CN107652437A - A kind of 4 one-dimensional banding coordination polymers of chlorobenzoic acid double-core manganese (II) and preparation method thereof - Google Patents
A kind of 4 one-dimensional banding coordination polymers of chlorobenzoic acid double-core manganese (II) and preparation method thereof Download PDFInfo
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 28
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 28
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 239000011572 manganese Substances 0.000 claims abstract description 31
- 239000013078 crystal Substances 0.000 claims abstract description 21
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 claims description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 20
- -1 4- chlorobenzoic acid radical ion Chemical class 0.000 claims description 14
- 125000004429 atom Chemical group 0.000 claims description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910018648 Mn—N Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 235000000621 Bidens tripartita Nutrition 0.000 claims description 3
- 240000004082 Bidens tripartita Species 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 208000006637 fused teeth Diseases 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 239000003960 organic solvent Substances 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims 1
- 229910018663 Mn O Inorganic materials 0.000 claims 1
- 229910003176 Mn-O Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical class ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000001413 cellular effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 239000013384 organic framework Substances 0.000 abstract 1
- LBQMIAVIGLLBGW-UHFFFAOYSA-N 2,5-difluorobenzoic acid Chemical compound OC(=O)C1=CC(F)=CC=C1F LBQMIAVIGLLBGW-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000011656 manganese carbonate Substances 0.000 description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JLZVIWSFUPLSOR-UHFFFAOYSA-N 2,3-difluorobenzoic acid Chemical compound OC(=O)C1=CC=CC(F)=C1F JLZVIWSFUPLSOR-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 159000000032 aromatic acids Chemical class 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- GPAAEXYTRXIWHR-UHFFFAOYSA-N (1-methylpiperidin-1-ium-1-yl)methanesulfonate Chemical compound [O-]S(=O)(=O)C[N+]1(C)CCCCC1 GPAAEXYTRXIWHR-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000238366 Cephalopoda Species 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- VWERREPJZABDMK-UHFFFAOYSA-N [Tb].FC1=C(C(=O)O)C=CC=C1F Chemical compound [Tb].FC1=C(C(=O)O)C=CC=C1F VWERREPJZABDMK-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to Inorganic-organic Hybrid Material, inorganic organic framework materials and crystal engineering field, more particularly to a kind of 4 one-dimensional banding coordination polymers of chlorobenzoic acid double-core manganese (II) and preparation method thereof.The compound has below formula：{ [(H2O) 2 of Mn 2 (4,4 ' bpy) 2 (L) 4] 3H2O } n, 4,4 ' bpy is 4,4 ' bipyridyls, and HL is 4 chlorobenzoic acids.Advantages of the present invention：The compound has the three-dimensional tube of a variety of micropore compositions, and the crystallization water is located in pipeline micro cellular voids, has potential application prospect in absorption, catalysis etc..
Description
Technical field
The present invention relates to functional material, crystallography field, matches somebody with somebody more particularly to a kind of new double-core manganese (II) one-dimensional banding
Position polymer and preparation method thereof.
Background technology
Metal organic frame (metal-organic frameworks, MOFs) material is one kind by organic ligand and metal
The material with adjustable aperture being self-assembly of is passed through at center.Compared with traditional inorganic porous material, MOFs materials have
Bigger specific surface area, higher porosity, structure and function are more various, thus be widely used in gas absorption with
It is all in nonlinear optical material, magnetic material, superconductor etc. in the fields such as separation, sensor, medicament slow release, catalytic reaction
Many-side shows fabulous application prospect.Solid material can be predicted using organic bridge ligand and metal ion assembling acquisition
Geometry, wherein coordinate bond or hydrogen bond, π-π aromaticring stackings weak interaction, electrostatic interaction and space support act on tune
Control MOF topological structures and aspect of performance have very important effect.The bridge ligands such as halogenated aromatic acid, 4,4 '-bipyridyl can
One-dimensional, two and three dimensions supermolecule is assembled into various metals, relevant non-linear optical property, catalytic action, photoelectric conversion
The achievement in research of energy has been appeared in the newspapers.
