CN107033363A - Based on rare earth compounding, preparation method, structure and its application that 2 HNCP and the carboxylic acid of pyridine 3 are mixed ligand - Google Patents

Based on rare earth compounding, preparation method, structure and its application that 2 HNCP and the carboxylic acid of pyridine 3 are mixed ligand Download PDF

Info

Publication number
CN107033363A
CN107033363A CN201611016417.2A CN201611016417A CN107033363A CN 107033363 A CN107033363 A CN 107033363A CN 201611016417 A CN201611016417 A CN 201611016417A CN 107033363 A CN107033363 A CN 107033363A
Authority
CN
China
Prior art keywords
rare earth
hncp
ncp
pyridine
carboxylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201611016417.2A
Other languages
Chinese (zh)
Inventor
乔宇
周艳凤
车广波
胡博
王炫博
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin Normal University
Original Assignee
Jilin Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin Normal University filed Critical Jilin Normal University
Priority to CN201611016417.2A priority Critical patent/CN107033363A/en
Publication of CN107033363A publication Critical patent/CN107033363A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/102—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/104—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/108—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B01D2257/7025—Methane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/37—Lanthanum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/38—Lanthanides other than lanthanum
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Catalysts (AREA)

Abstract

The present invention relates to a kind of based on rare earth compounding, preparation method, crystal structure and its application that 2 HNCP and the carboxylic acid of pyridine 3 are mixed ligand.Rare earth compounding molecular formula is [RE (2 NCP)2(3‑pyc)]n.Preparation method is using the ratio of the amount of material as 1 by trivalent rare earth salt, 2 HNCP and the carboxylic acid of pyridine 3:0.5~1.5:0.5~1.5 is mixed, a certain amount of water is added to stir after a period of time, pH is reconciled between 5~8 with NaOH solution, then mixed solution is transferred in the reactor that liner is polytetrafluoroethylene (PTFE), after reaction a period of time in the range of 140~180 DEG C, room temperature is gradually cooling to, room temperature after product is washed with water dries that to obtain bulk crystals be rare earth compounding of the present invention.This complex is applied to catalysis organic synthesis, selective absorption, separation CO2、CH4、H2、N2、O2In terms of gas, and selective absorption, separation, photocatalytically degradating organic dye and phenols endocrine disruptors.This synthetic method has the features such as repeatability is strong, yield is high, properties of product are stable.

