Trinuclear 2, 2 ': 6', 2 ''-terpyridyl metal complex with cathode aggregation-induced electrochemiluminescence and synthesis method of trinuclear 2, 2 ': 6', 2 ''-terpyridyl metal complex

Abstract

The invention discloses a trinuclear 2, 2 ': 6', 2 ''-terpyridyl metal complex with cathode aggregation-induced electrochemiluminescence and a synthesis method thereof, and the chemical structural formula of the trinuclear 2, 2 ': 6', 2 ''-terpyridyl metal complex is # imgabs0 #. The trinuclear 2, 2 ': 6', 2 ''-terpyridyl metal complex is prepared by chelating 4 '-(3, 4-dimethoxyphenyl)-2, 2': 6 ', 2 ''-terpyridyl and 1, 3, 5-tris [4-(2, 2': 6 ', 2''-pyridine-4'-yl) phenyl] benzene with Ir (III) or Ru (II) ions in an NNN coordination manner, and respectively synthesizing the trinuclear 2, 2 ': 6', 2 ''-terpyridyl metal complex with cathode aggregation-induced electrochemiluminescence. The trinuclear 2, 2 ': 6', 2 ''-terpyridyl metal complex has aggregation-induced electrochemiluminescence, the metal iridium complex has strong cathode aggregation-induced electrochemiluminescence, and theoretical and application support is provided for the fields of analysis and detection, electrochemiluminescence and the like.

Description

Technical Field

[0001] The invention relates to the field of aggregation-induced electrochemiluminescence, and in particular to a trinuclear 2,2':6',2"-terpyridine metal complex with cathode aggregation-induced electrochemiluminescence and a synthesis method thereof. Background Art

[0002] De Cola's team formally proposed the new concept of aggregation-induced electrochemiluminescence in 2017, which shows that aggregation-induced emission also exists in electrochemiluminescence systems. This discovery opened up a new field of electrochemiluminescence research and stimulated research enthusiasm for finding luminescent molecules with aggregation-induced electrochemiluminescence properties. In recent years, it has been reported that Ru (II) complexes and Ir (III) complexes exhibit excellent electroluminescence in the aggregated state. However, there are only a few reports on Ru (II) complexes and Ir (III) complexes with aggregation-induced electrochemiluminescence properties, and trinuclear 2,2′:6′,2″-terpyridine metal complexes with aggregation-induced electrochemiluminescence have never been reported. Therefore, it is still of great significance to discover new molecules with aggregation-induced electrochemiluminescence properties. Summary of the invention

[0003] To this end, the present invention provides a trinuclear 2,2':6',2"-terpyridine metal complex having cathode aggregation-induced electrochemiluminescence.

[0004] The present invention provides a trinuclear 2,2′:6′,2″-terpyridine metal complex with cathode aggregation-induced electrochemiluminescence, and its chemical structure is as follows:

[0005]

[0006] in,

[0007] M is Ir(III) or Ru(II),

[0008] R1 and R2 are each independently hydrogen, C1-C8 alkyl, C1-C8 alkene alkyl or C1-C8 ether alkyl.

[0009] The present invention provides a method for preparing the trinuclear 2,2′:6′,2″-terpyridine metal complex of the present invention, the method comprising: synthesizing the trinuclear 2,2′:6′,2″-terpyridine metal complex by the following one-step complexation reaction:

[0010]

[0011]

[0012] The raw material 1 is used to undergo a one-step complexation reaction with the raw material 2 and the raw material 3 to generate the corresponding trinuclear 2,2':6',2"-terpyridine metal iridium complex and trinuclear 2,2':6',2"-terpyridine metal ruthenium complex.

[0013] The complexing reaction is carried out in an organic solvent.

[0014] Compared with the prior art, the beneficial technical effects of the present invention are:

[0015] The present invention designs and synthesizes a metal complex luminescent body composed of a trinuclear 2,2′:6′,2″-terpyridine metal complex, wherein the trinuclear 2,2′:6′,2″-terpyridine metal iridium complex has strong cathode aggregation-induced electrochemiluminescence and is successfully used in the field of aggregation-induced electrochemiluminescence, and can be applied to the field of sensing, with broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 : Electrochemiluminescence intensity diagram of trinuclear 2,2′:6′,2″-terpyridine metal iridium complex and trinuclear 2,2′:6′,2″-terpyridine metal ruthenium complex in the aggregated state. DETAILED DESCRIPTION

[0017] Unless otherwise specified, the reagents involved in the following examples are commercial products with a purity of chemical grade. In order to more clearly explain the technical problems and technical solutions solved by the present invention, the specific embodiments described below further describe the present invention in detail. The specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0018] Example 1

