nuclear magnetic resonance 13 C spectrum, only coordination tube Tube-Pd-Zn(NO3) (Example 3) has high-efficiency CO2 conversion reaction phenomenon, realizing enzyme-like catalytic reaction. Other heteronuclear coordination tube structures do not have carbonic anhydrase-like phenomenon, indicating that this type of heteronuclear coordination tube structure has specific selectivity in the field of catalytic performance. Figure 29 C) is coordination tube Tube-Pd-Zn(NO3), CO3 2- @Solid-state infrared spectrum of Tube-Pd-Zn(NO3) and Na2CO3, from which it can be seen that: due to the shielding effect of the carbonate ion being wrapped inside the cavity, the wave number occurs red shift phenomenon (free state 1450cm -1 , wrapped state 1350cm -1 ). Figure 29 D) is the host-guest single crystal structure obtained by solvent evaporation method (Tube-Pd-Zn(NO3) (Example 3) is the host, CO3 2- is the guest), from which it can be seen that: single crystal structure shows that carbonate ions are perfectly wrapped in the coordination tube cavity through multiple hydrogen bonding. Figure 30 C spectrum of coordination tube Tube-Pd-Co(NO3 SbF6) (Example 7) and Tube-Pd-Ni(NO3 SbF6) (Example 8) catalyzing CO2 conversion, because coordination tube Tube-Pd-Cu(NO3 SbF6) (Example 9) has magnetic properties, its nuclear magnetic carbon spectrum cannot be detected. Among them Figure 30 A) is the nuclear magnetic carbon spectrum of Tube-Pd-Co(NO3 SbF6) (Example 7) after catalyzing CO2 conversion, Figure 30 B) is the nuclear magnetic carbon spectrum of Tube-Pd-Ni(NO3 SbF6) (Example 8) after catalyzing CO2 conversion, analyzing the nuclear magnetic carbon spectrum Figure 30 There is no signal, proving that coordination tube Tube-Pd-Co(NO3 SbF6) (Example 7) and Tube-Pd-Ni(NO3 SbF6) (Example 8) do not have the performance of catalyzing CO2 to CO3 2- . Similarly, we guess that coordination tube Tube-Pd-Cu(NO3 SbF6) (Example 9) also does not have this catalytic ability. Further confirm that the reason why this type of coordination tube structure catalyzes CO2 to CO3 2- is: active Zn2+ and the internal cavity synergistic catalytic effect, both indispensable.

[0136] Ca 2+ as a precipitant, to achieve coordination tube cycle catalytic reaction, such as Figure 29 A) coordination tube Tube-Pd-Zn(NO3) (Example 3) to promote CO2 into CO3 2- as shown in the schematic, blank and control reaction studies fully demonstrated that the heteronuclear coordination tube Tube-Pd-Zn(NO3) (Example 3) structure can efficiently catalyze CO2 conversion, is by unsaturated coordination of Zn 2+ and can be perfectly matched with carbonate ions, flexible cavity synergistic effect, such as Figure 29 B) shown in the carbon nuclear magnetic resonance spectrum, wherein a is the carbon nuclear magnetic resonance spectrum of CO2, b is the carbon nuclear magnetic resonance spectrum of the blank experiment, c is the carbon nuclear magnetic resonance spectrum of coordination tube Tube-Pd-Zn(NO3) (Example 3), d is the carbon nuclear magnetic resonance spectrum of catalytic reaction, e is the carbon nuclear magnetic resonance spectrum of CO3 2- precipitated carbon nuclear magnetic resonance spectrum, f is the carbon nuclear magnetic resonance spectrum of the cycle catalytic experiment.

[0137] The above, only for the preferred specific embodiments of the present application, but the scope of the present application is not limited to this, any skilled in the art of the technical personnel in the technical range of the present application disclosed, can easily think of changes or replacement, should be covered within the scope of the present application.

Claims

1. A class of heteronuclear supramolecular coordination assemblies, characterized in that, The coordination cage has a stereostructure as shown in (I), and the coordination tube has a stereostructure as shown in (II). (I) (II) wherein R is selected from ethylenediamine, N,N,N,N-tetramethylethylenediamine, bipyridine or cyclohexanediamine; M1is Ag + ; M2is Co 2+ , Ni 2 + , Cu 2+ or Zn 2+ ; M3is Pd 2+ .

2. A preparation method of the heteronuclear supramolecular coordination assembly according to claim 1, characterized in that, the preparation method of the coordination cage comprises the following steps: dissolving ligand L, cis-terminated M3 metal node and M1 metal salt in a solvent, and preparing the coordination cage through a coordination-directed self-assembly reaction. The preparation method of the coordination tube comprises the following steps: dissolving ligand L, cis-terminated M3 metal node and M2 metal salt in a solvent, and preparing the coordination tube through a coordination-directed self-assembly reaction. In the preparation of the coordination cage, the molar ratio of ligand L, M3 metal node and M1 metal ion is 1:2:1; the dosage ratio of ligand L and solvent is 0.022 mmol:3 mL; in the preparation of the coordination tube, the molar ratio of ligand L, M3 metal node and M2 metal ion is 1:2:1; the dosage ratio of ligand L and solvent is 0.054 mmol:5 mL.

3. The method of preparing a heteronuclear supramolecular coordination assembly according to claim 2, characterized in that, The structural formula of the ligand L is .

4. The method of preparing a heteronuclear supramolecular coordination assembly according to claim 2, characterized in that, said cis-capped M3 metal node is a cis-Pd capped with ethylenediamine, N,N,N,N-tetramethylethylenediamine, bipyridine or cyclohexanediamine 2+ complex; said M1 metal salt is a silver salt; said M2 metal salt is selected from a cobalt salt, a nickel salt, a copper salt or a zinc salt.

5. The method of preparing a heteronuclear supramolecular coordination assembly according to claim 4, characterized in that, the anions in the M3metal nodes, M1metal salts and M2metal salts are independently selected from NO3 - , BF4 - , SO4 2- or SbF6 - ; the anions are single anions when making the coordination cage; the anions are single anions or mixed anions when making the coordination tube.

6. The method of preparing a heteronuclear supramolecular coordination assembly according to claim 2, characterized in that, The solvent is selected from water, an organic solvent or a mixed solvent of an organic solvent and water; the organic solvent is selected from dimethyl sulfoxide, CH3CN, CH3OH or CH3COCH3.

7. The method of preparing a heteronuclear supramolecular coordination assembly according to claim 2, characterized in that, In the preparation of the coordination cage and coordination tube, the temperature of the coordination-directed self-assembly reaction is 70 ℃.

8. The method of preparing a heteronuclear supramolecular coordination assembly according to claim 2, characterized in that, 9. Application of the heteronuclear supramolecular coordination assembly according to claim 1 in enzyme-mimetic catalysis or molecular recognition. ​

Images