CN108516954A - A kind of Spin crossover crystal and preparation method thereof - Google Patents
A kind of Spin crossover crystal and preparation method thereof Download PDFInfo
- Publication number
- CN108516954A CN108516954A CN201810308771.5A CN201810308771A CN108516954A CN 108516954 A CN108516954 A CN 108516954A CN 201810308771 A CN201810308771 A CN 201810308771A CN 108516954 A CN108516954 A CN 108516954A
- Authority
- CN
- China
- Prior art keywords
- crystal
- preparation
- solvent
- spin crossover
- spin
- 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
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims abstract description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 10
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical class NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 150000003222 pyridines Chemical class 0.000 claims description 6
- MOMFXATYAINJML-UHFFFAOYSA-N 2-Acetylthiazole Chemical group CC(=O)C1=NC=CS1 MOMFXATYAINJML-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- CKFMJXZQTNRXGX-UHFFFAOYSA-L iron(2+);diperchlorate Chemical class [Fe+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O CKFMJXZQTNRXGX-UHFFFAOYSA-L 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 2
- -1 ferrous perchlorates Salt Chemical class 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 6
- 241000736199 Paeonia Species 0.000 description 5
- 235000006484 Paeonia officinalis Nutrition 0.000 description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 0 *NCC1C=C=CC=C1 Chemical compound *NCC1C=C=CC=C1 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 241001614291 Anoplistes Species 0.000 description 1
- UEKUATXMFCXVSX-UHFFFAOYSA-N BC1=CCCC(C(C)=[N]=C)=CC=C1 Chemical compound BC1=CCCC(C(C)=[N]=C)=CC=C1 UEKUATXMFCXVSX-UHFFFAOYSA-N 0.000 description 1
- UMULUDKNGDJLTM-UHFFFAOYSA-N CC1N=CC=CC1 Chemical compound CC1N=CC=CC1 UMULUDKNGDJLTM-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/72—Nitrogen atoms
- C07D213/76—Nitrogen atoms to which a second hetero atom is attached
- C07D213/77—Hydrazine radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a kind of Spin crossover crystal and preparation method thereof, it is related to a kind of spin crossover material and preparation method thereof.The invention aims to solve the problem of that existing Spin crossover ligand diversity preparation method is cumbersome and low yield.A kind of expression formula of Spin crossover crystal is { [Fe (Br Pphep)2]·(ClO4)2}·CH3CN, structural formula are as follows：。
Description
Technical field
The invention belongs to Material Fields, and in particular to a kind of Spin crossover crystal and preparation method thereof.
Background technology
When the electron configuration of the central ion of Octahedral Complexes is d4~d7And in the suitable Ligand Field of intensity
When, if the crystal field splitting energy Δ of complex is close with electronics pairing energy P, at the energy level difference between high low spin state and kT
In the same order of magnitude, then complex molecule can under an appropriate and controllable extraneous perturbation (such as temperature, pressure, light radiation)
The conversion between high spin state and low spin state occurs, this phenomenon is known as spin crossover or Spin transition.
By taking Fe (II) as an example, 5 d tracks of degeneracy split into two groups, respectively three-fold degeneracy under octahedra field action
The d of statexy、dyzAnd dxz, use t2gExpression and double degenerate state dx2-y2And dz2, use egIt indicates.In feeble field, Δ<P, electronics group
State is t4 2ge2 g, high spin state (HS) is stable, spin quantum number S=2；In high field, Δ>P, electron configuration t6 2g, low spin
State (LS) is stablized, spin quantum number S=0.
Research in relation to Spin crossover starts from (the Cambi L, Cagnasso such as Cami in 1931
A.Atti.Accad.Naz.L incei.,1931,13:809) to the research of a kind of Fe (III) complex, Baker in 1964 etc.
(Baker W A,Bobonich H M.Inorg.Chem.,1964,3:First 1184-1188) is found that caused by temperature
Fe (II) Spin crossover [Fe (phen)2(NCX)2], hereafter, people gradually increase the research of Spin crossover.
Since Spin crossover is under a kind of lasting extraneous perturbation (such as temperature, pressure, light radiation), a kind of stable state can occur
Transformation to another stable state, to play the role of information storage and switch.Display can be made using this property
The different kinds of molecules sill device such as activeleg, temperature sensor, photoswitch and the imformation memory of device, storage.
