CN116199642A - High-efficiency near infrared luminous chiral copper cluster material and application thereof in night vision imaging - Google Patents
High-efficiency near infrared luminous chiral copper cluster material and application thereof in night vision imaging Download PDFInfo
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- CN116199642A CN116199642A CN202310073226.3A CN202310073226A CN116199642A CN 116199642 A CN116199642 A CN 116199642A CN 202310073226 A CN202310073226 A CN 202310073226A CN 116199642 A CN116199642 A CN 116199642A
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- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
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- C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention discloses a chiral copper cluster material with high-efficiency near infrared luminescence, belonging to the crossing field of coordination chemistry and nano materials. The copper cluster enantiomer adopts chiral ligandS/R) -4-isopropylthiazolidine-2-thione (abbreviated as:R/S-iptt) is used as a protective ligand, and the chiral copper cluster material with high-efficiency near infrared luminescence is synthesized by a simple one-pot method. The enantiomer cluster has the chemical formula of C 38.67 H 66 Cu 6 N 6 S 12 Cl 0.67 O, abbreviated as:R/SCS1, belonging to the cubic system, the space group is chiral space groupP2 1 3，S‑CS1：a=17.8373Å,b=17.8373Å,c=17.8373Å,α=90°,β= 90°,γ=90°,V=5675.28Å 3 ；R‑CS1：a=17.8736Å,b=17.8736Å,c=17.8736Å,α=90°,β=90°,γ= 90°,V=5710.0Å 3 。 The material has high-efficiency near infrared luminescence at room temperature, and the fluorescence quantum yield can reach 45%; the structure has higher thermal stability. The fluorescent powder can be used as a near infrared fluorescent powder material for preparing a near infrared LED to realize night vision near infrared light illumination.
Description
Technical Field
The invention belongs to the crossing field of coordination chemistry and nano materials, and mainly synthesizes a chiral copper cluster material with high-efficiency near infrared luminescence.
Background
Coin metal nanoclusters with sizes between atoms, molecules and macroscopic solid substances have wide application prospects in the fields of luminescence, catalysis, biology, nanoscience and the like due to accurate structures, unique quantum size effects and excellent photophysical and chemical characteristics.
Cu clusters are more sensitive to oxides in air than Au and Ag nanoclusters. Therefore, in recent years, research on synthesis and application of atom-accurate Cu (I)/Cu (0) cluster compounds has been greatly hampered. The most widely studied Cu cluster performance is the attractive photophysical property, and the Cu cluster has become a novel nano optical material and has wide application value in the fields of illumination, optical detection, biological imaging and the like.
The wavelength of short-wave near infrared light is generally in the range of 780-1100 nm, and cannot be recognized by human eyes. Near infrared light has stronger penetrability, can be through using near infrared luminescent material as the phosphor powder, through high energy low wavelength light excitation production near infrared fluorescence, shine on the object under low illuminance condition and realize near infrared illumination, the purpose that the near infrared camera of rethread configuration is collected the near infrared light of reflection reaches formation of image, and then realizes night vision illumination. At present, no report is available on the use of Cu cluster compounds in near infrared luminescence imaging.
Disclosure of Invention
The invention aims to synthesize a chiral copper cluster material with high-efficiency near infrared luminescence.
Therefore, the invention develops a chiral copper cluster material with high-efficiency near infrared luminescence, and the chemical formula is as follows: c (C) 38.67 H 66 Cu 6 N 6 S 12 Cl 0.67 O, abbreviated as: R/S-CS1 belongs to a cubic system, and the space group is chiral space group P2 1 3，S-CS1：
α＝90°,β＝90°,γ＝90°,/>
R-CS1：/>
α＝90°,β＝90°,γ＝90°,
Wherein the chiral ligand is (S/R) -4-isopropyl thiazolidine-2-thioketone (abbreviated as R/S-iptt), and the structural formula is as follows:
the preparation method of the chiral copper cluster material is realized by the following steps:
dissolving copper trifluoroacetate in a mixed solvent of dichloromethane, methanol and acetone, adding a ligand (S/R) -4-isopropyl thiazolidine-2-thione, stirring for reaction, volatilizing in a dark place after the reaction is finished to obtain crystals, filtering, washing, and airing at room temperature.
The copper cluster material is composed of a core composed of six copper atoms and a periphery composed of six organic ligands (shown in fig. 1 and 2); six copper atoms are arranged in an octahedron, six organic ligands are respectively distributed on six faces of the octahedron, mercapto sulfur atoms on each ligand are simultaneously coordinated with two copper atoms on one face, and each nitrogen atom is connected with the other copper atom on one face (shown in figure 3).
The chiral copper cluster material with high-efficiency near-infrared luminescence is applied to near-infrared fluorescence illumination, and the properties of the chiral copper cluster material are specifically described as follows:
the material is a yellow crystalline material with high thermal stability, and the decomposition temperature can reach 250 degrees centigrade (shown in fig. 4). The fluorescent light has stronger near infrared fluorescence under the condition of air room temperature, and the optimal emission wavelength position is 776nm (excitation wavelength 370 nm) (shown in figure 5); the fluorescence quantum yield was 45% at room temperature. The material can be excited by blue light to emit stronger light (shown in fig. 6) at room temperature, and a near-infrared LED device excited by the blue light can be prepared. The solid powder of the material is uniformly mixed with glue and smeared on the surface of a blue light LED bulb, the LED bulb is lightened, the blue light excites the material to emit near infrared fluorescence, and night vision illumination under dark conditions is realized (shown in figure 7).
