3-methylpyridine cantilever macrocyclic binuclear copper complex as well as preparation method and application thereof

Abstract

The invention discloses a 3-methylpyridine cantilever macrocyclic binuclear copper complex, and relates to the technical field of organic synthesis, and the specific structure is as follows: # imgabs0 #, a preparation method comprises the following steps: (1) mixing 1, 2-bis (3-pyridine methylamino) ethane and triethylamine, then adding 3-bromomethyl-5-methyl salicylaldehyde, and carrying out a reaction to obtain a first mixed solution; and (2) sequentially adding copper acetate, 2-hydroxy-1, 3-propane diamine and Cu (ClO4) 2 into the first mixed solution, and after the reaction is completed, obtaining the 3-methylpyridine cantilever macrocyclic binuclear copper complex. The preparation method provided by the invention is simple, the target complex can be efficiently prepared by utilizing a one-pot method, and experiments prove that the complex prepared by the invention has an obvious binding effect with calf thymus DNA, has excellent catalytic activity, and is applied to the fields of preparation of novel medicines, environmental protection and energy conversion catalysts.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a 3-methylpyridine cantilever macrocyclic binuclear copper complex and a preparation method and application thereof. Background Art

[0002] The study of macrocyclic complexes has a long history. They exist in large quantities in nature and organisms, such as hemoglobin porphyrin iron derivatives, chlorophyll porphyrin magnesium derivatives, and cyclic ion carriers. Because of the potential of macrocyclic complexes in structural properties and biological activity, people have been interested in the study of this large class of complexes. Research in recent years has found that macrocyclic complexes containing N, O, and S heteroatoms, especially macrocyclic tetraimine Schiff bases (Schiffbase), can not only transfer energy, are sensitive to light, electricity, and heat, and have functions such as recognition, selective transmission, and catalysis, but also have good biological activity in anti-cancer, anti-viral, and bactericidal effects, which has prompted people to conduct extensive research on Schiff base binuclear macrocyclic complexes.

[0003] N(amine)2N(imine)2O2 type phenolic oxygen-containing macrocyclic complexes are a type of binuclear Schiff base macrocyclic complexes. In 1992, the Bosnich group first synthesized a polynitrogen macrocyclic complex of N(amine)2N(imine)2O2 type precursor ligand with a pyridine ring cantilever, and reported the redox effect of the metal center in the complex. The Ōkawa group and the Pan Zhiquan group successively synthesized N(amine)2N(imine)2O2 type precursor ligands with methyl substitution on N(amine)2, and did some meaningful research work in the synthesis, magnetic properties and electrochemical properties of the complexes; Pan Zhiquan's group also synthesized N(amine)2N(imine)2O2 type precursor ligands with furan ring cantilever through the Mannich reaction and studied the DNA cleavage effect of the synthesized heterobinuclear complex.

[0004] Due to the good bioaffinity and bioactivity of pyridine compounds and the strong coordination ability of the nitrogen atom on the pyridine ring, the synthesis and property research of N(amine)2N(imine)2O2 type complexes containing pyridine ring cantilevers have attracted more and more attention recently. However, due to the complexity of the synthesis and purification steps of the ligand precursors, the period of obtaining the pure product is too long and the product yield is low, which limits the research on the application properties of this type of complex. Therefore, design energy has become a hot topic in current research.

[0005] Therefore, it is a technical problem that needs to be solved urgently in the art to provide a ligand precursor synthesis step with improved yield and a N(amine)2N(imine)2O2 type binuclear macrocyclic complex containing a pyridine ring cantilever with a novel structure. Summary of the invention

[0006] In view of the problems existing in the prior art, the present invention provides a 3-methylpyridine cantilever macrocyclic binuclear copper complex and a preparation method and application thereof.

[0007] In order to achieve the above object, the present invention adopts the following technical solution:

[0008] A 3-methylpyridine cantilever macrocyclic binuclear copper complex, the structural formula of the complex is:

[0009]

[0010] The method for preparing the 3-methylpyridine cantilever macrocyclic binuclear copper complex as described above comprises the following steps:

[0011] (1) mixing 1,2-di(3-pyridylmethylamino)ethane and triethylamine, and then adding 3-bromomethyl-5-methylsalicylaldehyde to react to obtain a first mixed solution;

[0012] (2) adding copper acetate, 2-hydroxy-1,3-propylenediamine and Cu(ClO4)2 to the first mixed solution in sequence to react, and after the reaction is completed, the 3-methylpyridine cantilever macrocyclic binuclear copper complex is obtained.

