A kind of pt(ii)-m(i) heterotrinuclear complex and its preparation method and use

A technology of complexes and complexes, applied in the field of Pt2M heterotrinuclear metal organic alkyne complexes and their preparation, to achieve the effect of sensitive photochromic response

Active Publication Date: 2021-09-21
FUJIAN INST OF RES ON THE STRUCTURE OF MATTER CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

So far, no photochromic phenomenon that can be spontaneously restored has been reported, that is, the use of single-wavelength light irradiation as the only external stimulus can achieve photochromic reversible switching between two different color states.

Method used

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  • A kind of pt(ii)-m(i) heterotrinuclear complex and its preparation method and use
  • A kind of pt(ii)-m(i) heterotrinuclear complex and its preparation method and use
  • A kind of pt(ii)-m(i) heterotrinuclear complex and its preparation method and use

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0055] Example 1: Pt 2 Au complex [Pt 2 Au(μ-dpmp) 2 (C≡CC 6 h 5 ) 4 ](ClO 4 ) (Complex 1) Preparation

[0056] Add [Au(tht) 2 ](ClO 4 ) (23.6mg, 0.05mmol) was stirred until the solid was completely dissolved, and then stirred for another 5min. The solution continues to add Pt(PPh 3 ) 2 (C≡CPh) 2 (92.2mg, 0.1mmol), the platinum complex dissolved rapidly, the color of the solution changed from colorless or light to light yellow, stirred at room temperature for 4h. The solution was concentrated to 2 mL, separated on a silica gel column, and eluted with dichloromethane-acetone (10:1).

[0057] Yield: 83%. Elemental Analysis C 96 h 78 AuClO 4 P 6 Pt 2 Calculated: C, 54.80; H, 3.74. Measured: C, 54.73; H, 3.78. ESI-MS (%): 2004.9 (100) [M-ClO 4 ] + .Proton NMR spectrum (CD 2 Cl 2 ,ppm):7.86-7.80(m,12H),7.72-7.67(m,8H),7.40-7.33(m,12H),7.17-7.11(m,6H),7.05-6.81(m,24H),6.47 -6.46(d, 4H, J=7.4Hz), 6.28-6.26(d, 4H, J=7.0Hz), 4,40-4.23(m, 8H). Nuclear Magnetic Reso...

Embodiment 2

[0058] Example 2: Pt 2 Ag complex [Pt 2 Ag(μ-dpmp) 2 (C≡CC 6 h 5 ) 4 ](ClO 4 ) (complex 2) preparation

[0059] Synthetic method is similar to embodiment 1, difference is to adopt Ag(tht)(ClO 4 ) instead of [Au(tht) 2 ](ClO 4 ).

[0060] Yield: 79%. Elemental Analysis C 96 h 78 AgClO 4 P 6 Pt 2 Calculated: C, 57.22; H, 3.90. Measured: C, 57.19; H, 3.96. ESI-MS (%): 1915.6 (100) [M-ClO 4 ] + .Proton NMR spectrum (CD 2 Cl 2,ppm):7.80-7.73(m,12H),7.60–7.55(m,8H),7.40-7.30(m,12H),7.21-7.16(m,6H),7.06–7.00(m,12H),6.93 -6.84(m,12H),6.58-6.56(d,4H,J=7.2Hz),6.27–6.25(d,4H,J=7.1Hz),3.97–3.90(m,4H),3.74–3.69(m ,4H). Nuclear Magnetic Resonance Phosphorus Spectrum (CD 2 Cl 2 ,ppm): 10.9(t,4P,J P-P =37.4Hz,J Pt-P =266Hz), 13.0 (m, 2P, J P-P =43.0HZ,J Ag-P =496Hz). Infrared spectrum (KBr, cm -1 ): 2104(w), 1103(s).

Embodiment 3

[0061] Example 3: Pt 2 Cu complex [Pt 2 Cu(μ-dpmp) 2 (C≡CC 6 h 5 ) 4 ](ClO 4 ) (complex 3) preparation

[0062] Synthetic method is similar to embodiment 1, just adopts [Cu(MeCN) 4 ](ClO 4 ) instead of [Au(tht) 2 ](ClO 4 ).

[0063] Yield: 75%. Elemental Analysis C 96 h 78 ClCuO 4 P 6 Pt 2 ·H 2 O calculated value: C, 57.98; H, 4.05. Measured value: C, 58.04; H, 4.12. High resolution mass spectrum m / z (%): 1870.3123 (100) [M-ClO 4 ] + , calculated value: 1870.3124. H NMR spectrum (CD 2 Cl 2 ,ppm):8.02–7.98(m,4H),7.89–7.84(m,8H),7.52-7.49(t,4H,J=7.3Hz),7.44-7.35(m,10H),7.26–7.17(m ,12H),7.13–7.10(t,4H,J=7.5Hz),7.03–7.00(t,8H,J=7.6Hz),6.93–6.81(m,8H),6.69–6.65(t,4H,J =7.8Hz),6.53–6.51(d,4H,J=7.2Hz),6.04–6.02(d,4H,J=7.9Hz),3.95–3.80(m,4H),3.71–3.63(m,4H) . Nuclear Magnetic Resonance Phosphorus Spectrum (CD 2 Cl 2 ,ppm): 11.2(t,4P,J P-P =37.2Hz,J Pt-P =2548Hz), 13.4(m,2P,J P-P =41.0Hz). Infrared spectrum (KBr, cm -1 ): 2115(w), 1101(s).

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Abstract

The present invention relates to a Pt 2 M heterotrinuclear metal organic alkyne complex, its structure is as shown in the following formula (I): [Pt 2 M(μ‑PR 2 CH 2 PRCH 2 PR 2 ) 2 (C≡CR') 2 (C≡CR") 2 ] + m A m‑ ; (I) wherein, μ represents bridge connection; PR 2 CH 2 PRCH 2 PR 2 It is a kind of tridentate phosphine ligand; the subscript numbers of letters indicate the number of groups. In addition, the present invention also provides its preparation method and use. The complex has phosphorescence emission, and the color distribution of the emitted light is wide, ranging from blue-green to orange-red, and can be used as a photoluminescence material in the fields of display, illumination, sensing and biomarking. Among them, the copper complex also has self-recovery photochromic properties. The colorless or light-colored state is rapidly transformed into a dark state by ultraviolet light irradiation, and the original colorless or light-colored state is gradually restored when the ultraviolet light irradiation is stopped. This self-recovery photochromic phenomenon has important application value in the fields of anti-counterfeiting and information encryption and decryption.

Description

technical field [0001] The invention belongs to the technical field of photochromic materials, in particular to a Pt 2 M (M=Cu, Ag, Au) heterotrinuclear metal organic alkyne complex and its preparation method and use. Background technique [0002] Photochromism means that the molecular structure of a substance will change under the irradiation of light of a certain wavelength, which will lead to a corresponding change in its absorption peak of light, that is, the color, and this change is generally reversible. Photochromic substances typically switch reversibly between two stable or metastable states with different electronic absorption spectra, and the switch in at least one direction is triggered by light. Due to the different electronic structures and molecular structures, the two stable or metastable states often exhibit different colors and various physical properties such as light, electricity, and magnetism. According to the composition and structure of photochromic...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F19/00C09K11/06
CPCC07F15/0086C09K11/06C09K2211/185C09B57/10C09K9/02C07F15/0013C09K2211/1007C09K2211/1014C09K2211/188
Inventor 陈忠宁张续王金云张礼仪
Owner FUJIAN INST OF RES ON THE STRUCTURE OF MATTER CHINESE ACAD OF SCI
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