Synthesis, crystal structure and the photoluminescent property of 2,3- difluoro-benzoic acid terbium coordination compounds characterize, Capital Normal University's journal
(natural science edition) the 2nd phase of volume 31, in April, 2010, P28~31, disclose and double-core terbium coordination compound has been synthesized using solwution method
[Tb (2,3-DFBA) 3 (2,2 '-bipy)] 2 (2,3-DFBA=2,3- difluoro-benzoic acid root, 2,2 '-bipy=2,2 '-connection pyrrole
Pyridine), and the complexs are determined with X-ray single crystal diffraction to its crystal structure and belong to monoclinic system, P2 (1)/n spaces
Group is in complex, 2 Tb3+Ion is connected by 42,3- difluoro-benzoic acids roots in a manner of bridging bidentate；Each Tb3+From
Son ligancy be 8, respectively with 4 bridging bidentates 2,4 oxygen atoms of 3- difluoro-benzoic acid roots, the 2,3- of 1 chelating bidentate
2 oxygen atoms of difluoro-benzoic acid root and 12,2 nitrogen-atoms coordination of 2 '-bipyridyl complexs are in ultra violet lamp
Under send strong green glow, there are 4 spectral lines at 489,545,583 and 618nm in its fluorescence spectrum, and this is by Tb3+Ion
Caused by 5D4 → 7Fj (j=6~3) transition.
Binuclear Europium and 2,5- difluoro-benzoic acid and 2, synthesis, crystal structure and the sign of 2 '-bipyridyl complex are inorganization
Journal is learned, the 10th phase of volume 24, in October, 2008, P1621~1625, discloses and has synthesized mixed ligand coordination compound [Eu with solwution method
(2,5-DFBA) 3 (2,2 '-bipy)] 2 (2,5-DFBA=2,5- difluoro-benzoic acid roots, 2,2 '-bipy=2,2 '-bipyridyl),
And determine its crystal structure.The crystal belongs to anorthic system, P1 space groups.In complex, 2 Eu3+Ion is by 4 2,5-
Difluoro-benzoic acid root connects in a manner of bidentate bridging and three bridge works join 2 kinds；Each Eu3+The ligancy of ion be 9, respectively with 4
5 oxygen atoms of bridging 2,5- difluoro-benzoic acid roots, 2 oxygen atoms of 1 bidentate chelating 2,5- difluoro-benzoic acid roots and 1
2 nitrogen-atoms coordination of bipy 2,2' bipyridyl molecule.The complex sends strong feux rouges under ultra violet lamp, in fluorescence light
Occur 5 spectral lines at 580,591,613,648 and 693nm of spectrum, be by Eu respectively3+5D0 → 7Fj (j=0~4) jumps of ion
Caused by moving.
The content of the invention
It is an object of the present invention to provide a kind of one-dimensional banding coordination polymer of double-core manganese (II), the polymer with 4,
4 '-bipyridyl and halogenated aromatic acid are part, the ion centered on transition metal, are assembled into by coordination bonding with one-dimensional banding
The supermolecule of structure.Another object of the present invention is to provide the system of the above-mentioned one-dimensional banding coordination polymer of double-core manganese (II)
Preparation Method,
In order to realize first above-mentioned purpose, present invention employs following technical scheme：
A kind of one-dimensional banding coordination polymer of 4- chlorobenzoic acids double-core manganese (II), its structural formula are as follows：
Described 4,4 '-bpy are 4,4'-Bipyridine, and HL is 4- chlorobenzoic acids.
One-dimensional banding coordination polymer is made up of coordination polymer molecule and crystalline water molecules, in coordination polymer,
The coordination mode of Mn1 atoms and Mn2 atoms is different, each Mn2 atoms and 4 oxygen atoms from 3 4- chlorobenzoic acids
It is coordinated with 2 nitrogen-atoms from 24,4 '-bpy, constitutes the hexa-coordinate MnN slightly to distort2O4Octahedral coordination environment；And
Mn1 atoms except with 3 oxygen atoms from 3 2- chlorobenzoic acids and from 24,4 '-bpy 2 nitrogen-atoms coordination is outer,
Also with 1 hydrone oxygen atom ligand, the hexa-coordinate MnN of distortion is also formed2O4Octahedral coordination environment.
