An anionic iridium complex that can be used for oxygen sensing, and its preparation and application

Abstract

The invention discloses an anionic type iridium complex for oxygen sensing, and a preparation method and the application of the anionic type iridium complex. The anionic type iridium complex can be expressed by a general formula: [Ir(C-N)2(CN)2]-nBuN+, wherein a counter ion is a tetrabutyl ammonium ion nBuN+; a C-N ligand is selected from 2-phenylpyridine (ppy), 2,4-difluoro phenylpyridine (dfppy), 2-thiophene-quinoline (thq), 2-phenyl-quinoline (bqu) and 1-phenylisoquinoline (piq), and a molecular structure formula of the C-N ligand is as shown in the description. A preparation process of the anionic type iridium complex is simple and is easy to operate. The anionic type iridium complex can be used in the field of the oxygen sensing and has higher response sensitivity on oxygen and better selectivity; the anionic type iridium complex can also be used in the field of bio-sensing, can be used for carrying out oxygen detection in a cell or a living body and has good biocompatibility; the anionic type iridium complex has the characteristics of long phosphorescence lifetime, large Stokes shift, high light stability and the like, has relatively-sensitive luminous intensity on the oxygen and is a good oxygen probe.

Description

technical field

[0001] The invention belongs to the technical field of transition metal complexes and luminescent materials, and in particular relates to the preparation of an anionic iridium complex with oxygen response and its application in the fields of cell labeling, imaging and oxygen sensing. technical background

[0002] In recent years, since heavy metal atoms in transition metal complexes (such as iridium, platinum, osmium, ruthenium, etc.) 6 , d 8 and d 10 The electronic structure can increase the spin-orbit coupling, add some singlet properties to the original triplet state, increase the intersystem crossing ability, and make the spin-forbidden triplet excited state transition to the ground state T 1 →S 0 It becomes partially allowed, so that phosphorescence can be emitted smoothly, the luminous efficiency is improved, and the internal quantum efficiency can reach 100%, making these complexes more and more used in OLEDs, electrochemiluminescence, photovoltaic ...

Examples

Embodiment 1

[0029] Embodiment 1, anionic iridium complex [Ir(dfppy) 2 (EN) 2 ] - wxya + preparation.

[0030] (1) Determine and prepare the C^N ligand. The C^N ligand is determined to be 2,4-difluorophenylpyridine (dfppy), which can be prepared according to the existing preparation methods in the prior art.

[0031] The reaction formula for preparing the monomer 2,4-difluoro-2-phenylpyridine is shown below.

[0032]

[0033] The specific process is: weigh 2-bromopyridine (1.0g, 6.37mmol), 2,4-difluorophenylboronic acid (1.03g, 6.5mmol) and tetrakis(triphenylphosphine)palladium (0.370g, 0.32mmol) and add In a 50mL two-necked bottle, vacuumize and blow nitrogen for three times, then inject toluene (9mL) and saturated K 2 CO 3 (aq) (3 mL), ethanol (3 mL), reflux at 80° C. for 15 hours. Cool to room temperature, extract with dichloromethane and distilled water, combine the organic phases, and spin dry under reduced pressure to obtain 1.12 g of the product with a yield of 90%. 1H NM...

Embodiment 2

[0041] Embodiment 2, anion iridium complex [Ir(ppy) 2 (EN) 2 ] - wxya + Preparation of:

[0042] (1) Determine and prepare the C^N ligand, confirm that the C^N ligand is 2-phenylpyridine (ppy), which can be prepared according to the existing preparation methods in the prior art.

[0043] (2) Anionic iridium complex [Ir(ppy) 2 (EN) 2] - wxya + Preparation of:

[0044] (A) Dimer iridium complex (C^N) 2 Ir(μ-Cl) 2 Ir(C^N) 2 The synthesis of 2-phenylpyridine dichloro bridge, the specific reaction is: weigh IrCl 3 .3H 2 O (528mg, 1.50mmol) and 2-phenylpyridine (ppy) (864mg, 4.50mmol) were added into a 50mL two-neck flask, and nitrogen was circulated three times under vacuum. Ethylene glycol ether (15 mL) and distilled water (3 mL) were injected with a syringe, the reaction temperature was 100° C., and the mixture was stirred under reflux for 36 hours under a nitrogen atmosphere until a precipitate formed. After stopping the reaction, cool to room temperature, filter t...

Embodiment 3

[0047] Embodiment 3, anion iridium complex [Ir(thq) 2 (EN) 2 ] - wxya + preparation.

[0048] (1) Determine and prepare the C^N ligand, confirm that the C^N ligand is 2-thienyl quinoline (thq), which can be prepared according to the existing preparation methods in the prior art.

