Mononuclear 2, 2 ': 6', 2 ''-terpyridyl ruthenium (II) complex with electrochemiluminescence dual emission

Abstract

The invention discloses a mononuclear 2, 2 ': 6', 2 ''-terpyridyl ruthenium (II) complex with electrochemiluminescence dual-emission performance, the chemical structural formula is shown in the specification, or the complex is formed by connecting 2, 2 ': 6', 2 ''-terpyridyl ligands with different substituents with tetraphenyl ethylene ligands with different substituents, and the complex is formed by synthesizing the 2, 2 ': 6', 2 ''-terpyridyl ruthenium (II) complex with the electrochemiluminescence dual-emission performance. And then chelating a ruthenium (II) ion in an NNN coordination mode to synthesize the metal complex illuminant consisting of a mononuclear 2, 2 ': 6', 2 ''-terpyridyl ruthenium (II) complex. The complex disclosed by the invention has strong electrochemical luminescence performance, can be applied to the sensing field, is wide in application prospect, provides reference for designing the mononuclear tridentate ruthenium (II) complex with good electrochemical luminescence performance, and expands the potential application of the mononuclear tridentate ruthenium (II) complex in related fields.

Description

Technical Field

[0001] The present invention relates to the field of electrochemiluminescence, and particularly to a mononuclear ruthenium (II) complex of 2,2':6',2''-terpyridine with dual electrochemiluminescence emission. Background Art

[0002] 2,2':6',2''-Terpyridine ruthenium (II) complexes have excellent photophysical properties and have been widely studied for applications in photoelectric conversion, light-emitting electrochemical cells, electroluminescence systems, nonlinear optical devices, and luminescence sensors, etc. They have strong electron donor and acceptor capabilities and can form stable complexes with various metals. In the binding with metal ions, the coordination bond strength of the 2,2':6',2''-terpyridine ligand increases in the order of Cd(II) < Zn(II) < Ni(II) < Fe(II) < Ru(II). Traditional electrochemiluminescent materials are mainly luminol and [Ru(bpy)3] 2+ , while luminol has poor water solubility and [Ru(bpy)3] 2+ can only emit within a limited wavelength of 600 nm, which limits its development. Therefore, it is of great significance to develop mononuclear ruthenium (II) complexes of 2,2':6',2''-terpyridine with electrochemiluminescent properties. Summary of the Invention

[0003] For this reason, the present invention provides a mononuclear ruthenium (II) complex of 2,2':6',2''-terpyridine with dual electrochemiluminescence emission.

[0004] In the first aspect of the present invention, there is provided a mononuclear ruthenium (II) complex of 2,2':6',2''-terpyridine with dual electrochemiluminescence emission, and its chemical structure is as follows:

[0005] or

[0006]

[0007] wherein, R is a C1-C12 alkyl group or a C1-C12 ether alkyl group, and X is F, Cl, Br or I.

[0008] In the second aspect of the present invention, there is provided a method for preparing the mononuclear ruthenium (II) complex of 2,2':6',2''-terpyridine described in the present invention. This method includes: synthesizing the mononuclear ruthenium (II) complex [Ru(L1)(L2)] of 2,2':6',2''-terpyridine through the following one-step complexation reaction 2+ :

[0009]

[0010] Using raw material L2, a one-step complexation reaction with the ruthenium complex Ru(L1)Cl3 was conducted to generate the mononuclear 2,2′:6′,2″-terpyridine ruthenium(II) complex [Ru(L1)(L2)]. 2+ ;

[0011] The complexation reaction is carried out in an organic solvent.

[0012] A third aspect of the present invention provides a method for preparing the mononuclear 2,2′:6′,2″-terpyridine ruthenium(II) complex described herein, the method comprising: synthesizing the mononuclear 2,2′:6′,2″-terpyridine ruthenium(II) complex [Ru(L2)2] via the following one-step complexation reaction. 2+ :

[0013]

[0014] Using raw material L2, a one-step complexation reaction with reagent RuCl3 was conducted to generate the mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru(L2)2]. 2+ ;

[0015] The complexation reaction is carried out in an organic solvent.

[0016] Compared with the prior art, the beneficial technical effects of the present invention are as follows:

[0017] This invention designs and synthesizes a dual-emission metal complex luminescent material composed of a mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complex, and successfully applies it to the field of electrochemiluminescence. It can be applied to the field of electrochemiluminescence sensing and has broad application prospects. Attached Figure Description

[0018] Figure 1 Anodic electrochemiluminescence intensity diagrams of mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complexes [Ru(L1-1)(L2-1)] (PF6)2, [Ru(L1-2)(L2-2)] (PF6)2, [Ru(L2-1)2] (PF6)2 and [Ru(L2-2)2] (PF6)2.

[0019] Figure 2 Cathodoluminescence intensity diagrams of mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complexes [Ru(L1-1)(L2-1)] (PF6)2, [Ru(L1-2)(L2-2)] (PF6)2, [Ru(L2-1)2] (PF6)2 and [Ru(L2-2)2] (PF6)2. Detailed Implementation

[0020] Unless otherwise specified, the reagents used in the following examples are commercially available products of chemical grade purity. To more clearly explain the technical problems and solutions solved by this invention, the following specific embodiments provide further detailed descriptions. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the invention.