2 4- chlorobenzoic acids radical ion bridging Mn1 double-core manganese node with Mn2 atomic buildings, 2 4,4'-Bipyridine molecules while 2 Mn (II) nodes of bridging, form and infinitely extend along [100] direction
One-dimensional condensation zone；Its bond distance and bond angle are ∠ (N-Mn-N) is 175.42 (17) ° and 176.18 (16) ° respectively, d (Mn (1)-Mn (1)i) and d (Mn
(1)–Mn(1)i) distance it is equal, be all ford(Mn(1)–Mn(1)i), (i=1+x, y, z).
4 4- chlorobenzoic acids radical ions on same node are divided into bridging and single, double tooth coordination 2 by coordination mode difference
Group, the 4- chlorobenzoic acids radical ion of double coordination on the connecting line of 2 manganese atoms, the 4- chlorobenzoic acids root of monodentate ligand from
Son because monodentate ligand deviate from the connecting line of 2 manganese atoms, bridging group perpendicular to 2 manganese atoms connecting line, then by 24,
4 '-bpy molecules bridgings form one-dimensional coordination polymerization band.
Mutually stagger between band and band, and by O-H ... O, O-H ... Cl, strong, the weak hydrogen bonds of tri- kinds of C-H ... O constitute three
Tie up supramolecular network structure.Wherein bond distance, bond angle are respectively： ∠ (O-H ... O)=
114-176 °, ∠ (O-H ... Cl)=179 °, ∠ (C-H ... O)=119-161 °.
In order to realize second above-mentioned purpose, present invention employs following technical scheme：
A kind of preparation method for preparing the above-mentioned one-dimensional banding coordination polymer of 4- chlorobenzoic acid double-core manganese (II), this method include
Following step：Freshly prepared MnCO3, 4- chlorobenzoic acids ClC6H4COOH, 4,4-Bipyridine, with CH3OH/H2O(v:V=1:
2) mixed solvent 15mL mixes stirring 2.0 hours, then the khaki suspension of gained is enclosed inner liner polytetrafluoroethylene not
Become rusty in steel reactor, reactor is finally placed in 160 DEG C of temperature programmed control of baking oven inside holding one week by compactedness 60-85%.From
Room temperature so is cooled to, is filtered to remove khaki insoluble matter.Gained pale yellow filtrate is placed in natural evaporation at room temperature, after one month
To the yellow crystals tested suitable for monocrystalline；With distillation water washing after spontaneously dry.
The features of the present invention：When crystal structure by 4,4-bipyridyl and 4- chlorobenzoic acids radical ion two kinds of parts difference
From [100], [010] both direction coordination 2 manganese atoms of bridging, the new one-dimensional banded structure of double-core manganese is formed, then pass through interband
Three-dimensional Supramolecular Network structure is formed with interlayer O-H ... O, O-H ... Cl, strong, the weak hydrogen bond actions of tri- kinds of C-H ... O, is constituted
The three-dimensional tube being made up of a variety of micropores；Second, compact crystal structure is staggeredly accumulated, the crystallization water is located in pipeline micro cellular voids.Newly
Type coordination polymer is stablized at normal temperatures, 110 DEG C of beginning dehydrations, before all many-sides such as absorption, catalysis have good application
Scape.
Brief description of the drawings
Fig. 1 is the crystal structure unit (50%probability) of the compounds of this invention.
Fig. 2 is one-dimensional Langmuir-Blodgett Film of the compounds of this invention along the extension of [101] direction.
Fig. 3 is accumulation graph of the compounds of this invention along [101] direction.
Fig. 4 is the infrared spectrum of the compounds of this invention.
Fig. 5 is the TG curves of the compounds of this invention.
Fig. 6 is the powder diagram of the compounds of this invention.