[0019] Preparation of Trinuclear 2,2′:6′,2″-terpyridine Iridium Complex Ir3(1)

[0020]

[0021] 1 (0.05 mmol, 0.05 g) and 2 (0.15 mmol, 0.1 g) were dissolved in 17 mL of ethylene glycol, heated to reflux under nitrogen protection, reacted for 2 h, and cooled to room temperature. The filtrate was filtered and collected, and an excess of saturated aqueous solution of ammonium hexafluorophosphate was added. Water was added to promote precipitation, stirred for more than 1 h, filtered, and the solid was washed with water and ethanol, and dried under high vacuum to obtain 0.0685 g of yellow solid, with a yield of 38.16%.

[0022] HRMS (ESI) m / z calcd for C 138 H 102 Ir318 O6 ([M] 9+ ): 298.3014; found:298.3014 .

[0023] Example 2

[0024] Preparation of Trinuclear 2,2′:6′,2″-terpyridine Ruthenium Complex Ru3(1)

[0025]

[0026] 1 (0.1 g, 0.1 mmol, 3 eq.) and 3 (0.173 g, 0.3 mmol, 1 eq.) were dissolved in 27 mL of ethylene glycol, 14 drops of n-ethylmorpholine were added, and the mixture was heated under reflux for 24 h under nitrogen protection, and the resulting solution was cooled to room temperature. The mixture was filtered, and the filtrate was collected. An excess of saturated aqueous solution of ammonium hexafluorophosphate was added to the filtrate, and 40 mL of deionized water was added (to promote the formation of precipitation), and the mixture was filtered, washed with a large amount of ethanol and water, and dried under high vacuum for more than 24 h to obtain a black-red solid with a yield of 0.2542 g and a yield of 77.41%.

[0027] HRMS (ESI) m / z calcd for C 138 H 102 N 18 O6Ru3 ([M] 6+ ): 402.0893; found:402.0867.

[0028] Example 3

[0029] The bare glassy carbon electrode (GCE) was polished with 1.0 μm and 0.3 μm alumina powders. The electrode was then rinsed with distilled water and dried at room temperature. Subsequently, 4 μL of 2 mg mL -1 The trinuclear 2,2′:6′,2″-terpyridine metal complex Ir3(1) or Ru3(1) solution was drop-coated on GCE and dried naturally to obtain a modified GCE electrode.

[0030] 3 mL of 0.2 M PBS (pH 7.4) solution containing 0.1 M potassium chloride and 60 mM potassium persulfate was used as the electrolyte. Then, on the electrochemiluminescence (ECL) analysis system, the modified GCE electrode was used as the working electrode, the Ag / AgCl (containing saturated KCl solution) electrode was used as the reference electrode, and the platinum wire electrode was used as the counter electrode. The voltage was set to -1.1 ~ 0 V, and the scan rate was 0.3 V s -1, the photomultiplier tube high voltage is 700 V, the amplification level is 3, and electrochemiluminescence measurement is performed. The trinuclear 2,2′:6′,2″-terpyridine metal iridium complex Ir3(l) and the trinuclear 2,2′:6′,2″-terpyridine metal ruthenium complex Ru3(l) both show aggregation-induced electrochemiluminescence effect under cathode potential scanning, such as Figure 1 shown.

[0031] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any changes, equivalent substitutions and improvements made within the principles and spirit of the present invention are included in the protection scope of the present invention.

Claims

1. A trinuclear 2,2′:6′,2″-terpyridine metal complex with cathode aggregation-induced electrochemiluminescence and a method for synthesizing the same, characterized in that: The chemical structure of the trinuclear 2,2′:6′,2″-terpyridine metal complex is as follows: ,in, M is Ir(III) or Ru(II), R1 and R2 are each independently hydrogen, C1-C8 alkyl, C1-C8 alkene alkyl or C1-C8 ether alkyl.

2. The method for synthesizing the trinuclear 2,2′:6′,2″-terpyridine metal complex according to claim 1, characterized in that The method for preparing a trinuclear 2,2′:6′,2″-terpyridine metal complex comprises: synthesizing the trinuclear 2,2′:6′,2″-terpyridine metal complex by the following one-step complexation reaction: ; ， Raw material 1 is used to generate a corresponding trinuclear 2,2':6',2"-terpyridine metal iridium complex and trinuclear 2,2':6',2"-terpyridine metal ruthenium complex through a one-step complex reaction with raw material 2 and raw material 3; The complexing reaction is carried out in an organic solvent.

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