The current existing report about Spin crossover concentrates on the complex of Fe (II), Fe (III), wherein Fe
(II) can occur'sTransformation, therefore design and synthesize such Spin crossover crystalline substance
Body makes great sense for making molecular switch material devices.
Invention content
Goal of the invention：To solve the technical problems existing in the prior art, the present invention proposes a kind of spin crossover cooperation
Object crystal and preparation method thereof.
Technical solution：Spin crossover crystal proposed by the present invention, expression formula are { [Fe (Br-Pphep)2]·
(ClO4)2}·CH3CN, structural formula are as follows：
Wherein, the { [Fe (Br-
Pphep)2]·(ClO4)2}·CH3Br-Pphep in CN is the bromo- 6- of (anti-) -2- (1- (Asias 2- phenyl -2- (2- pyridyl groups) hydrazines
Base) ethyl) pyridine, structural formula is as follows：
Present invention further proposes the preparation methods of the Spin crossover crystal, include the following steps：
(1) it is 0.7 according to the amount ratio of substance by 2- (1- phenylhydrazines) pyridines and 2- acetyl group -6- bromopyridines：1~1.3：1 adds
Enter into certain solvent, reaction 1h~3h is stirred at reflux at 70 DEG C~90 DEG C, cooling revolving obtains rufous oily liquids
The bromo- 6- of (anti-) -2- (1- (2- phenyl -2- (2- pyridyl groups) hydrazono-) ethyl) pyridine, reaction equation are：
Wherein, 2- (1- benzene
Hydrazine) pyridine press document the method (K.Ghosh, N.Tyagi, P.Kumar, Inorg.Chem.Commun.2010,13,380-
383) it synthesizes.
(2) at room temperature, crystal culture solvent is prepared；
(3) the bromo- 6- of (anti-) -2- (1- (2- phenyl -2- (2- pyridyl groups) hydrazono-) ethyl) pyridines and nine water perchloric acid are pressed
The amount ratio of the substance of ferrous salt is 3:1~1:1 is added in the crystal culture solvent described in step (2), and reaction is stirred at room temperature
10min~30min is refiltered, and obtains filtrate；
(4) filtrate added drop-wise that step (3) obtains is entered into small test tube, small test tube is put into the carboy for filling appropriate ether
In, and carboy is sealed, stand more days, crystal is precipitated on test tube wall to get to a kind of Spin crossover crystal.
Wherein, in step (1), certain solvent is methanol, a kind of solvent in ethyl alcohol, acetonitrile or a variety of mixing are molten
Agent.
In step (1), the amount ratio of the volume of certain solvent and the substance of 2- (1- phenylhydrazines) pyridine is 10.0mL:
0.01mol~50.0mL:0.01mol.
In step (2), the crystal culture solvent is any one or more in methanol, acetonitrile, dichloromethane
Mixture.The volume of crystal culture solvent described in step (3) and the amount ratio of the substance of nine water ferrous perchlorate's salt are
1.0mL:0.05mmol~10.0mL:0.05mmol.
In step (3), it is 200r/min~250r/min that speed, which is stirred at room temperature,.
Time of repose described in step (4) is 2d~10d.
Advantageous effect：Compared with prior art, the invention has the advantages that：
(1) a kind of Spin crossover crystal prepared in the present invention, possesses the suitable Novel Ligands of Ligand Field, has
Good spin crossover property；
(2) preparation method of the invention, complex synthetic method is simple, at low cost, and product is stablized at normal temperatures chemically
Matter is stablized；
(3) preparation method provided by the invention can obtain regular crystal forms by the optimal synthesis path of a variety of experiment sievings,
A kind of good Spin crossover crystal of crystal data；
(4) a kind of yield of Spin crossover crystal prepared by the present invention is 73%~75%.
Description of the drawings
Fig. 1 is that a kind of Spin crossover crystal prepared by the specific embodiment of the invention one is spread out using X-ray monocrystalline
Penetrate the molecular structure of instrument determination；
Fig. 2 is a kind of alternating temperature DC magnetic susceptibility of Spin crossover crystal prepared by the specific embodiment of the invention one
Curve, wherein external magnetic field are 1000Oe；
Fig. 3 is a kind of X-ray powder diffraction of Spin crossover crystal prepared by the specific embodiment of the invention one
Datagram；
Fig. 4 is a kind of infrared spectrogram of Spin crossover crystal prepared by the specific embodiment of the invention one.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.Term as used in the present invention, unless
It is otherwise noted, generally there is the normally understood meaning of those of ordinary skill in the art.It will be helpful into one by following embodiments
Step understands the present invention, but does not limit present disclosure.