Embodiment
1.1 reagents and instrument
Agents useful for same is ommercially available AR, VarioIII types elemental analyser (German Elementar companies), FT-IR
Instrument (Nicolet companies of U.S. EXUS670 types)；TGA/SDTA 851eInstrument (Meltter-Toludo companies of Switzerland)；BIUKER is public
Take charge of APEX CCD II type single crystal diffractometers；SQUID Quantum Design Model MPMS -7 type magnetometers
The synthesis of 1.2 complexs
Weigh MnCl2·2H2O 0.163g (1.00mmol) are dissolved in appropriate distilled water, then add enough saturated sodium carbonates
Solution, centrifuge and wash MnCO35 times, take freshly prepared MnCO3, then add 4- chlorobenzoic acids ClC6H4COOH 0.157g
(1.00mmol), 4,4-Bipyridine 0.160g (1.02mmol), with CH3OH/H2O(v:V=1:2) mixed solvent 15mL
Stirring 2.0 hours is mixed, then the khaki suspension of gained is enclosed in the stainless steel cauldron of inner liner polytetrafluoroethylene, filling
60-85% is spent, reactor is finally placed in 160 DEG C of temperature programmed control of baking oven inside holding one week.Room temperature is naturally cooled to, is filtered
Remove colour of loess insoluble matter.Gained pale yellow filtrate is placed in natural evaporation at room temperature, obtains being applied to monocrystalline test after one month
Yellow crystals.With distillation water washing after spontaneously dry.
1.3 crystal structure determination
Selection size is 0.540mm × 0.250mm × 0.200mm monocrystalline, is collected on APEX CCD II type single crystal diffractometers
Diffraction data, using MoK alpha raysIn the range of 3.09 °≤θ≤25.00 ° with ω andScanning
Mode is collected into 19858 data altogether, wherein independent point diffraction 8831 [R (int) >=0.0273], 6232 [F0 2≥2σ
(F0 2)] observable point diffraction is used for structural modifications, diffracted intensity data are through the Lp factors and empirical absorption correction.Whole non-hydrogen atoms
Obtained using direct method, non-hydrogen atom coordinate and its anisotropic temperature factor use complete matrix least square method amendment, carbon original
Hydrogen atom on son is obtained by theory hydrogenation.Predominant crystal data is listed in table 1.W=1/ [σ2(F0 2)+(0.1474×P)2+
4.70 × P], P=(F0 2+2Fc 2)/3.The S values of last wheel amendment are 1.061, (Δ/σ)maxFor 0.001, difference Fourier
On maximum remaining peak Δ ρmax=1741e/nm3, peak Δ ρ more than Minimum Residualmin=-814e/nm3.All calculating use SHELX -97
Program[6,7], carried out on PentiumIV 300.
The crystallographic data of the complex of table 1
2.1 infrared spectrum
Infrared spectrum (shown in Fig. 4) principal character peak of the compounds of this invention is attributed to：3070cm-1, stretched for C-H on aromatic ring
Contracting absorption of vibrations, 3420cm-1Absorbed for the stretching vibration of water of coordination and crystallization water O-H keys, 1610cm-1,1560cm-1,
1450cm-1, 1420cm-1For aromatic ring frame absorption of vibrations, 1610cm-1,1420cm-1For double coordination carboxylate anion (-
COO–) asymmetric and symmetric stretching vibration absorb, wherein 1610cm-1Absworption peak it is especially strong, be due to aromatic ring frame vibration
Absorb caused by the bimodal degeneracy of asymmetric absorption with carboxylic acid ion.
2.2 differential thermal-thermogravimetric analysis
Differential thermal-thermogravimetric analysis is carried out under nitrogen protection, nitrogen rate 20mLmin–1, heating rate is 10 DEG C of min–1, mark
The TG curves of topic complex sample show (shown in Fig. 5), stablize at normal temperatures, are heated to 110 DEG C and start to lose the crystallization water and match somebody with somebody
Position water, there is the essential characteristic of functional material.