The invention has the beneficial effects that: the copper cluster material has a very wide excitation wave band (300-560 nm), and can be excited by blue light to emit strong near infrared fluorescence; in addition, the copper cluster material has higher thermal stability (the decomposition temperature can reach 250 ℃), higher luminous efficiency (the fluorescence quantum yield can reach 45%), and good application prospect in the aspect of near infrared LED night vision illumination.
Drawings
FIG. 1 is a schematic diagram of a pair of enantiomer structures of a copper cluster material of the present invention.
FIG. 2 is a schematic diagram of the core structure of the copper cluster material of the present invention.
FIG. 3 is a schematic representation of ligand coordination patterns of copper cluster materials of the present invention.
FIG. 4 is a graph of a thermal analysis of a copper cluster material of the present invention.
FIG. 5 is a graph showing fluorescence spectra of the copper cluster material of the present invention at room temperature.
FIG. 6 is a graph of the emission spectra of copper cluster materials of the present invention at different excitation wavelengths.
Fig. 7 is a photograph of an LED device (a) prepared by using the copper cluster material of the present invention as a near infrared fluorescent material, a spectrum (b) of the device when it is lighted, and night vision illumination (c-d) achieved by near infrared light emitted from the near infrared LED device.
Detailed Description
The invention is further illustrated by the following examples:
example 1: synthesis of copper Cluster Material according to the invention
Copper trifluoroacetate (29 mg,0.1 mmol) was weighed and dissolved in 2mL of methylene chloride, 2.00mL of acetone and 2.00mL of methanol to obtain a blue clear liquid, and then (S/R) -4-isopropylthiazolidine-2-thione (32 mg,0.2 mmol) was added thereto, followed by stirring to obtain a pale yellow clear liquid. And standing at room temperature and slowly volatilizing for 2 days to obtain yellow blocky crystals, washing the crystals with acetonitrile, filtering and collecting the crystals, and airing the crystals at room temperature for property testing.
The copper cluster material of the invention prepared in example 1 was further characterized by the following procedure:
(1) Crystal structure determination
The X-ray single crystal diffraction data of the complex was measured on a Rigaku XtaLAB Pro single crystal diffractometer using a single crystal sample of appropriate size. The data are all obtained by using CuK alpha rays which are monochromized by graphite
The diffraction sources were collected by ω scan at 300K temperature and subjected to Lp factor correction and semi-empirical absorption correction. The structural analysis is that the initial structure is obtained by a direct method through the SHELXS-97 program, and then the SHELXL-97 program is used for finishing by a full matrix least square method. All non-hydrogen atoms were refined using anisotropic thermal parameters. All hydrogen atoms were refined using isotropic thermal parametric methods. The detailed crystal measurement data are shown in Table 1.
TABLE 1 principal crystallographic data of copper Cluster Material according to the invention
TABLE 1 primary crystallographic data
R 1 ＝∑||F o |-|F c ||/∑|F o |.wR 2 ＝[∑w(F o 2 -F c 2 ) 2 /∑w(F o 2 ) 2 ] 1/2
The above examples are only for illustrating the contents of the present invention, and other embodiments of the present invention are also provided. However, all technical solutions formed by adopting equivalent substitution or equivalent deformation are within the protection scope of the present invention.
Claims (3)
1. A chiral copper cluster compound characterized by: the chemical formula is as follows: c (C) 38.67 H 66 Cu 6 N 6 S 12 Cl 0.67 O, abbreviated as: R/S-CS1 belongs to a cubic system, and the space group is chiral space group P2 1 3，S-CS1：
α＝90°,β＝90°,γ＝90°,/>
R-CS1：/>
α＝90°,β＝90°,γ＝90°,/>
Wherein the chiral ligand is (S/R) -4-isopropyl thiazolidine-2-thioketone (abbreviated as R/S-iptt), and the structural formula is as follows:
2. the chiral copper cluster material of claim 1, characterized in that: which consists of a core of six copper atoms, the periphery is protected by six organic ligands; six copper atoms are arranged in an octahedron, six organic ligands are respectively distributed on six faces of the octahedron, mercapto sulfur atoms on each ligand are simultaneously coordinated with two copper atoms on one face, and each nitrogen atom is connected with another copper atom on one face.
3. Use of a chiral copper cluster material according to claim 2 as luminescent material, characterized in that: the solid powder of the material is uniformly mixed with glue, and the mixture is smeared on the surface of a blue light LED bulb, and an LED lamp is lightened, so that near infrared night vision illumination is realized.
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| CN202310073226.3A CN116199642A (en) | 2023-02-07 | 2023-02-07 | High-efficiency near infrared luminous chiral copper cluster material and application thereof in night vision imaging |
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