Description

Rare earth compounding, preparation side based on 2-HNCP and pyridine-3-carboxylic acid for mixed ligand Method, structure and its application
Technical field
It is more particularly to a kind of to be based on 2-HNCP and pyridine-3-carboxylic acid the invention belongs to complex science and technology field Rare earth compounding, preparation method, crystal structure and its application of mixed ligand.
Background technology
Complex is a kind of new function material with periodic structure.Complex be mostly by metal ion with it is many The organoligand coordination of functional group is formed.Because such material typically has the spies such as big specific surface area, porosity, various structures Point, catalysis, magnetic, gas storage with separating, luminescent material (J.M.Zhou, H.M.Li, N.Xu, P.Cheng, Inorg.Chem.Commun.2013,37,30；B.Liu,W.P.Wu,L.Hou,Y.Y.Wang,Chem.Commun.2014,50, 8731；X.Zhao,X.Y.Yu,T.L.Chen,Y.H.Luo,J.J.Yang,H.Zhang,Inorg.Chem.Commun.2012, Etc. 20,247) field has a wide range of applications.
In the organic ligand of complex is constructed, N, the multi-functional parts of O- are the very important parts of a class, and these contain N, O- parts include imidazoles -4,5- dicarboxylic acids (Z.G.Gu, J.H.Chen, Y.N.Chen, Y.Ying, H.M.Peng, H.Y.Jia, M.F.Wang, S.S.Li, Y.P.Cai.Inorg.Chem.Commun.2012,14,68), pyridine -2,5- dicarboxylic acids (P.Mahata, K.V.Ramya, S.Natarajan, Inorg.Chem.2009,48,4942), pyridine -2,6- dicarboxylic acids (S.K.Ghosh, P.K.Bharadwaj, Inorg.Chem.2003,42,8250), 4- (4- pyridine radicals) benzoic acid (M.H.Zeng,Z.Yin,Y.X.Tan,W.X.Zhang,Y.P.He,M.Kurmoo,J.Am.Chem.Soc.2014,136, 4680) etc..During 2-HNCP (2- (2- carboxyl phenyls) imidazo (4,5-f) (1,10) Phen) is also N, the multi-functional parts of O- A member, with more coordination site, larger conjugated system, imidazole ring and carboxyl functional group, it is easy to formed π-π interaction And hydrogen bond, it is to build the good part of metal organic complex.Because most of rare earth compounding is the hair with property Luminescent material, thus had a wide range of applications in analytical chemistry, biology, medicine and other fields.2-HNCP is such as contained into N with other, O- matches somebody with somebody Body is collectively incorporated into rare earth compounding, can greatly enrich complex functional material.According to investigation, so far, with 2-HNCP The rare earth compounding constructed with pyridine-3-carboxylic acid (being abbreviated as 3-Hpyc) as mixed ligand is not reported also.
The content of the invention
The technical problem to be solved in the present invention is to disclose a kind of rare earth constructed by 2-HNCP and 3-Hpyc for mixed ligand Complex, preparation method, structure and application, the synthetic method have the advantages that repeated strong, yield height, properties of product are stable.
The technical scheme is that：
It is the rare earth compounding of mixed ligand based on 2-HNCP and pyridine-3-carboxylic acid, molecular formula is [RE (2-NCP)2(3- pyc)]n, chemical formula is C46H26N9O6RE, wherein RE are La3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Gd3+、Tb3+、Dy3+、 Ho3+、Er3+、Tm3+、Yb3+、Lu3+In one kind, wherein 2-NCP-And 3-pyc-The respectively 2-HNCP and 3-Hpyc of deprotonation Anion ligand.
The beneficial effects of the invention are as follows：
1. rare earth compounding of the present invention has Three-dimensional Supramolecular Network structure, it is mainly used in and catalyzes and synthesizes, selectivity is inhaled Attached, separation CO2、CH4、H2、N2、O2Deng gas, and interior point of selective absorption, separation, photocatalytically degradating organic dye and phenols Secrete chaff interference.
2. the synthetic method of the present invention has the features such as repeatability is strong, yield is high, properties of product are stable.
Brief description of the drawings
Fig. 1 is rare earth Pr complexs [Pr (2-NCP)2(3-pyc)]nCoordination context diagram.
Fig. 2 is the one-dimensional catenary structure figure of rare earth Pr complexs.
Fig. 3 is the two-dimensional layered structure figure for connecting into one-dimensional chain that interacted by π-π of rare earth Pr complexs.