2.3 crystal structure
Complex of the present invention Main bond distance and bond angle be shown in Table 2, crystal structure (shown in Fig. 1,2,3).Crystal structure analysis
Show, the complex is the one-dimensional banding coordination polymer of double-core, one-dimensional banding coordination polymer be by coordination polymer molecule and
Crystalline water molecules form, and in coordination polymer, the coordination mode of Mn1 atoms and Mn2 atoms is different, each Mn2 atoms
With 4 oxygen atoms from 3 4- chlorobenzoic acids and from 24,4 '-bpy 2 nitrogen-atoms are coordinated, and are constituted and are slightly distorted
Hexa-coordinate MnN2O4Octahedral coordination environment；And Mn1 atoms are with 3 oxygen atoms from 3 2- chlorobenzoic acids and from 2
4,4 '-bpy 2 nitrogen-atoms coordination are outer, also the oxygen atom ligand with 1 hydrone, also form the hexa-coordinate MnN of distortion2O4Eight
Face body coordination environment.
2 4- chlorobenzoic acids radical ion bridging Mn1 double-core manganese node with Mn2 atomic buildings,
2 4,4'-Bipyridine molecules distinguish 2 Mn (II) nodes of bridging, form infinitely extend along [100] direction it is one-dimensional poly-
Crossed belt；Its bond distance and bond angle areD (Mn-N)=2.265 (4) -2.288 (4)∠ (N-Mn-N) is 175.42 (17) ° and 176.18 (16) ° respectively, d (Mn (1)-Mn (1)i) and d (Mn (1)-Mn (1)i)
Apart from equal, be all ford(Mn(1)–Mn(1)i), (i=1+x, y, z)；Illustrate two N atoms of axial direction with
Heart Mm atoms are almost on the same line.
4 4- chlorobenzoic acids radical ions on same node are divided into bridging according to coordination mode and single, double tooth is coordinated 2 groups, bidentate
The 4- chlorobenzoic acids radical ion of coordination on the connecting line of 2 manganese atoms, the 4- chlorobenzoic acids radical ion of monodentate ligand due to
Monodentate with deviate from the connecting line of 2 manganese atoms, bridging group perpendicular to 2 manganese atoms connecting line, then by 4,4 '-bpy points
Sub further bridging forms one-dimensional condensation zone；
Mutually stagger between band and band, and by O-H ... O, O-H ... Cl, strong, the weak hydrogen bonds of tri- kinds of C-H ... O constitute three-dimensional oversubscription
Sub-network structure.Wherein bond distance, bond angle are respectively： ∠ (O-H ... O)=114-176 °, ∠
(O-H ... Cl)=179 °, ∠ (C-H ... O)=119-161 °.
The unique distinction of this crystal structure, first, part 4- chlorobenzoic acids radical ion and 4,4-bipyridyl respectively from [010],
[100] both direction matches somebody with somebody 2 manganese atoms of bridging, O, O-H ... Cl that forms the one-dimensional banded structure of double-core manganese, then pass through O-H ...,
Strong, the weak hydrogen bond actions of tri- kinds of C-H ... O form two dimension, Three-dimensional Supramolecular Network structure, constitute the three-dimensional tube being made up of micropore
Road；Second, crystal structure heavily fortified point closs packing, in the space of crystalline water molecules position frame structure, can be taken by other small solvent molecules
In generation, meet the primary condition of metal-organic framework material.
2. main bond distance of tableWith bond angle [°]
Symmetry transformations used to generate equivalent atoms:#1 x+1,y,z #2
x-1,y,z 。
Claims (8)
- The one-dimensional banding coordination polymer of 1.4- chlorobenzoic acid double-core manganese (II), it is characterised in that：The compound has following structure Formula：[Mn2(4,4’ -bpy)2(L)4(H2O)2] ·3H2O；Described 4,4 '-bpy are 4,4'-Bipyridine, and HL is 4- chlorobenzoic acids.
- 2. according to the one-dimensional banding coordination polymer of 4- chlorobenzoic acids double-core manganese (II) described in right 1, it is characterised in that：The one-dimensional band Shape coordination polymer is made up of coordination polymer molecule and crystalline water molecules, and in coordination polymer, Mn1 atoms are former with Mn2 Son coordination mode it is different, each Mn2 atoms with from 3 4- chlorobenzoic acids 4 oxygen atoms and from 24,4 '- Bpy 2 nitrogen-atoms coordination, constitutes the hexa-coordinate MnN slightly to distort2O4Octahedral coordination environment；And Mn1 atoms are with coming from 3 3 oxygen atoms of individual 2- chlorobenzoic acids and from 24,4 '-bpy 2 nitrogen-atoms coordination is outer, also former with the oxygen of 1 hydrone Son coordination, also form the hexa-coordinate MnN of distortion2O4Octahedral coordination environment.
