Binuclear 2, 2 ': 6', 2 ''-terpyridyl ruthenium (II) complex with dual-emission electrochemical luminescence performance

Abstract

The invention discloses a binuclear 2, 2 ': 6', 2 ''-terpyridyl ruthenium (II) complex with dual-emission electrochemical luminescence performance, and the chemical structural formula is shown in the specification. According to the complex, 2, 2 ': 6', 2 ''-terpyridyl ligands with different substituent groups are chelated with two ruthenium (II) ions in an NNN coordination mode, and a metal complex illuminant composed of a binuclear 2, 2 ': 6', 2 ''-terpyridyl ruthenium (II) complex is synthesized. The complex provided by the invention has strong electrochemical luminescence performance, can be applied to the sensing field, has wide application prospects, provides reference for designing the binuclear tridentate ruthenium (II) complex with good electrochemical luminescence performance, and expands the potential application of the binuclear tridentate ruthenium (II) complex in related fields.

Description

Technical Field

[0001] This invention relates to the field of electrochemiluminescence, and more particularly to a binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex with dual-emission electrochemiluminescence properties. Background Technology

[0002] Ruthenium(II) complexes possess excellent chemical, electrochemical, and photophysical properties, and are widely used in electrochemiluminescence (ECL) research. Among them, ter(bipyridine)ruthenium(II) and its derivatives, as classic ECL emitters, are among the most widely studied ECL systems due to their good ECL characteristics, water solubility, redox reversibility, and electrochemical performance. However, traditional ter(bipyridine)ruthenium(II) complexes suffer from aggregation-induced quenching effects, which significantly impair ECL efficiency. Furthermore, there are only a few reports on ruthenium metal complexes with aggregation-induced ECL properties. Therefore, developing binuclear 2,2′:6′,2″-terbipyridineruthenium(II) complexes with aggregation-induced ECL properties is of great significance. Summary of the Invention

[0003] Therefore, the present invention provides a binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex with dual-emission electrochemiluminescence properties.

[0004] In a first aspect, the present invention provides a binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex with dual-emission electrochemiluminescence properties, the chemical structure of which is as follows:

[0005]

[0006] Wherein, R is a C1-C12 alkyl, C1-C12 ether alkyl, or C1-C12 olefin alkyl.

[0007] A second aspect of the present invention provides a method for preparing the binuclear 2,2′:6′,2″-terpyridine ruthenium(II) complex described herein, the method comprising: synthesizing the binuclear 2,2′:6′,2″-terpyridine ruthenium(II) complex [Ru2(L1)(L2)2] via the following one-step complexation reaction. 4+ :

[0008]

[0009] Using raw material L1, a one-step complexation reaction with the metal complex Ru(L2)Cl3 is conducted to generate the binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru2(L1)(L2)2]. 4+ ;

[0010] The complexation reaction is carried out in an organic solvent.

[0011] Compared with the prior art, the beneficial technical effects of the present invention are as follows:

[0012] This invention designs and synthesizes a dual-emission metal complex luminescent material composed of a binuclear 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

[0013] Figure 1 :Binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru2(L1)(L2-1)2] 4+ (PF6)4、[Ru2(L1)(L2-2)2] 4+ (PF6)4 and [Ru2(L1)(L2-3)2] 4+ Anodic electrochemiluminescence intensity diagram of (PF6)4.

[0014] Figure 2 :Binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru2(L1)(L2-1)2] 4+ (PF6)4、[Ru2(L1)(L2-2)2] 4+ (PF6)4 and [Ru2(L1)(L2-3)2] 4+ Cathodic electrochemiluminescence intensity diagram of (PF6)4. Detailed Implementation

[0015] 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.

[0016] Example 1

[0017] Binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru2(L1)(L2-1)2] 4+ Preparation of (PF6)4

[0018]

[0019] In a 100 mL round-bottom flask, L1 (0.1 g, 0.1 mmol), Ru(L2-1)Cl3 (0.129 g, 0.2 mmol), and ethylene glycol (40 mL) were added. The mixture was purged with nitrogen three times and heated to 180 °C for 24 hours, resulting in a dark red solution. The solution was cooled to room temperature and filtered through diatomaceous earth. 20 mL of saturated ammonium hexafluorophosphate solution was added to the filtrate, and the mixture was stirred at room temperature for 1 hour. The solution was filtered again, and the solid was washed with ethanol, recrystallized from methanol / ethyl acetate, and dried to obtain a dark red solid in 80% yield. HRMS(ESI):calcd for C 124 H 104 N 12 O4Ru2[M+H] 2+ , 1353.0975; found 1353.0408, calcd forC 124 H 104 N 12 O4Ru2[M+H] 4+ 507.4115, found 507.4115.