Fig. 4 is that two-dimensional layered structure is connected into Three-dimensional Supramolecular Network knot by rare earth Pr complexs by π-π interactions Composition.
Fig. 5 is the fluorescence emission spectrogram of compound of the visual field of rare earth Pr complexs.
Fig. 6 is the fluorescence emission spectrogram of compound of the near infrared region of rare earth Pr complexs.
Embodiment
Rare earth compounding of the present invention, which can be widely used in, to be catalyzed and synthesized, selective absorption, separation CO2、CH4、H2、N2、 O2Deng gas, and selective absorption, separation, photocatalytically degradating organic dye and phenols endocrine disruptors.
The molecular formula of the serial rare-earth complex is [RE (2-NCP)2(3-pyc)]n, chemical formula is C46H26N9O6RE, wherein RE is La3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Gd3+、Tb3+、Dy3+、Ho3+、Er3+、Tm3+、Yb3+、Lu3+In one kind, Wherein 2-NCP-And 3-pyc-The respectively 2-HNCP and 3-Hpyc of deprotonation anion ligand.
The crystal structure of the serial rare-earth complex is：The crystal of the complex belongs to anorthic system, and space group is P- 1.Include a RE in the asymmetric unit of complex3+, two 2-NCP-Part, a 3-pyc-Part.Metal center from Sub- RE3+In coordination environment in ten coordinations, RE3+Respectively from 6 O atoms (4 O atoms 2-NCP that to come from 2 different-Match somebody with somebody Body, 2 O atoms are from 1 3-pyc-Part) (come from 2 different 2-NCP with 4 N atoms-Part) coordination.With RE3+For Tie point constitutes unlimited one-dimensional rectangle chain or double-strand.Pass through 2-NCP between adjacent one-dimensional chain-π-π phase interactions between part With foring two-dimensional layered structure.Meanwhile, these adjacent two-dimensional layered structures further pass through 2-NCP-π-π between part Interaction, the Three-dimensional Supramolecular Network structure that most complex is connected at last.
The preparation method of the serial rare-earth complex is：By trivalent rare earth La3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、 Gd3+、Tb3+、Dy3+、Ho3+、Er3+、Tm3+、Yb3+、Lu3+Salt (nitrate, hydrochloride, acetate, sulfate etc.), 2-HNCP and 3-Hpyc is using the ratio of the amount of material as 1:0.5~1.5:0.5~1.5 is mixed, and is added water and is stirred after a period of time, uses NaOH Solution reconciles pH between 5~8, and then mixed solution is transferred in the reactor that liner is polytetrafluoroethylene (PTFE), 140~ Reacted in the range of 180 DEG C after a period of time, be gradually cooling to room temperature, room temperature after product is washed with water dried and obtain bulk crystals i.e. For rare earth compounding of the present invention.
Embodiment 1：
Chemical formula of the present invention is C46H26N9O6Pr rare earth Pr complexs [Pr (2-NCP)2(3-pyc)]nPreparation Method is as follows：
By Pr (NO3)3·6H2O (0.087g, 0.2mmol), 2-HNCP (0.0340g, 0.1mmol) and 3-Hpyc (0.0123g, 0.1mmol), adds deionized water 10mL stirring 10min, adjusts pH to 6.5 with 1mol/L NaOH solutions, be placed on In 25mL ptfe autoclaves, 180 DEG C are heated to, is reacted 3 days, is gradually cooling to room temperature, room temperature is washed with deionized Dry and obtain yellow bulk crystals, as rare earth Pr complexs, yield is 52% (being based on Pr).The theoretical value of elementary analysis (%)：C 58.67, H 2.78, N 13.39；Experiment value (%)：C 58.31, H 2.80, N 13.32.
The relevant characterization of complex
(1) crystal structure determination of rare earth Pr complexs
The diffraction data of complex is collected on Oxford Diffraction Gemini R Ultra diffractometers, Mo- KαRay293K.It is corrected using technology scanning.Crystal structure is by SHELEXL-97 journeys Sequence is solved with direct method, and refine is carried out using SHELEXL-97 with complete matrix least square method.The temperature factor of non-hydrogen atom is used Anisotropy is modified.Detailed axonometry data are shown in Table 1；Important bond distance and bond angle data is shown in Table 2；Crystal structure is shown in Fig. 1-Fig. 4.