[0013] Preferably, the process route of the preparation method is:

[0014]

[0015] Preferably, in step (1), the molar ratio of 1,2-bis(3-pyridylmethylamino)ethane, the triethylamine and the 3-bromomethyl-5-methylsalicylaldehyde is 0.25-0.4:1-1.5:0.6-0.9.

[0016] Preferably, the reaction time in step (1) is 1-4 h, and the stirring speed is 200-400 rpm.

[0017] Preferably, the 3-bromomethyl-5-methylsalicylaldehyde in step (1) may also be 3-chloromethyl-5-methylsalicylaldehyde.

[0018] Preferably, in step (2), the molar ratio of the 3-bromomethyl-5-methylsalicylaldehyde, the cupric acetate, the 2-hydroxy-1,3-propylenediamine and the Cu(ClO4)2 is 2-4:1-1.5:1-1.5:1-1.5.

[0019] Preferably, the reaction time of the copper acetate in step (2) is 1-3 h, the stirring speed is 200-400 rpm, and the dripping rate of the copper acetate is 1-4 drops / second.

[0020] Preferably, the reaction time of the 2-hydroxy-1,3-propylenediamine in step (2) is 2-5 h, the stirring speed is 200-300 rpm, and the dripping rate of the copper acetate is 1-4 drops / second.

[0021] Preferably, the reaction time of Cu(ClO4)2 in step (2) is 3-6h, the stirring speed is 250-400rpm, and the dripping rate of the copper acetate is 1-4 drops / second.

[0022] As mentioned above, the 3-methylpyridine cantilever macrocyclic binuclear copper complex is used in the preparation of drugs and catalysts.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] The preparation method of the invention directly adopts 1,2-bis(3-pyridinemethylamino)ethane, 3-bromo(chloro)methyl-5-methylsalicylaldehyde and 2-hydroxy-1,3-propylenediamine for reaction, and then adds metal to directly obtain a complex. The one-pot method is adopted for direct synthesis, and the target complex can be efficiently prepared. Experimental verification shows that the 3-methylpyridine cantilever macrocyclic binuclear copper complex prepared by the invention has obvious binding effect with calf thymus DNA and excellent catalytic activity, and is applied in the fields of preparing new drugs, environmental protection and energy conversion catalysts. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. The drawings in this description are only embodiments of the present invention.

[0026] Figure 1 This is the infrared spectrum of the complex prepared in Example 1 of the present invention;

[0027] Figure 2 This is the electrospray mass spectrum of the complex prepared in Example 1 of the present invention;

[0028] Figure 3 The crystal structure diagram of the complex prepared in Example 1 of the present invention;

[0029] Figure 4 The stacking diagram of the complex molecules prepared in Example 1 of the present invention along the c-axis;

[0030] Figure 5 The cyclic voltammogram of the complex prepared in Example 1 of the present invention;

[0031] Figure 6 The cyclic voltammogram of the complex prepared in Example 1 of the present invention and DNA;

[0032] Figure 7 The DNA viscosity of the complex prepared in Example 1 of the present invention as the concentration of the complex changes: [DNA] = 2×10 -4 M. DETAILED DESCRIPTION

[0033] Embodiments of the present invention are described below. Examples of the embodiments are shown in the accompanying drawings. The embodiments described with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, but are not to be construed as limiting the present invention.

