CN112142765A - Crystal structure of isophthalic acid cadmium complex and fluorescence property thereof - Google Patents
Crystal structure of isophthalic acid cadmium complex and fluorescence property thereof Download PDFInfo
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- CN112142765A CN112142765A CN202011058222.0A CN202011058222A CN112142765A CN 112142765 A CN112142765 A CN 112142765A CN 202011058222 A CN202011058222 A CN 202011058222A CN 112142765 A CN112142765 A CN 112142765A
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- 239000013078 crystal Substances 0.000 title claims abstract description 14
- YTMDTJVKFWXZCI-UHFFFAOYSA-N [Cd].C(C1=CC(C(=O)O)=CC=C1)(=O)O Chemical compound [Cd].C(C1=CC(C(=O)O)=CC=C1)(=O)O YTMDTJVKFWXZCI-UHFFFAOYSA-N 0.000 title description 4
- JVZRCNQLWOELDU-UHFFFAOYSA-N 4-Phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 claims abstract description 24
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- TYKIQKDIXLZEHF-UHFFFAOYSA-L C(C1=CC(C(=O)[O-])=CC=C1)(=O)[O-].[Cd+2] Chemical compound C(C1=CC(C(=O)[O-])=CC=C1)(=O)[O-].[Cd+2] TYKIQKDIXLZEHF-UHFFFAOYSA-L 0.000 claims description 5
- 230000005284 excitation Effects 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 abstract description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 150000001661 cadmium Chemical class 0.000 abstract description 2
- -1 isophthalate anion Chemical class 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 150000005362 4-phenylpyridines Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 150000002531 isophthalic acids Chemical class 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a crystal structure of a cadmium complex and a fluorescence property research thereof. The cadmium complex belongs to a triclinic system, the space group is P-1, and the central metal ion is Cd (II) ion. The minimum structural unit of the complex consists of one Cd (II) ion, one isophthalate anion and two 4-phenylpyridine neutral molecules. Solid-state fluorescence test studies indicate that the complex has excellent fluorescence properties relative to the ligand. The invention successfully synthesizes the m-phthalic acid cadmium complex and cultivates a single crystal, utilizes an X-ray single crystal diffractometer to measure the crystal structure, and carries out solid fluorescence test, thereby providing a certain basis for the research and application of complex crystals in luminescent materials.
Description
Technical Field
The invention belongs to the technical field of complex property research, and particularly relates to a crystal structure of a cadmium isophthalate complex and fluorescence property research thereof.
Background
Aromatic carboxylic acid compounds (Aromatic carboxylic acid compounds) contain carboxyl groups having a very strong coordination ability, and transition metal complexes having different steric structures can be constructed depending on the number and position of the carboxyl groups. The organic carboxylic acid ligand with various structures can react with a plurality of metal ions to form complexes with different structures and special properties. The aromatic acid complex has certain rigidity in structure, so that intramolecular radiation transition of the aromatic acid complex is greatly enhanced. In recent years, aromatic acid complexes have been widely used in the field of luminescent materials, and research on luminescent materials has become one of leading-edge research fields spanning multiple disciplines such as physics, chemistry, material science, and life science.
Disclosure of Invention
The invention aims to provide a structure of a cadmium complex and fluorescence properties of the cadmium complex.
The idea of the invention is as follows: the cadmium complex is obtained by using isophthalic acid and 4-phenylpyridine as ligands and cadmium chloride through a solvothermal method.