The rare earth Pr complex crystals of invention belong to anorthic system, and space group is P-1, and cell parameter is a=10.5710 (8), b=13.6022 (10),α=79.0110 (10), β=80.1630 (10), γ= 68.4180 (10) °,The coordination environment of complex is as shown in figure 1, in the asymmetric unit of complex In include Pr (III), two 2-NCP-Part, a 3-pyc-Part.Metal center ion Pr (III) is in ten coordinations In coordination environment, Pr (III) respectively from 6 O atoms (4 O atoms 2-NCP that to come from 2 different-Part, 2 O atoms come From 1 3-pyc-Part) (come from 2 different 2-NCP with 4 N atoms-Part) coordination.With Pr3+It is unlimited to be constituted for tie point One-dimensional rectangle chain or double-strand (Fig. 2).Pass through 2-NCP between adjacent one-dimensional chain-π-π interactions between part form two Tie up layer structure (Fig. 3).Meanwhile, these adjacent two-dimensional layered structures further pass through 2-NCP-π-π between part are mutual Effect, the Three-dimensional Supramolecular Network structure (Fig. 4) that most complex is connected at last.
(2) the photoluminescent property research (Perkin-Elmer LS55 XRFs) of complex
Complex obtains strong emission peak in the case where the light of 362nm wavelength is excited in 600nm and 610nm, in 490,548 and Three weak emission peaks (see Fig. 5) are obtained at 646nm, corresponding characteristic emission is rare earth element Pr (III)1D2→3H4,3P0 →3H6,3P0→3H4,3P0→3H5,3P0→3F2；Complex obtains characteristic emission peak and existed in the case where the light of 466nm wavelength is excited 1024nm (see Fig. 6), comes from1D2→3F4Transformation (Edinburgh FLSP920 XRFs).
Embodiment 2：
Chemical formula of the present invention is C46H26N9O6La rare earth La complex [La (2-NCP)2(3-pyc)]nPreparation Method is as follows：
By LaCl3·6H2O (0.0706g, 0.2mmol), 2-HNCP (0.0680g, 0.2mmol) and 3-Hpyc (0.0246g, 0.2mmol), adds deionized water 10mL stirring 15min, adjusts pH to 7 with 1.1mol/L NaOH solutions, be placed on In 25mL ptfe autoclaves, 170 DEG C are heated to, is reacted 3 days, is gradually cooling to room temperature, room temperature is washed with deionized Dry and obtain yellow bulk crystals, selecting suitable crystal progress X-ray single crystal diffraction analysis, (yield is 49%, based on metal La).Elementary analysis is：(theoretical value)：C,58.80；H,2.79；N,13.42；(experiment value)：C,58.48；H,2.82；N, 13.34.
The crystal structure determination of rare earth La complex is with Pr complexs.Detailed crystallographic data is shown in Table 1；Important bond distance 2 are shown in Table with bond angle data；Crystal structure is similar to rare earth Pr complexs.
The rare earth La complex crystal of invention belongs to anorthic system, and space group is P-1, and cell parameter is α=79.2200 (10) °, β= 80.140 (2) °, γ=68.149 (2) °,
Embodiment 3：
Synthesis chemical formula is C46H26N9O6Nd rare earth compounding [Nd (2-NCP)2(3-pyc)]n：
By Nd (CH3COO)3·2H2O (0.0357g, 0.1mmol), 2-HNCP (0.0680g, 0.2mmol) and 3-Hpyc (0.0185g, 0.15mmol), adds deionized water 12mL stirring 8min, adjusts pH to 6 with 0.7mol/LNaOH solution, be placed on In 25mL ptfe autoclaves, 160 DEG C are heated to, is reacted 3 days, is gradually cooling to room temperature, room temperature is washed with deionized Dry and obtain yellow bulk crystals, selecting suitable crystal progress X-ray single crystal diffraction analysis, (yield is 45%, based on metal Nd).Elementary analysis is：(theoretical value)：C,58.47；H,2.77；N,13.34；(experiment value)：C,58.15；H,2.81；N, 13.27.
The crystal structure determination of rare earth Nd complex is with Pr complexs.Detailed crystallographic data is shown in Table 1；Important bond distance 2 are shown in Table with bond angle data；Crystal structure is similar to rare earth Pr complexs.
The rare earth Nd complex of invention belongs to anorthic system, and space group is P-1, and cell parameter is α=78.8790 (10) °, β= 80.1200 (10) °, γ=68.4370 (10) °,
Table 1：Three kinds of representational Pr (1), La (2), predominant crystal datas of Nd (3) rare earth compounding
Table 2：Three kinds of representational Pr (1), La (2), selective bond distances of Nd (3) rare earth compoundingWith bond angle (°).
Symmetry transformations used to generate equivalent atoms:1:#1-x+1,- y,-z；#2-x,-y+1,-z-1.2：#1-x+1,-y,-z+2；#2-x,-y+1,-z+1.3:#1-x,-y+2,-z；#2-x+1,-y+ 1,-z+1.