[0034] Example 1

[0035] The present invention provides a 3-methylpyridine cantilever macrocyclic binuclear copper complex, and the preparation method specifically comprises the following steps:

[0036] Weigh 3-bromomethyl-5-methyl salicylaldehyde (0.142 g, 0.6 mmol) and dissolve it in 10 ml of dichloromethane, and stir it magnetically; mix 1,2-bis(3-pyridylmethylamino)ethane (0.06 g, 0.25 mmol) and triethylamine (0.11 g, 1 mmol) dried over potassium hydroxide and dissolved in 10 ml of dichloromethane, and slowly drip it into the above solution using a constant pressure funnel at a dripping speed of 2 drops / second. After the dripping is completed, continue stirring for 4 hours at a stirring speed of 300 rpm;

[0037] Slowly add 10mL of anhydrous methanol solution of Cu(OAc)2·H2O (0.049g, 0.25mmol) to the above solution, while stirring magnetically at a rate of 3 drops / second. The solution turns dark green. After the addition is completed, stirring is continued for 2h at a speed of 300rpm. After the reaction is completed, 10mL of anhydrous methanol solution containing 2-hydroxy-1,3-propylenediamine (0.0225g, 0.25mmol) is slowly dropped into the above solution at a rate of 3 drops / second. After stirring for 4h, 10mL of anhydrous acetonitrile solution of Cu(ClO4)2·6H2O (0.093g, 0.25mmol) is slowly dropped into the above solution at a rate of 2 drops / second. After the addition is completed, stirring is continued for 5h at a speed of 250rpm. Filter, and evaporate the solution at room temperature for three weeks to obtain dark green block single crystals suitable for X-ray crystal diffraction, with a yield of 78%. Elemental analysis (%): Found: C 57.19, H 4.91, N 10.82; Calculated (Cu2C 37 H 37 N6O5): C 57.50, H 4.83, N 10.87. IR(KBr, cm -1 ):3482(ν N-H ),2934,2852(ν CH ),1632(ν C＝N ),1544,1441(stCOO - ).

[0038] The infrared spectrum of the complex is shown in Figure 1 As shown, the complex has a peak at 1632 cm -1 The sharp peaks appearing near are the stretching vibration peaks of C=N, indicating that the Schiff base complex has been formed; -1 The medium-intensity peaks at the positions are the asymmetric stretching vibration peaks and symmetric stretching vibration peaks of carboxylates. According to the literature, if the wavelength difference between the asymmetric stretching vibration peak and the symmetric stretching vibration peak of carboxylates is between 130 and 200 cm -1 The range of 590 cm -1 The multiple absorption peaks in the inner fingerprint region are the stretching vibration peaks of MO and MN, at 3482 cm -1 The broad peak appearing nearby is the stretching vibration peak of the secondary amine;

[0039] The Cu2L(OAc) complex (L is the abbreviation of the macrocyclic ligand) prepared in this example was dissolved in anhydrous methanol and analyzed by electrospray mass spectrometry. The results are as follows: Figure 2 As shown, the mass spectrum peak abundance of m / z 775.92 is 100%, which is attributed to [Cu2L(OAc)] (calculated value: 774.82), which is a molecular ion peak; the mass spectrum peak abundance of m / z 717.08 is 23%, which is the [Cu2L] (calculated value: 713.78) species after losing acetate; the abundance of other fragment peaks in the figure is very small, which shows that the complex can exist stably in methanol solution;

[0040] The crystal structure data of the complex and the related data collection and structure optimization data are shown in Table 1, and some of its building block length bond angle data are listed in Table 2.

[0041] Table 1 Crystallographic data and structural refinement data of the complexes

[0042]

[0043] Table 2 Some bond lengths and bond angles of complexes

[0044]

[0045] The crystal structure of the complex is shown in Figure 3As can be seen from the figure, the straight line connecting the two copper atoms is the symmetry axis of the complex molecule. One copper atom is located on the side of the macrocyclic ligand (N(amine)2O2), and the other copper atom is located on the side of the macrocyclic ligand (N(imine)2O2). The coordination environment of the copper atom can be approximately regarded as a square pyramid structure. The two copper atoms are bridged by phenol oxygen and acetate. The two oxygen atoms of the acetate are the axial vertices of the square pyramid. The bond angles of the two Cu1-O-Cu2 structures are 101.5°, and the distance between the two Cu is The distance between Cu1 and its coordinating atoms is The distance between Cu2 and its coordinating atoms is The average distance between Cu1 and Cu2 from the coordination plane of their respective N2O2 compositions is and This is much smaller than the average distance of metal ions from their respective N2O2 in similar meta-pyridine macrocyclic complexes, indicating that the metal atoms in the complex are closer to the average plane of the macrocyclic ring and are more easily exposed. Therefore, it is speculated that the complex will have better catalytic activity than the literature complex. The acetate group and the two pyridine rings are located on the same side of the macrocyclic plane, and the angle between the planes where the two pyridine rings are located is Figure 4 This is the stacking diagram of the complex molecules along the c-axis. As can be seen from the figure, it is hexagonal petal-like.