Specific implementation mode one：Present embodiment is a kind of preparation method of Spin crossover crystal, is by following
Prepared by step：
(1) press document the method (K.Ghosh, N.Tyagi, P.Kumar, Inorg.Chem.Commun.2010,13,
380-383) 2- (1- phenylhydrazines) pyridine is synthesized；
(2) the amount ratio for pressing 2- (1- phenylhydrazines) pyridines and the substance of 2- acetyl group -6- bromopyridines is 1:1 is added to etoh solvent
In, reaction 3h is stirred at reflux at 85 DEG C, cooling revolving obtains rufous oily liquids (anti-) -2- bromo- 6- (1- (2- phenyl -
2- (2- pyridyl groups) hydrazono-) ethyl) pyridine；
The amount ratio of the volume of etoh solvent described in step (2) and the substance of 2- (1- phenylhydrazines) pyridine is 20.0mL:
0.01mol；
(3) at room temperature, using solvent acetonitrile as crystal culture solvent；
(4) the bromo- 6- of (anti-) -2- (1- (2- phenyl -2- (2- pyridyl groups) hydrazono-) ethyl) pyridines and nine water perchloric acid are pressed
The amount ratio of the substance of ferrous salt is 2:1 is added in the crystal culture solvent described in step (3), is stirred to react 10min at room temperature, then
Filtering, obtains filtrate；
The volume of crystal culture solvent described in step (4) and the amount ratio of the substance of nine water ferrous perchlorate's salt are
4.0mL:0.05mmol；
(5) filtrate added drop-wise that step (4) obtains is entered into small test tube, small test tube is put into the carboy for filling appropriate ether
In, and carboy is sealed, stand 5 days, crystal is precipitated on test tube wall to get to a kind of Spin crossover crystal；
The volume ratio of ether and filtrate described in step (5) is 3:1.
The molecular formula of 2- acetyl group -6- bromopyridines is C in present embodiment7H6BrNO；
The molecular formula of nine water ferrous perchlorate's salt is Fe (ClO in present embodiment4)2·9H2O。
The advantages of specific implementation mode one：
One, a kind of Spin crossover crystal prepared in present embodiment has good spin crossover property,
Magnetic property characterization is shown in Fig. 2；
Two, a kind of Spin crossover crystal prepared in present embodiment, chemical property stabilization, is deep at normal temperatures
Red bulk crystals；
Three, present embodiment passes through the optimal synthesis path of a variety of experiment sievings, can obtain regular crystal forms, crystal data is good
A kind of Spin crossover crystal；
Four, a kind of yield of Spin crossover crystal prepared by present embodiment is 75%.
Present embodiment can get a kind of Spin crossover crystal and preparation method thereof.
A kind of Spin crossover crystal obtained in specific implementation mode one, after testing, yield 75%, molecule
Structure chart is as shown in Figure 1；Fig. 1 is that a kind of Spin crossover crystal prepared in specific implementation mode one utilizes X-ray list
The molecular structure that brilliant diffractometer determines.
Fig. 2 is that a kind of alternating temperature DC magnetic susceptibility of the Spin crossover crystal prepared in specific implementation mode one is bent
Line, wherein external magnetic field are 1000Oe；It can determine that it is Spin crossover by Fig. 2, vary with temperature and high low spin state occurs
Transformation；By studying magnetic property, show that it, with spin crossover property, has in fields such as molecular-based magnets switches and actually answer
With value.
Fig. 3 is a kind of X-ray powder diffraction data of the Spin crossover crystal prepared in specific implementation mode one
Figure.As can be seen from Figure 3, the powder diffraction data and monocrystalline of a kind of Spin crossover crystal prepared in specific implementation mode one
Fitting data matches, and illustrates that a kind of Spin crossover crystal prepared in experiment one is high-purity.
Fig. 4 is a kind of infrared spectrogram of the Spin crossover crystal prepared in specific implementation mode one.It can from Fig. 4
Know, characteristic infrared spectrum peak (KBr, the cm of a kind of Spin crossover crystal prepared in specific implementation mode one-1) be
3443 (m), 3085 (m), 1584 (s), 1538 (m), 1450 (b, s), 1303 (s), 1086 (vs), 775 (m), 623 (s), wherein
1584cm-1For the feature stretching vibration peak of R-C=C-R ', 1450cm-1The bimodal C- for methyl in solvent acetonitrile molecule of left and right
The flexural vibrations peak of H, 1086cm-1For the fingerprint absorption peak of the C-H on phenyl ring.