Claims (5)

1. based on the rare earth compounding that 2-HNCP and pyridine-3-carboxylic acid are mixed ligand, it is characterised in that：Molecular formula is [RE (2- NCP)2(3-pyc)]n, chemical formula is C46H26N9O6RE, wherein RE are La3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Gd3+、 Tb3+、Dy3+、Ho3+、Er3+、Tm3+、Yb3+、Lu3+In one kind, wherein 2-NCP-And 3-pyc-The respectively 2- of deprotonation HNCP and 3-Hpyc anion ligand.
2. according to claim 1 is the rare earth compounding of mixed ligand, its feature based on 2-HNCP and pyridine-3-carboxylic acid It is：Its crystal belongs to anorthic system, and space group is P-1.Include a RE in the asymmetric unit of complex3+, two 2-NCP-Part, a 3-pyc-Part.Metal center ion RE3+In coordination environment in ten coordinations, RE3+Respectively with 6 O (4 O atoms come from 2 different 2-NCP to atom-Part, 2 O atoms are from 1 3-pyc-Part) and 4 N atoms (come From in 2 difference 2-NCP-Part) coordination.With RE3+Unlimited one-dimensional rectangle chain or double-strand are constituted for tie point.Adjacent one-dimensional chain Between pass through 2-NCP-π-π interactions between part form two-dimensional layered structure.Meanwhile, these adjacent two-dimensional layers Structure further passes through 2-NCP-π-π interactions between part, the Three-dimensional Supramolecular Network that most complex is connected at last Structure.
3. it is according to claim 1 based on 2-HNCP and preparation of the pyridine-3-carboxylic acid for the rare earth compounding of mixed ligand Method, it is characterised in that：
By trivalent rare earth salt, 2-HNCP and pyridine-3-carboxylic acid using the ratio of the amount of material as 1:0.5~1.5:0.5~1.5 is mixed Close, add water and stir after a period of time, mixed solution is transferred into liner between 5~8, then with NaOH solution conciliation pH is In the reactor of polytetrafluoroethylene (PTFE), after reaction a period of time in the range of 140~180 DEG C, room temperature is gradually cooling to, is washed with water Room temperature dries that to obtain bulk crystals be rare earth compounding of the present invention after product.
4. it is according to claim 3 based on the preparation of 2-HNCP and pyridine-3-carboxylic acid for the rare earth compounding of mixed ligand Method, it is characterised in that：The trivalent rare earth salt is trivalent rare earth La3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Gd3+、Tb3 +、Dy3+、Ho3+、Er3+、Tm3+、Yb3+、Lu3+Nitrate or hydrochloride or acetate or sulfate.
5. rare earth compounding according to claim 1 can be applicable to catalysis organic synthesis, selective absorption, separation CO2、 CH4、H2、N2、O2Deng gas, and selective absorption, separation, photocatalytically degradating organic dye and phenols endocrine disruptors side Face.
CN201611016417.2A 2016-11-18 2016-11-18 Based on rare earth compounding, preparation method, structure and its application that 2 HNCP and the carboxylic acid of pyridine 3 are mixed ligand Pending CN107033363A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611016417.2A CN107033363A (en) 2016-11-18 2016-11-18 Based on rare earth compounding, preparation method, structure and its application that 2 HNCP and the carboxylic acid of pyridine 3 are mixed ligand

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611016417.2A CN107033363A (en) 2016-11-18 2016-11-18 Based on rare earth compounding, preparation method, structure and its application that 2 HNCP and the carboxylic acid of pyridine 3 are mixed ligand

Publications (1)

Publication Number Publication Date
CN107033363A true CN107033363A (en) 2017-08-11

Family

ID=59531081

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611016417.2A Pending CN107033363A (en) 2016-11-18 2016-11-18 Based on rare earth compounding, preparation method, structure and its application that 2 HNCP and the carboxylic acid of pyridine 3 are mixed ligand

Country Status (1)