- 3. according to the one-dimensional banding coordination polymer of 4- chlorobenzoic acids double-core manganese (II) described in right 2, it is characterised in that：The one-dimensional band Mn1, Mn2 atom in shape coordination polymer structure first constitutes double-core manganese node, d by 2 4- chlorobenzoic acid radical ion bridgings (Mn(1)–Mn(2))= 4.278(2)Å；Distinguish 2 Mn (II) nodes of bridging by 2 4,4'-Bipyridine molecules again, form edge [100] the one-dimensional condensation zone that direction infinitely extends；Its bond distance and bond angle are d (Mn-O)=2.073 (4) -2.271 (4), d (4) -2.288 (4) of (Mn-N)=2.265, ∠ (N-Mn-N) is 175.42 (17) ° and 176.18 respectively（16）°, d (Mn (1)- Mn(1)i) and d (Mn (1)-Mn (1)i) distance it is equal, be all for 11.625 (2), d (Mn (1)-Mn (1)i), (i=1+x, Y, z).
- 4. according to the one-dimensional banding coordination polymer of 4- chlorobenzoic acids double-core manganese (II) described in right 3, it is characterised in that：Same node On 4 4- chlorobenzoic acids radical ions bridging and single, double tooth are divided into according to coordination mode are coordinated 2 groups, the 4- chlorobenzenes of double coordination Formate ion is on the connecting line of 2 manganese atoms, and the 4- chlorobenzoic acids radical ion of monodentate ligand is due to monodentate ligand deviation The connecting line of 2 manganese atoms, bridging group is perpendicular to the connecting line of 2 manganese atoms, 24,4 '-bpy molecules bridging Mn simultaneously (II) the one-dimensional banding coordination polymer of 2 Mn atomic buildings on node；Mutually stagger between band and band, and by O-H ... O, O-H ... Cl, strong, the weak hydrogen bonds of tri- kinds of C-H ... O constitute Three-dimensional Supramolecular Network structure.
- 5. according to the one-dimensional banding coordination polymer of 4- chlorobenzoic acids double-core manganese (II) described in right 4, it is characterised in that：Wherein key Length, bond angle are respectively：d(O—H…O）= 2.5527(3)–2.8484(3) Å、d（O—H…Cl）= 3.4012(3) Å、d （C—H…O）= 3.1120(3)–3.3568(3) Å, ∠（O—H…O）=114–176°、∠（O—H…Cl）=179°、∠ （C—H…O）=119–161°.
- 6. the preparation method of the one-dimensional banding coordination polymer of 4- chlorobenzoic acids double-core manganese (II) according to claim 1, its It is characterised by that this method comprises the following steps：1）Make fresh MnCO by oneself3, 4- chlorobenzoic acid roots, 4,4'-Bipyridine, with CH3OH/H2O(v:v = 1:2) mixing is molten Agent mixes stirring a few hours, then the khaki suspension of gained is enclosed in the stainless steel cauldron of inner liner polytetrafluoroethylene, fills out Reactor, is finally placed in 160 DEG C of temperature programmed control of baking oven inside holding one week by degree of filling 60-85%；2）Room temperature is naturally cooled to, is filtered to remove khaki insoluble matter；3）Gained pale yellow filtrate is placed in natural evaporation at room temperature, obtains being applied to the yellow crystals of monocrystalline test after one month；4）With distillation water washing after spontaneously dry.
- 7. the preparation side of the one-dimensional banding coordination polymer of 4- chlorobenzoic acid double-core manganese (II) according to preparing claim 6 Method, it is characterised in that：Step 1）In organic solvent be methanol or ethanol.
- 8. the preparation side of the one-dimensional banding coordination polymer of 4- chlorobenzoic acid double-core manganese (II) according to preparing claim 6,7 Method, it is characterised in that：The volume ratio of organic solvent and distilled water is 1：2.0~2.5.
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