Specific embodiment two：The difference of present embodiment and specific implementation mode one is：By 2- (1- benzene in step (2)
Hydrazine) pyridine and 2- acetyl group -6- bromopyridines according to the amount ratio of substance be 1:1 is added in solvent methanol, is stirred back at 80 DEG C
Stream reaction 2h；It is at room temperature 1 by volume by solvent methanol and acetonitrile in step (3):1 is mixed to get crystal culture solvent.
Other are same as the specific embodiment one.
A kind of Spin crossover obtained in specific implementation mode two is that peony is needle-shaped and rhabdolith, yield are
56%.
Comparative example one：The difference of this comparative example and specific implementation mode two is：In step (3), at room temperature by solvent
Methanol, acetonitrile and dichloromethane are 1 by volume:1:2 are mixed to get crystal culture solvent.Other are identical as embodiment two.
For this comparative example compared with specific implementation mode two, a kind of obtained Spin crossover is the needle-shaped crystalline substance of peony
Body, yield 51%.
Specific embodiment three：The difference of present embodiment and specific implementation mode one or two is：In step (3), in room
Under temperature by solvent acetonitrile and dichloromethane by volume be 1:1 is mixed to get crystal culture solvent.Other with embodiment one or
Two is identical.
A kind of Spin crossover obtained in specific implementation mode three is peony acicular crystal, yield 62%.
Specific embodiment four：The difference of present embodiment and specific implementation mode one, two or three is：In step (3),
It is at room temperature 1 by volume by solvent methanol and dichloromethane:1 is mixed to prepare crystal culture solvent.Other and specific embodiment party
Formula one, two or three are identical.
Obtain peony acicular crystal in specific implementation mode four, yield 37%, the Spin crossover of gained
Contained solvent is different from a kind of lattice solvent of Spin crossover of the present invention in lattice.
Comparative example two：The difference of this comparative example and specific implementation mode four is：In step (3), at room temperature by solvent
Methanol is as crystal culture solvent.Other are identical as embodiment four.
For this comparative example compared with specific implementation mode four, obtained peony acicular crystal yield is 24%.
In conclusion by selecting suitable crystal culture solvent, one kind can be prepared certainly using the method for the present invention
Rotation intersects complex crystal, possesses the suitable Novel Ligands of Ligand Field, has good spin crossover property.
Above-described is only embodiments of the present invention, it should be noted here that for those of ordinary skill in the art
For, without departing from the concept of the premise of the invention, improvement can also be made, but these belong to the protection model of the present invention
It encloses.
Claims (8)
1. a kind of Spin crossover crystal, which is characterized in that the expression formula of the Spin crossover crystal is { [Fe
(Br-Pphep)2]·(ClO4)2}·CH3CN, structural formula are as follows：
Wherein, the { [Fe (Br-Pphep)2]·(ClO4)2}·CH3Br-Pphep in CN is the bromo- 6- (1- of (anti-) -2-
(2- phenyl -2- (2- pyridyl groups) hydrazono-) ethyl) pyridine, structural formula is as follows：
2. the preparation method of Spin crossover crystal described in claim 1, which is characterized in that include the following steps：
(1) it is 0.7 according to the amount ratio of substance by 2- (1- phenylhydrazines) pyridines and 2- acetyl group -6- bromopyridines：1~1.3：1 is added to
In certain solvent, reaction 1h~3h is stirred at reflux at 70 DEG C~90 DEG C, cooling revolving obtains rufous oily liquids (anti-)-
The bromo- 6- of 2- (1- (2- phenyl -2- (2- pyridyl groups) hydrazono-) ethyl) pyridine, reaction equation are：
(2) at room temperature, crystal culture solvent is prepared；
(3) by the bromo- 6- of (anti-) -2- (1- (2- phenyl -2- (2- pyridyl groups) hydrazono-) ethyl) pyridines and nine water ferrous perchlorates
Salt is 3 according to the amount ratio of substance:1~1:1 is added in the crystal culture solvent described in step (3), is stirred to react at room temperature
10min~30min is refiltered, and obtains filtrate；
(4) filtrate added drop-wise that step (3) obtains is entered into small test tube, small test tube is put into the carboy for filling appropriate ether,
And seal carboy, several days are stood, are precipitated crystal on test tube wall to get to a kind of Spin crossover crystal.