[0046] The cyclic voltammetry of the complex at different scan rates within the scanning range of -1.0 to -0.4 V is as follows: Figure 5 As shown in Figure 2, a pair of redox peaks was found at each scan rate, which was the Cu(II)Cu(II) / Cu(II)Cu(I) redox pair. -1 When the anode peak potential (E pa ) and the cathode peak potential (E pc ) are -0.659V and -0.823V respectively; the half-wave potential E 1 / 2 It is the average value of the sum of the anodic peak potential and the cathodic peak potential, which is -0.741V, 0.020V less than the half-wave potential of the reported pyridine cantilever heterobinuclear copper-zinc complex, which may be caused by the different coordination environments of the metal ions. For the redox system with only one electron transfer, the potential difference △Ep between the oxidation peak and the reduction peak is greater than 59mV, and the cathode peak current and the anodic peak current intensity are not equivalent, indicating that this is a quasi-reversible electrochemical process. At 50-200mV -1 In the scanning rate, i pc / υ 1 / 2 The change in the value is very small, indicating that this process is mainly controlled by diffusion, and its redox process can be expressed as follows:

[0047]

[0048] Figure 6 Figure 1 is the cyclic voltammogram of the complex acting on CT-DNA. Figure 1 is the cyclic voltammogram of the complex without adding CT-DNA, and Figure 2 is the cyclic voltammogram of the complex after adding CT-DNA. The study found that with the addition of CT-DNA, both the peak potential and the peak current of the redox peak changed, indicating that the metal complex acted on CT-DNA. Generally speaking, the positive shift of the peak potential is caused by the insertion of the complex into the double helix structure of DNA, while the negative shift of the peak potential is caused by the electrostatic interaction between the complex and the phosphate on the DNA backbone. Data analysis shows that the anode peak potential shifted positively by 0.080V, the cathode peak potential shifted positively by 0.015V, the anode peak current decreased by 55.1%, and the cathode peak current decreased by 21.8%. These results indicate that the complex acts on CT-DNA by insertion, and the larger cathode peak potential indicates that the metal ions in the complex are not easily reduced under the current conditions.

[0049] Viscosity experiments are widely used to study the interaction between metal complexes and DNA. The present invention uses an Ubbelohde viscometer to measure the viscosity, and the experimental temperature is 25.0±0.1°C. When the metal complex interacts with DNA in an insertion mode, the distance between base pairs in DNA needs to be enlarged to accommodate the incoming complex, resulting in the growth of the DNA double helix structure and an increase in the viscosity of the solution; when the metal complex and DNA are electrostatically bonded or groove-bonded, the viscosity of the solution will not change significantly; Figure 7 It is a viscosity curve diagram of the interaction between the complex and CT-DNA. The data are shown as the ratio of (F / F0)1 / 3 to the concentration of the complex and the concentration of CT-DNA, where F0 is the viscosity of CT-DNA; F is the viscosity of the solution after adding the complex. It can be seen from the figure that with the increase of the concentration of the complex, the viscosity of DNA increases, indicating that the binding mode of the complex and DNA is insertion binding, which is consistent with the conclusion of the cyclic voltammetry spectrum of the previous complex.