[0020] Example 2

[0021] Binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru2(L1)(L2-2)2] 4+ Preparation of (PF6)4

[0022]

[0023] In a 100 mL round-bottom flask, L1 (0.1 g, 0.1 mmol), Ru(L2-2)Cl3 (0.1416 g, 0.2 mmol), and ethylene glycol (50 mL) were added. The mixture was purged with nitrogen three times and heated to 180 °C for 24 hours, yielding a dark red solution. The solution was cooled to room temperature and filtered through diatomaceous earth. 20 mL of saturated ammonium hexafluorophosphate solution was added to the filtrate, and the mixture was stirred at room temperature for 1 hour. The solution was filtered again, and the solid was washed with ethanol, recrystallized from methanol / ethyl acetate, and dried to obtain a dark red solid with a yield of 55%. HRMS(ESI):calcd for C 126 H 108 N 12 O 10 Ru2[M+H] 2+ , 1366.7519; found 1366.7519, calcd forC 124 H 104 N 12 O4Ru2[M+H] 3+991.1679, found 991.1679, calcd for C 124 H 104 N 12 O4Ru2[M+H] 4+ 683.3759, found 683.3759.

[0024] Example 3

[0025] Binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru2(L1)(L2-3)2] 4+ Preparation of (PF6)4

[0026]

[0027] In a 100 mL round-bottom flask, L1 (0.1 g, 0.1 mmol), Ru(L2-3)Cl3 (0.1416 g, 0.2 mmol), and ethylene glycol (50 mL) were added. The mixture was purged with nitrogen three times and heated to 180 °C for 24 hours, resulting in a dark red solution. The solution was cooled to room temperature and filtered through diatomaceous earth. 20 mL of saturated ammonium hexafluorophosphate solution was added to the filtrate, and the mixture was stirred at room temperature for 1 hour. The solution was filtered again, and the solid was washed with ethanol, recrystallized from methanol:ethyl acetate, and dried to obtain a dark red solid with a yield of 71%. HRMS(ESI):calcd for C 124 H 104 N 12 O4Ru2[M+H] 3+ 812.4531, found 812.4531, calcd forC 124 H 104 N 12 O4Ru2[M+H] 4+ 609.3398, found 609.3398.

[0028] Example 4

[0029] The bare glassy carbon electrode (GCE) was 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) of the binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru2(L1)(L2-1)2] was added. 4+ (PF6)4、[Ru2(L1)(L2-2)2] 4+ (PF6)4 and [Ru2(L1)(L2-3)2] 4+ (PF6)4 solution was drop-coated onto GCE and allowed to dry naturally to obtain the corresponding modified GCE electrode.

[0030] 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 0–1.1 V, and the scan rate was 0.3 V / s. -1 The photomultiplier tube was set to 700 V with 4 amplification stages. Electrochemiluminescence measurements were performed on the binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru2(L1)(L2-1)2]. 4+ (PF6)4、[Ru2(L1)(L2-2)2] 4+ (PF6)4 and [Ru2(L1)(L2-3)2] 4+ (PF6)4 all exhibited aggregation-induced electrochemiluminescence effects, such as Figure 1 As shown.

[0031] Example 5

[0032] The bare glassy carbon electrode (GCE) was 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) of the binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru2(L1)(L2-1)2] was added. 4+ (PF6)4、[Ru2(L1)(L2-2)2] 4+ (PF6)4 and [Ru2(L1)(L2-3)2] 4+ (PF6)4 dispersion was drop-coated onto GCE and allowed to dry naturally to obtain the modified GCE electrode.

[0033] 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, 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 -1.2 V and the scan rate to 0.3 V / s. -1 The photomultiplier tube was set to 600 V with 3 amplification stages. Electrochemiluminescence measurements were performed on the binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru2(L1)(L2-1)2]. 4+ (PF6)4、[Ru2(L1)(L2-2)2] 4+(PF6)4 and [Ru2(L1)(L2-3)2] 4+ (PF6)4 all exhibit electrochemiluminescence effects, such as Figure 2 As shown.

[0034] 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 binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex with dual-emission electrochemiluminescence properties, characterized in that, The chemical structure of the binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex is as follows: ， Wherein, R is a C1-C12 alkyl, C1-C12 ether alkyl, or C1-C12 olefin alkyl.

2. The method for synthesizing the binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex according to claim 1, characterized in that, The method for synthesizing the binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex comprises: synthesizing the binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru2(L1)(L2)2] via the following one-step complexation reaction. 4+ : ， Using raw material L1, a one-step complexation reaction with the metal complex Ru(L2)Cl3 is conducted to generate the binuclear 2,2′:6′,2″-terpyridineruthenium(II) complex [Ru2(L1)(L2)2]. 4+ ; The complexation reaction is carried out in an organic solvent.

Images