Country Link
CN (1) CN107033363A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108250451A (en) * 2018-01-29 2018-07-06 河南大学 Iron-dysprosium different metal antimony tungstates frame material that binary organic carboxyl acid participates in and preparation method and application
CN114479830A (en) * 2021-12-30 2022-05-13 吉林师范大学 Organic eutectic @ rare earth complex core-shell structure with dual light emission characteristics
CN114605654A (en) * 2022-02-16 2022-06-10 广东石油化工学院 MOFs, preparation method and application thereof
CN114618438A (en) * 2020-12-10 2022-06-14 中国科学院大连化学物理研究所 Oxygen selective adsorbent and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105040140A (en) * 2015-08-21 2015-11-11 北京石油化工学院 Terbium-doped composite conductive green-light-emitting nano-fibers and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105040140A (en) * 2015-08-21 2015-11-11 北京石油化工学院 Terbium-doped composite conductive green-light-emitting nano-fibers and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
张青: "几种新颖的配位聚合物的水热合成、晶体结构及性质研究", 《江苏大学硕士学位论文》 *
王春杰: "邻菲罗啉衍生物配体HNCP金属配合物的合成、结果和性能研究", 《江苏大学硕士学位论文》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108250451A (en) * 2018-01-29 2018-07-06 河南大学 Iron-dysprosium different metal antimony tungstates frame material that binary organic carboxyl acid participates in and preparation method and application
CN108250451B (en) * 2018-01-29 2020-12-25 河南大学 Iron-dysprosium dissimilar metal antimony tungstate framework material with participation of binary organic carboxylic acid and preparation method and application thereof
CN114618438A (en) * 2020-12-10 2022-06-14 中国科学院大连化学物理研究所 Oxygen selective adsorbent and preparation method and application thereof
CN114618438B (en) * 2020-12-10 2023-06-06 中国科学院大连化学物理研究所 Oxygen selective adsorbent and preparation method and application thereof
CN114479830A (en) * 2021-12-30 2022-05-13 吉林师范大学 Organic eutectic @ rare earth complex core-shell structure with dual light emission characteristics
CN114605654A (en) * 2022-02-16 2022-06-10 广东石油化工学院 MOFs, preparation method and application thereof
CN114605654B (en) * 2022-02-16 2023-01-17 广东石油化工学院 MOFs, preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN107033363A (en) Based on rare earth compounding, preparation method, structure and its application that 2 HNCP and the carboxylic acid of pyridine 3 are mixed ligand
Li et al. Zinc and cobalt complexes with (2-carboxyphenoxy) acetic acid ligand: syntheses, structures, fluorescent and magnetic properties
Feng et al. A facile route for tuning emission and magnetic properties by controlling lanthanide ions in coordination polymers incorporating mixed aromatic carboxylate ligands
Li et al. Synthesis, structure, photoluminescence and magnetic properties of new 3-D lanthanide-pyridine-2, 4, 6-tricarboxylate frameworks
Srinivasan et al. Synthesis and characterization of calcium (II) coordination polymers based on phenylacetic acid
Han et al. Hydrothermal syntheses, crystal structures and magnetic properties of two copper (II) complexes involved in situ ligand synthesis
Gangu et al. A 3D supramolecular assembly of Co (II) MOF constructed with 2, 5-pyridinedicarboxylate strut and its catalytic activity towards synthesis of tetrahydrobiphenylene-1, 3-dicarbonitriles
Li et al. 2D lanthanide–organic frameworks constructed from lanthanide acetate skeletons and benzotriazole-5-carboxylic acid connectors: synthesis, structure, luminescence and magnetic properties
Song et al. Three coordination polymers based on M2 (M= Co, Ni and Zn) clusters: Structures, magnetic and fluorescent properties
Hu et al. Preparation and characterization of [Pr (2, 5-pyridinedicarboxylic acid)(NA) H2O] n (NA= nicotinic acid anion)
Li et al. A bimetallic CoII–DyIII complex bridged by oxydiacetate ligand: Synthesis, structure, magnetic, spectral and TG properties of {[DyCo (oda) 3] 4 [Co (H2O) 6] 2· 6H2O} n
Yang et al. 3D metal–organic frameworks polymers of Pr (III) and Eu (III) with pyridine-2, 6-dicarboxylic acid: synthesis, structure and luminescent properties
Zhang et al. Syntheses, structures, and luminescent properties of three novel two-dimensional lanthanide coordination polymers with mixed aromatic carboxylate ligands
Tabatabaee et al. A Three-Dimensional Samarium Coordination Polymer with Benzene-1, 2, 4, 5-tetracarboxylic Acid, Synthesis, Characterization and Thermal Decomposition to Sm 2 O 3 Nanoparticles
Mo et al. Hydrothermal syntheses and structural diversity of cobalt complexes with 2, 2′-bibenzimidazole ligand by temperature tuning strategy
He et al. A series of three-dimensional 3d–4f heterometallic coordination frameworks based on pyridinedicarboxylic acid
Wang et al. Synthesis and luminescent properties of the first series of lanthanide complexes based on sebacate and 2, 5-pyridinedicarboxylate
Chen et al. Ferroelectricity based on coordination compound: Transition metal Co (II) sulfates templated by homochiral 2-methylpiperazine (C5H14N2)[Co (H2O) 6](SO4) 2
Tan et al. Two tetranuclear 3d–4f complexes: Syntheses, structures and magnetic properties
CN106589396B (en) It is rare earth compounding, preparation method, crystal structure and its application of mixed ligand based on 4-HNCP and terephthalic acid (TPA)
Huo et al. Syntheses, characterization, luminescence, and thermal decomposition mechanism of four lanthanide complexes with 4-ethylbenzoic acid and terpyridine
Mal et al. Control formation of rigid linear and flexible zig-zig complexes based on Zn (II) and hydroxyquinoline carboxylate ligand system
Li et al. Two-dimensional decanuclear erbium wheel supported by mixed hemimellitate and 4-chlorobenzoate ligands
Shi et al. Assembly of dinuclear copper (II) secondary building units into polymeric complexes: Crystal structures and magnetic properties
Shen et al. Crystal structures, luminescent and thermal properties of lanthanide complexes with 3, 4-dimethylbenzoic acid and 2, 2′-bipyridine

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170811