[0050] Example 2

[0051] The present invention provides a 3-methylpyridine cantilever macrocyclic binuclear copper complex, and the preparation method specifically comprises the following steps:

[0052] Weigh 3-chloromethyl-5-methyl salicylaldehyde (0.122 g, 0.6 mmol) and dissolve it in 10 ml of dichloromethane with magnetic stirring; mix 1,2-bis(3-pyridylmethylamino)ethane (0.06 g, 0.25 mmol) and triethylamine (0.11 g, 1 mmol) dried over potassium hydroxide and dissolved in 10 ml of dichloromethane, and slowly drip into the above solution using a constant pressure funnel at a dripping speed of 3 drops / second. After the dripping is completed, continue stirring for 4 hours at a stirring speed of 300 rpm;

[0053] Slowly add 10mL of anhydrous methanol solution of Cu(OAc)2·H2O (0.049g, 0.25mmol) to the above solution, while stirring magnetically at a rate of 2 drops / second. The solution turns dark green. After the addition is completed, stirring is continued for 2.5h at a speed of 300rpm. After the reaction is completed, 10mL of anhydrous methanol solution containing 2-hydroxy-1,3-propylenediamine (0.0225g, 0.25mmol) is slowly added to the above solution at a rate of 3 drops / second. After stirring for 4h, 10mL of anhydrous acetonitrile solution of Cu(ClO4)2·6H2O (0.093g, 0.25mmol) is slowly added to the above solution at a rate of 2 drops / second. After the addition is completed, stirring is continued for 5h at a speed of 300rpm. Filter, and evaporate the solution at room temperature for three weeks to obtain dark green block single crystals suitable for X-ray crystal diffraction, with a yield of 73%.

[0054] Example 3

[0055] The present invention provides a 3-methylpyridine cantilever macrocyclic binuclear copper complex, and the preparation method specifically comprises the following steps:

[0056] Weigh 3-bromomethyl-5-methyl salicylaldehyde (0.214 g, 0.9 mmol) and dissolve it in 20 ml of dichloromethane, and stir it magnetically; mix 1,2-bis(3-pyridylmethylamino)ethane (0.091 g, 0.38 mmol) and triethylamine (0.16 g, 1.5 mmol) dried over potassium hydroxide and dissolved in 15 ml of dichloromethane, and slowly drip it into the above solution using a constant pressure funnel at a dripping speed of 3 drops / second. After the dripping is completed, continue stirring for 3 hours at a stirring speed of 350 rpm;

[0057] Slowly add 15mL of anhydrous methanol solution of Cu(OAc)2·H2O (0.098g, 0.5mmol) to the above solution, while stirring magnetically at a rate of 3 drops / second. The solution turns dark green. After the addition is completed, stirring is continued for 3h at a speed of 400rpm. After the reaction is completed, 15mL of anhydrous methanol solution containing 2-hydroxy-1,3-propylenediamine (0.045g, 0.5mmol) is slowly added to the above solution at a rate of 2 drops / second. After stirring for 4.5h, 20mL of anhydrous acetonitrile solution of Cu(ClO4)2·6H2O (0.186g, 0.5mmol) is slowly added to the above solution at a rate of 2 drops / second. After the addition is completed, stirring is continued for 5h at a speed of 350rpm. Filter, and evaporate the solution at room temperature for three weeks to obtain dark green block single crystals suitable for X-ray crystal diffraction, with a yield of 75%.

[0058] Example 4

[0059] The present invention provides a 3-methylpyridine cantilever macrocyclic binuclear copper complex, and the preparation method specifically comprises the following steps:

[0060] Weigh 3-chloromethyl-5-methyl salicylaldehyde (0.163 g, 0.8 mmol) and dissolve it in 15 ml of dichloromethane, and stir it magnetically; mix 1,2-bis(3-pyridylmethylamino)ethane (0.079 g, 0.33 mmol) and triethylamine (0.15 g, 1.5 mmol) dried over potassium hydroxide and dissolved in 15 ml of dichloromethane, and slowly drip it into the above solution using a constant pressure funnel at a dripping speed of 4 drops / second. After the dripping is completed, continue stirring for 3 hours at a stirring speed of 350 rpm;

[0061] Slowly add 20mL of anhydrous methanol solution of Cu(OAc)2·H2O (0.095g, 0.5mmol) to the above solution, while stirring magnetically at a rate of 3 drops / second. The solution turns dark green. After the addition is completed, stirring is continued for 2h at a speed of 400rpm. After the reaction is completed, 15mL of anhydrous methanol solution containing 2-hydroxy-1,3-propylenediamine (0.045g, 0.5mmol) is slowly added to the above solution at a rate of 2 drops / second. After stirring for 4.5h, 20mL of anhydrous acetonitrile solution of Cu(ClO4)2·6H2O (0.149g, 0.4mmol) is slowly added to the above solution at a rate of 1 drop / second. After the addition is completed, stirring is continued for 3h at a speed of 350rpm. Filter, and evaporate the solution at room temperature for three weeks to obtain dark green block single crystals suitable for X-ray crystal diffraction, with a yield of 70%.