[0049] (2) Anionic iridium complexes [Ir(thq) 2 (EN) 2 ] - wxya + Preparation of:

[0050] (A) Dimer iridium complex (C^N) 2 Ir(μ-Cl) 2 Ir(C^N) 2 The synthesis of, that is, the synthesis of 2-thiophene-quinoline dichloro bridge, its specific synthesis method is: weigh IrCl 3 ·3H 2 O (500mg, 1.42mmol) and 2-thiophene-quinoline (thq) (600.0mg, 2.84mmol) were added into a 50mL two-neck flask, and vacuum pumped and nitrogen was circulated three times. Ethylene glycol ether (12 mL) and distilled water (4 mL) were injected with a syringe, the reaction temperature was 120° C., and the mixture was refluxed and stirred for 36 hours under a nitrogen atmosphere until a precipitate formed. After st...

technical field

[0001] The invention belongs to the technical field of transition metal complexes and luminescent materials, and in particular relates to the preparation of an anionic iridium complex with oxygen response and its application in the fields of cell labeling, imaging and oxygen sensing. technical background

[0002] In recent years, since heavy metal atoms in transition metal complexes (such as iridium, platinum, osmium, ruthenium, etc.) 6 , d 8 and d 10 The electronic structure can increase the spin-orbit coupling, add some singlet properties to the original triplet state, increase the intersystem crossing ability, and make the spin-forbidden triplet excited state transition to the ground state T 1 →S 0 It becomes partially allowed, so that phosphorescence can be emitted smoothly, the luminous efficiency is improved, and the internal quantum efficiency can reach 100%, making these complexes more and more used in OLEDs, electrochemiluminescence, photovoltaic ...

Examples

Embodiment 1

[0029] Embodiment 1, anionic iridium complex [Ir(dfppy) 2 (EN) 2 ] - wxya + preparation.

[0030] (1) Determine and prepare the C^N ligand. The C^N ligand is determined to be 2,4-difluorophenylpyridine (dfppy), which can be prepared according to the existing preparation methods in the prior art.

[0031] The reaction formula for preparing the monomer 2,4-difluoro-2-phenylpyridine is shown below.

[0032]

[0033] The specific process is: weigh 2-bromopyridine (1.0g, 6.37mmol), 2,4-difluorophenylboronic acid (1.03g, 6.5mmol) and tetrakis(triphenylphosphine)palladium (0.370g, 0.32mmol) and add In a 50mL two-necked bottle, vacuumize and blow nitrogen for three times, then inject toluene (9mL) and saturated K 2 CO 3 (aq) (3 mL), ethanol (3 mL), reflux at 80° C. for 15 hours. Cool to room temperature, extract with dichloromethane and distilled water, combine the organic phases, and spin dry under reduced pressure to obtain 1.12 g of the product with a yield of 90%. 1H NM...

Embodiment 2

[0041] Embodiment 2, anion iridium complex [Ir(ppy) 2 (EN) 2 ] - wxya + Preparation of:

[0042] (1) Determine and prepare the C^N ligand, confirm that the C^N ligand is 2-phenylpyridine (ppy), which can be prepared according to the existing preparation methods in the prior art.

[0043] (2) Anionic iridium complex [Ir(ppy) 2 (EN) 2] - wxya + Preparation of:

[0044] (A) Dimer iridium complex (C^N) 2 Ir(μ-Cl) 2 Ir(C^N) 2 The synthesis of 2-phenylpyridine dichloro bridge, the specific reaction is: weigh IrCl 3 .3H 2 O (528mg, 1.50mmol) and 2-phenylpyridine (ppy) (864mg, 4.50mmol) were added into a 50mL two-neck flask, and nitrogen was circulated three times under vacuum. Ethylene glycol ether (15 mL) and distilled water (3 mL) were injected with a syringe, the reaction temperature was 100° C., and the mixture was stirred under reflux for 36 hours under a nitrogen atmosphere until a precipitate formed. After stopping the reaction, cool to room temperature, filter t...

Embodiment 3

[0047] Embodiment 3, anion iridium complex [Ir(thq) 2 (EN) 2 ] - wxya + preparation.

[0048] (1) Determine and prepare the C^N ligand, confirm that the C^N ligand is 2-thienyl quinoline (thq), which can be prepared according to the existing preparation methods in the prior art.

[0049] (2) Anionic iridium complexes [Ir(thq) 2 (EN) 2 ] - wxya + Preparation of:

[0050] (A) Dimer iridium complex (C^N) 2 Ir(μ-Cl) 2 Ir(C^N) 2 The synthesis of, that is, the synthesis of 2-thiophene-quinoline dichloro bridge, its specific synthesis method is: weigh IrCl 3 ·3H 2 O (500mg, 1.42mmol) and 2-thiophene-quinoline (thq) (600.0mg, 2.84mmol) were added into a 50mL two-neck flask, and vacuum pumped and nitrogen was circulated three times. Ethylene glycol ether (12 mL) and distilled water (4 mL) were injected with a syringe, the reaction temperature was 120° C., and the mixture was refluxed and stirred for 36 hours under a nitrogen atmosphere until a precipitate formed. After st...

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