3. preparation method according to claim 2, which is characterized in that in step (1), certain solvent be methanol,
The mixture of any one solvent or multi-solvents in ethyl alcohol, acetonitrile.
4. preparation method according to claim 2, which is characterized in that in step (2), the volume and 2- of certain solvent
The amount ratio of the substance of (1- phenylhydrazines) pyridine is 10.0mL:0.01mol~50.0mL:0.01mol.
5. preparation method according to claim 2, which is characterized in that in step (2), the crystal culture solvent is first
The mixture of any one or more in alcohol, acetonitrile, dichloromethane.
6. preparation method according to claim 2, which is characterized in that the body of the crystal culture solvent described in step (3)
The amount ratio of product and the substance of nine water ferrous perchlorate's salt is 1.0mL:0.05mmol~10.0mL:0.05mmol.
7. preparation method according to claim 2, which is characterized in that in step (3), it is 200r/min that speed, which is stirred at room temperature,
~250r/min.
8. preparation method according to claim 2, which is characterized in that time of repose described in step (4) be 2d~
10d。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810308771.5A CN108516954A (en) | 2018-04-09 | 2018-04-09 | A kind of Spin crossover crystal and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810308771.5A CN108516954A (en) | 2018-04-09 | 2018-04-09 | A kind of Spin crossover crystal and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108516954A true CN108516954A (en) | 2018-09-11 |
Family
ID=63431757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810308771.5A Pending CN108516954A (en) | 2018-04-09 | 2018-04-09 | A kind of Spin crossover crystal and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108516954A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369728A (en) * | 2018-11-27 | 2019-02-22 | 安庆师范大学 | A kind of nickel complex and preparation method thereof based on phenylenediacetic Acid and double pyridinylmethylene hydrazine ligands |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070081923A (en) * | 2006-02-14 | 2007-08-20 | (주)우리정도 | Spin crossover liquid crystal polymer |
| WO2009080138A2 (en) * | 2007-12-22 | 2009-07-02 | Forschungszentrum Karlsruhe Gmbh | The use of the spin crossover complex [mx+(l2)hw]an)z as a magnetic resonance imaging contrast agent |
| CN103193827A (en) * | 2013-04-22 | 2013-07-10 | 新疆大学 | N4O2 type mononuclear Fe(II) spin crossover complex and synthesis method thereof |
| CN106632504A (en) * | 2016-09-29 | 2017-05-10 | 大连理工大学 | Spin crossover-fluorescent difunctional complex as well as preparation method and application thereof |
-
2018
- 2018-04-09 CN CN201810308771.5A patent/CN108516954A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070081923A (en) * | 2006-02-14 | 2007-08-20 | (주)우리정도 | Spin crossover liquid crystal polymer |
| WO2009080138A2 (en) * | 2007-12-22 | 2009-07-02 | Forschungszentrum Karlsruhe Gmbh | The use of the spin crossover complex [mx+(l2)hw]an)z as a magnetic resonance imaging contrast agent |
| CN103193827A (en) * | 2013-04-22 | 2013-07-10 | 新疆大学 | N4O2 type mononuclear Fe(II) spin crossover complex and synthesis method thereof |
| CN106632504A (en) * | 2016-09-29 | 2017-05-10 | 大连理工大学 | Spin crossover-fluorescent difunctional complex as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| ANGELICA M. VECCHIO-SADUS: "Electrochemical synthesis of neutral transition metal(II) (Fe, Co, Ni,Cu, Zn) complexes of pyridine-2-carbaldehyde pyridin-2"-ylhydrazone and several analogues", 《TRANSITION METAL CHEMISTRY》 * |
| KAUSHIK GHOSH,ET AL.: "Spontaneous Reduction of Mononuclear High-Spin Iron(III) Complexes to Mononuclear Low-Spin Iron(III) Complexes in Aqueous Media and Nuclease Activity via Self-Activation", 《CHEMISTRY AN ASIAN JOURNAL》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369728A (en) * | 2018-11-27 | 2019-02-22 | 安庆师范大学 | A kind of nickel complex and preparation method thereof based on phenylenediacetic Acid and double pyridinylmethylene hydrazine ligands |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mautner et al. | Synthesis and structural characterization of isothiocyanato-4-methoxypyridine-cobalt (II) complexes with diverse geometries and a bridged 1D coordination polymer showing metamagnetic transition | |