[0062] The present invention uses a one-pot method to prepare a macrocyclic binuclear copper complex (CCDC: 2251158) with a meta-methylpyridine cantilever, and the synthesized complex is characterized by infrared spectroscopy, elemental analysis, electrospray mass spectrometry and X-ray single crystal diffraction, and the binding mode of the complex with CT-DNA is studied by electrochemical method and viscosity method. The results show that the coordination environment of the copper atom can be approximately regarded as a square pyramid structure, two copper atoms are bridged by phenoxy and acetate, the two oxygen atoms of the acetate are the axial vertices of the square pyramid, and the distance between the two central copper atoms is Electrochemical and viscosity experiments showed that the binding mode of the complex to CT-DNA was insertion binding.

[0063] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A 3-methylpyridine cantilever macrocyclic binuclear copper complex, characterized in that: The structural formula of the complex is:

2. A method for preparing a 3-methylpyridine cantilever macrocyclic binuclear copper complex as claimed in claim 1, characterized in that: The following steps are involved: (1) mixing 1,2-di(3-pyridylmethylamino)ethane and triethylamine, and then adding 3-bromomethyl-5-methylsalicylaldehyde to react to obtain a first mixed solution; (2) adding copper acetate, 2-hydroxy-1,3-propylenediamine and Cu(ClO4)2 to the first mixed solution in sequence to react, and after the reaction is completed, the 3-methylpyridine cantilever macrocyclic binuclear copper complex is obtained.

3. The method for preparing a 3-methylpyridine cantilever macrocyclic binuclear copper complex according to claim 2, characterized in that: The molar ratio of the 1,2-bis(3-pyridylmethylamino)ethane, the triethylamine and the 3-bromomethyl-5-methylsalicylaldehyde in step (1) is 0.25-0.4:1-1.5:0.6-0.

9.

4. The method for preparing a 3-methylpyridine cantilever macrocyclic binuclear copper complex according to claim 2, characterized in that: The reaction time in step (1) is 1-4 hours, and the stirring speed is 200-400 rpm.

5. The method for preparing a 3-methylpyridine cantilever macrocyclic binuclear copper complex according to claim 2, characterized in that: The 3-bromomethyl-5-methyl salicylaldehyde in step (1) may also be 3-chloromethyl-5-methyl salicylaldehyde.

6. The method for preparing a 3-methylpyridine cantilever macrocyclic binuclear copper complex according to claim 2, characterized in that: The molar ratio of the 3-bromomethyl-5-methyl salicylaldehyde, the cupric acetate, the 2-hydroxy-1,3-propylenediamine and the Cu(ClO4)2 in step (2) is 2-4:1-1.5:1-1.5:1-1.

5.

7. The method for preparing a 3-methylpyridine cantilever macrocyclic binuclear copper complex according to claim 2, characterized in that: The reaction time of the copper acetate in step (2) is 1-3 hours, the stirring speed is 200-400 rpm, and the dripping rate of the copper acetate is 1-4 drops / second.

8. The method for preparing a 3-methylpyridine cantilever macrocyclic binuclear copper complex according to claim 2, characterized in that: The reaction time of the 2-hydroxy-1,3-propylenediamine in step (2) is 2-5 hours, the stirring speed is 200-300 rpm, and the dripping rate of the copper acetate is 1-4 drops / second.

9. The method for preparing a 3-methylpyridine cantilever macrocyclic binuclear copper complex according to claim 2, characterized in that: The reaction time of Cu(ClO4)2 in step (2) is 3-6h, the stirring speed is 250-400rpm, and the dripping rate of the copper acetate is 1-4 drops / second.

10. Use of the 3-methylpyridine cantilever macrocyclic binuclear copper complex as claimed in claim 1 in the preparation of drugs and catalysts.

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