The crystal structure of the isophthalic acid cadmium complex is shown in figure 1. The complex belongs to a triclinic system, a P-1 space group, and unit cell parameters are as follows:
α＝69.373(15)°，β＝74.233(10)°，γ＝72.666(10)°，
Z＝2，Dc＝3.735g·cm-3，μ＝7.590mm-1f (000) ═ 1260.0. The minimum structure unit of the complex comprises a Cd (I) ion, an isophthalic anion and two 4-phenylpyridine neutral molecules. The metal central ion Cd (i) 1 is in a six-coordination mode, and Cd (i) 1 is chelated with carboxyl oxygen atoms (O3A, O4A) on one isophthalic acid respectively and is in bidentate coordination, bridged monodentate coordination with carboxyl oxygen atoms O1 and O2A on two other isophthalic acids, and is coordinated with nitrogen atoms (N1, N2) from two different 4-phenylpyridines respectively. Six coordination atoms form an irregular octahedral configuration around the Cd (I) 1 ion, four oxygen atoms of O1, O2A, O3A and O4A form an equatorial plane, and N1 and N2 are distributed along the axial direction respectively. Coordination mode (mu) of central cadmium ion chelating bidentate and cis-trans bridged bidentate through m-phthalic acid anion4-η1:η1:η1:η1) And 4-phenylpyridine monodentate coordination forms a one-dimensional chain structure
The fluorescence property research of the cadmium complex comprises the following steps:
the fluorescence spectrum of the isophthalic acid cadmium complex is shown in figure 2, and solid-state fluorescence tests are carried out on the complex, the main ligand isophthalic acid and the auxiliary ligand 4-phenylpyridine at normal temperature. The ligand and the complex both have certain fluorescence properties, and can be obtained from a fluorescence spectrogram, and the main ligand isophthalic acid has a stronger fluorescence emission peak at 350nm under the excitation wavelength of 298nm, which is mainly caused by pi-pi x transition inside the ligand. And the auxiliary ligand 4-phenylpyridine has a stronger fluorescence emission peak at 524nm under the excitation wavelength of 263 nm. The complex has a strong fluorescence emission peak at 388nm under an excitation wavelength of 319 nm. Due to metal central ion Cd2+After the ligand m-BDC is coordinated, the rigid structure of the m-BDC is changed, so that the fluorescence intensity of the m-BDC is obviously enhanced.
The invention successfully synthesizes the m-phthalic acid cadmium complex, cultivates the single crystal, analyzes the crystal structure, carries out solid-state fluorescence test and provides a certain basis for further researching luminescent materials
Drawings
FIG. 1 is a molecular structural diagram of a cadmium isophthalate complex according to the present invention.
FIG. 2 is a solid state fluorescence spectrum of the cadmium isophthalate complex of the present invention.
Description of the specific structure
The complex belongs to a triclinic system, a P-1 space group, and unit cell parameters are as follows:
α＝69.373(15)°，β＝74.233(10)°，γ＝72.666(10)°，
Z＝2，Dc＝3.735g·cm-3，μ＝7.590mm-1，F(000)＝1260.0。
the crystal diffraction shows that the minimum structural unit of the complex comprises one Cd (I) ion, one isophthalic acid anion and two 4-phenylpyridine neutral molecules. The metal central ion Cd (i) 1 is in a six-coordination mode, Cd (i) 1 is respectively coordinated with oxygen atoms (O1, O2A, O3A, and O4A) from three isophthalic acid anion carboxyl groups, wherein carboxyl oxygen atoms (O3A and O4A) on one isophthalic acid and the central ion Cd (i) are in chelating bidentate coordination, and carboxyl oxygen atoms O1 and O2A on the other two isophthalic acids and the central ion Cd (i) are in bridging monodentate coordination, and are respectively coordinated with nitrogen atoms (N1 and N2) from two different 4-phenylpyridines. Six coordination atoms form an irregular octahedral configuration around the Cd (I) 1 ion, four oxygen atoms of O1, O2A, O3A and O4A form an equatorial plane, and N1 and N2 are distributed along the axial direction respectively. Coordination mode (mu) of central cadmium ion chelating bidentate and cis-trans bridged bidentate through m-phthalic acid anion4-η1:η1:η1:η1) And 4-phenylpyridine monodentate coordination forms a one-dimensional chain structure. In addition, there is weak pi-pi stacking within the molecule, the distance between the two pyridine ring centers close to parallel 4-phenylpyridine being
These forces together form the three-dimensional structure of the complex.
Claims (2)
1. The crystal structure of the cadmium isophthalate complex belongs to a triclinic system and a P-1 space group, and crystal diffraction shows that the minimum structure unit of the complex comprises one Cd (I) ion, one isophthalic anion and two 4-phenylpyridine neutral molecules.
2. The fluorescence property of the cadmium isophthalate complex as described in claim 1, wherein solid-state fluorescence tests were performed on the complex, the main ligand isophthalic acid and the auxiliary ligand 4-phenylpyridine at room temperature, wherein isophthalic acid has a strong fluorescence emission peak at 350nm at an excitation wavelength of 298nm, the auxiliary ligand 4-phenylpyridine has a strong fluorescence emission peak at 263nm at 524nm, the complex has a strong fluorescence emission peak at 388nm at an excitation wavelength of 319nm, the complex is red-shifted with respect to m-BDC, and the fluorescence intensity of the complex is significantly enhanced.
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Application publication date: 20201229 |