[0021] Example 1

[0022] Preparation of mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru(L1-1)(L2-1)] (PF6)2

[0023]

[0024] In a 100 mL round-bottom flask, Ru(L1-1)Cl3 (0.077 g, 0.12 mmol), L2-1 (0.059 g, 0.05 mmol), and ethylene glycol (10 mL) were added. The solution was a brownish-black turbid liquid. After reflux for 24 hours, the solution became a dark red turbid liquid. After cooling to room temperature, the solution was filtered through diatomaceous earth. The residue was repeatedly washed with ethylene glycol to obtain a clear dark red filtrate. 4 mL of saturated ammonium hexafluorophosphate solution was added to the filtrate, and the mixture was stirred at room temperature for 1 hour. A red solid precipitated. The solid was filtered, repeatedly washed with water, recrystallized from acetonitrile / water, filtered, washed with ethyl acetate and water, and dried. The yield was 50%. HRMS(ESI): calcdfor C 87 H 85 ClN6O4Ru [M+H] + , 1415.5457; found 1415.5457, calcd for C 87 H 85 ClN6O4Ru[M+H] 2+ , 707.2628, found, 707.7728.

[0025] Example 2

[0026] Preparation of mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru(L1-2)(L2-2)] (PF6)2

[0027]

[0028] In a 100 mL round-bottom flask, Ru(L1-2)Cl3 (0.078 g, 0.1 mmol), L2-2 (0.11 g, 0.07 mmol), and ethylene glycol (20 mL) were added. The solution was a brownish-black turbid liquid. After reflux for 24 hours, the solution became a dark red turbid liquid. After cooling to room temperature, the solution was filtered through diatomaceous earth. The residue was repeatedly washed with ethylene glycol to obtain a clear dark red filtrate. 4 mL of saturated ammonium hexafluorophosphate solution was added to the filtrate, and the mixture was stirred at room temperature for 1 hour. A red solid precipitated. The solid was filtered, recrystallized from acetonitrile / water, filtered again, washed with ethyl acetate and water, and dried. The yield was 80%. HRMS(ESI): calcd for C 90 H 91 ClN6O 13 Ru [M+H] + , 1601.5470; found 1601.5470, calcd for C 90 H 91 ClN6O 13 Ru [M+H] 2+ , 800.7735, found, 800.775.

[0029] Example 3

[0030] Preparation of mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru(L2-1)2] (PF6)2

[0031]

[0032] In a 100 mL round-bottom flask, RuCl3·3H2O (0.0298 g, 0.1 mmol), L2-1 (0.21 g, 0.2 mmol), and ethylene glycol (30 mL) were added. The solution was a brownish-black turbid liquid. After reflux for 24 hours, the solution became a dark red turbid liquid. After cooling to room temperature, the solution was filtered through diatomaceous earth. The residue was repeatedly washed with ethylene glycol to obtain a clear dark red filtrate. 4 mL of saturated ammonium hexafluorophosphate solution was added to the filtrate, and the mixture was stirred at room temperature for 1 hour. A red solid precipitated out. The solid was filtered, repeatedly washed with water, and purified by column chromatography (neutral alumina, eluent: dichloromethane / methanol). After drying, the yield was 45%. HRMS(ESI): calcd for C 118 H 112 Cl2N6O4Ru [M+H] 2+ , 1032.8182; found 1032.8182.

[0033] Example 4

[0034] Preparation of mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru(L2-2)2] (PF6)2

[0035]

[0036] In a 100 mL round-bottom flask, RuCl3·3H2O (0.0149 g, 0.05 mmol), L2-2 (0.1 g, 0.1 mmol), and ethylene glycol (20 mL) were added. The mixture was purged with nitrogen three times and refluxed for 24 hours. The solution changed from brown to dark red. The mixture was cooled to room temperature and filtered through diatomaceous earth. The residue was repeatedly washed with ethylene glycol. 6 mL of saturated ammonium hexafluorophosphate was added to the filtrate, and the mixture was stirred for 3 hours. The mixture was then filtered again. The solid was washed with water and ethyl acetate and dried to obtain a dark red solid with a yield of 32%. HRMS(ESI): calcd for C 122 H 120 Cl2N6O 16 Ru [M+H] 2+ , 1048.8627; found 1048.8627.

[0037] Example 5

[0038] Bare glassy carbon electrodes (GCEs) were polished with 1.0 μm and 0.3 μm alumina powders, then rinsed with distilled water and dried at room temperature. Subsequently, 2 μL of 2 mM dispersions of mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complexes DTM1, DTM2, DTM3, and DTM4 were drop-coated onto the GCEs and allowed to air dry to obtain modified GCE electrodes.