| Liu et al. | Selectively sensing and adsorption properties of nickel (II) and cadmium (II) architectures with rigid 1H-imidazol-4-yl containing ligands and 1, 3, 5-tri (4-carboxyphenyl) benzene | |
| CN106977554B (en) | Four core silver different metal cluster compounds and preparation method thereof | |
| Akine et al. | Synthesis, stability, and complexation behavior of isolable salen-type N2S2 and N2SO ligands based on thiol and oxime functionalities | |
| CN108191895B (en) | Based on four core dysprosium cluster compounds of 2- aldehyde radical -8-hydroxyquinoline contracting trihydroxy aminomethane schiff bases and its synthetic method and application | |
| Abbati et al. | [Fe (OCH3) 2 (dbm)] 12: synthesis, solid-state characterization and reactivity of a new molecular ferric wheel | |
| Näther et al. | Thermal decomposition reactions as an alternative tool for the preparation of new coordination polymers: synthesis, crystal structure, thermal and magnetic properties of poly [bis (thiocyanato-N)-bis (μ2-pyrazine-N, N′)-manganese (II)] and poly [bis (μ2-thiocyanato-N, S)-(μ2-pyrazine-N, N′-manganese (II)] | |
| González-Pérez et al. | A Windmill-Shaped Hexacopper (II) Molecule Built Up by Template Core-Controlled Expansion of Diaquatetrakis (μ2-adeninato-N 3, N 9) dicopper (II) with Aqua (oxydiacetato) copper (II) | |
| Anguera et al. | Hexadecaphyrin-(1.0. 0.0. 1.1. 0.1. 1.0. 0.0. 1.1. 0.1): A Dual Site Ligand That Supports Thermal Conformational Changes | |
| Maalej et al. | A new square pyramidal copper (II) complex [Cu (C10H24N4) Br] Br: Crystal structure, thermal analysis, Hirschfeld surfaces, electrical and semiconducting properties | |
| CN108530350A (en) | A kind of monokaryon Fe (II) Spin crossover and preparation method thereof | |
| CN108516954A (en) | A kind of Spin crossover crystal and preparation method thereof | |
| CN107311881A (en) | A kind of gelator and its preparation and application | |
| CN108191896B (en) | Dinuclear dysprosium cluster compound using 2-aldehyde-8-hydroxyquinoline ethanolamine Schiff base as ligand and synthetic method and application thereof | |
| Kataoka et al. | Paddlewheel‐Type Dirhodium Tetrapivalate Based Coordination Polymer: Synthesis, Characterization, and Self‐Assembly and Disassembly Transformation Properties | |
| Meghdadi et al. | Synthesis, characterization and electrochemistry of carboxamido Co (III) complexes: The crystal structure of [CoIII (Mebpb)(N-MeIm) 2] BPh4· CH3OH | |
| Uma et al. | Synthesis, structure, spectra and redox interconversions in copper (II) complexes of 5, 6-diphenyl-3-(2-pyridyl)-1, 2, 4-triazine | |
| Li et al. | Synthesis, characterization and crystal structures of dibenzo-18-crown-6 sodium isopolytungstates | |
| CN103951709B (en) | A kind of cyclopentadienyl transiting metal nickel nitrogen complex and its preparation method and application | |
| Gilbert et al. | Some nickel (II) complexes with pentadentate and tridentate heterocyclic N-and S-donor ligands | |
| Samuels et al. | Synthesis and thermal and hydrolytic conversion of heterometallic copper oxide-alkoxides | |
| CN113956493B (en) | Non-alkyl tin oxygen cluster compound and synthetic method and application thereof | |
| Wang et al. | Syntheses and characterizations of two-dimensional supramolecular architectures based on hydrogen-bonded rectangular cavities | |
| Padhi et al. | Synthesis, structure, thermal studies on Zn (II), Cd (II) complexes of N-(2-pyridylmethyl) pyridine-2-carbaldimine and N-(2-pyridylmethyl) pyridine-2-methylketimine | |
| Bakir et al. | Optical, electrochemical and structural studies of the first rhenium compound of di-2-pyridylketone benzoylhydrazone (dpkbz) fac-Re (CO) 3 (dpkbh) Cl |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180911 |