[0039] Using 500 μL of 0.2 M PBS (pH 7.0) containing 0.1 M potassium chloride and 60 mM tri-n-propylamine as the electrolyte, an electrochemiluminescence (ECL) analysis system was used. The modified GCE electrode was used as the working electrode, the Ag / AgCl electrode (containing saturated KCl solution) as the reference electrode, and the platinum wire electrode as the counter electrode. The voltage was set to 0–1.3 V, and the scan rate was 0.3 V s. -1 The photomultiplier tube had a high voltage of 650 V and a magnification stage of 4. Electrochemiluminescence measurements were performed, and the mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complexes DTM1, DTM2, DTM3, and DTM4 all exhibited electrochemiluminescence effects, such as... Figure 1 As shown.

[0040] Example 6

[0041] Bare glassy carbon electrodes (GCEs) were polished with 1.0 μm and 0.3 μm alumina powders, then rinsed with distilled water and dried at room temperature. Subsequently, 3 μL (5 mg / mL) solutions of mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complexes [Ru(L1-1)(L2-1)](PF6)2, [Ru(L1-2)(L2-2)](PF6)2, [Ru(L2-1)2](PF6)2, and [Ru(L2-2)2](PF6)2 were drop-coated onto the GCEs and allowed to air dry to obtain the corresponding modified GCE electrodes.

[0042] Using 500 μL of 0.2 M PBS (pH 7.0) containing 0.1 M potassium chloride and 60 mM tri-n-propylamine as the electrolyte, an electrochemiluminescence (ECL) analysis system was used. The modified GCE electrode was used as the working electrode, an Ag / AgCl electrode (containing saturated KCl solution) as the reference electrode, and a platinum wire electrode as the counter electrode. The voltage was set to 0–1.3 V, and the scan rate was 0.3 V s. -1 The photomultiplier tube had a high voltage of 650 V and a magnification stage of 4. Electrochemiluminescence measurements were performed. The mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complexes [Ru(L1-1)(L2-1)](PF6)2, [Ru(L1-2)(L2-2)](PF6)2, [Ru(L2-1)2](PF6)2, and [Ru(L2-2)2](PF6)2 all exhibited aggregation-induced electrochemiluminescence effects, such as... Figure 1 As shown.

[0043] Example 7

[0044] Bare glassy carbon electrodes (GCEs) were polished with 1.0 μm and 0.3 μm alumina powders, then rinsed with distilled water and dried at room temperature. Subsequently, 2 μL of 2 mM dispersions of mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complexes [Ru(L1-1)(L2-1)](PF6)2, [Ru(L1-2)(L2-2)](PF6)2, [Ru(L2-1)2](PF6)2, and [Ru(L2-2)2](PF6)2 were drop-coated onto the GCEs and allowed to air dry to obtain the corresponding modified GCE electrodes.

[0045] Using 500 μL of 0.2 M PBS (pH 7.0) containing 0.1 M potassium chloride and 60 mM potassium persulfate as the electrolyte, an electrochemiluminescence (ECL) analysis system was used. The modified GCE electrode was used as the working electrode, the Ag / AgCl electrode (containing saturated KCl solution) as the reference electrode, and the platinum wire electrode as the counter electrode. The voltage was set to -1.3 V and the scan rate to 0.3 V s. -1 The photomultiplier tube had a high voltage of 550 V and a magnification stage of 3. Electrochemiluminescence measurements were performed. The mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complexes [Ru(L1-1)(L2-1)](PF6)2, [Ru(L1-2)(L2-2)](PF6)2, [Ru(L2-1)2](PF6)2, and [Ru(L2-2)2](PF6)2 all exhibited electrochemiluminescence effects, such as... Figure 2 As shown.

[0046] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the principles and spirit of the present invention are included within the protection scope of the present invention.

Claims

1. A mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complex with electrochemiluminescence dual emission properties, characterized in that, The chemical structure of the mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complex is as follows: or ， Wherein, R is a C1-C12 alkyl or C1-C12 ether alkyl, and X is F, Cl, Br or I.

2. The method for synthesizing the mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complex according to claim 1, characterized in that, The method for synthesizing the mononuclear 2,2′:6′,2″-terpyridine ruthenium(II) complex comprises: synthesizing the mononuclear 2,2′:6′,2″-terpyridine ruthenium(II) complex [Ru(L1)(L2)] via the following one-step complexation reaction. 2+ : ； Using raw material L2, a one-step complexation reaction with the ruthenium complex Ru(L1)Cl3 was conducted to generate the mononuclear 2,2′:6′,2″-terpyridine ruthenium(II) complex [Ru(L1)(L2)]. 2+ ; The complexation reaction is carried out in an organic solvent.

3. The method for synthesizing the mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complex according to claim 1, characterized in that, The method for synthesizing the mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complex comprises: synthesizing the mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru(L2)2] via the following one-step complexation reaction. 2+ : ； Using raw material L2, a one-step complexation reaction with reagent RuCl3 was conducted to generate the mononuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru(L2)2]. 2+ ; The complexation reaction is carried out in an organic solvent.

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