CN110028676A - A kind of easy, method for efficiently synthesizing stable metal organic backbone crystal - Google Patents
A kind of easy, method for efficiently synthesizing stable metal organic backbone crystal Download PDFInfo
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Abstract
A kind of simplicity efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2] n (solvent) x (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines) method.Solve existing [(ZnI2)3(TPT)2] time-consuming for n (solvent) x synthetic method, process is cumbersome, the problem of low yield and synthetic crystal stability difference.Synthesis step is as follows: by ZnI2It is dissolved in acetonitrile (CH3CN), TPT is dissolved in nitrobenzene (PhNO2) and methanol (CH3OH mixed solvent), two kinds of solution after mixing, certain time crystallization are passed through in the baking oven of certain temperature, forms the crystal of specific shape.This method have the advantage that: synthesis process only needs to stand in baking oven without slowly chromatography；The feature for cleverly promoting crystal growth using high temperature, the time required to shortening crystallization；Synthetic method can high yield obtain stable rhabdolith, continuous mode is not necessarily to nitrogen (N2) and low-temperature protection.The rodlike [(ZnI that the present invention obtains2)3(TPT)2] n (solvent) x crystal can be used as crystal sponge measurement small molecule, the absolute configuration of the structure and raceme of reaction intermediate and unknown metabolin.
Description
Technical field
The present invention designs a kind of synthetic method of metal organic framework crystal, and in particular to a kind of simplicity efficiently synthesizes steady
Determine metal organic framework crystal [(ZnI2)3(TPT)2] n (solvent) x (TPT=2,4,6- tri- (4- pyridyl groups) -1,3,5-
Triazine) method.
Background technique
Metal-organic framework materials (Metal-Organic Frameworks) are one kind by inorganic metal ion and have
A kind of Porous coordination polymer that machine ligand is self-assembly of.Adjustable with structure, permanent super large hole is coordinated unsaturated sites
With [1] the characteristics of controllable pore structure.Based on the above advantage, metal organic framework is widely used in optics [2], senses [3], point
From analysis [4], gas stores [5], is catalyzed [6] and drug transport [7].
The linear rigid ligand (1D) of metal organic framework such as 4,4 '-bipyridyls in recent years, are widely studied, but
Its analog 3D ligand 2,4,6- tri- (4- pyridyl group) -1,3,5-triazines) lack systematic research [8] at present.Has report at present
Road point out TPT with ZnI2It can be self-assembly of 3-dimensional metal network during complexation reaction, this complexation process is related to one kind
The dual percolating network of dynamic assembles: that is, hole is voluntarily shunk without destroying when guest molecule removes network pore
Its property [8] crystallized.
Fujita in 2013 and its seminar propose [(ZnI2)3(TPT)2] n (solvent) x crystal and report crystal
Application, and a detailed scheme has been delivered in 2014, the program utilizes " crystal sponge " method to pass through single crystal X-ray diffraction
Structure elucidation [9] are carried out to noncrystal compound.Wherein crystal sponge technology does not need sample to be tested itself and participates in crystallization process,
But with the volatilization of sample solvent, the dropping liquid state visitor containing target molecule is absorbed with metal organic framework crystal " sponge "
Body.This " sponge " contains micropore, can identify target molecule, and combines them in the form of an oldered array, so that
The object absorbed can be analyzed together with main body frame using single crystal X-ray diffraction.Therefore main crystal is also referred to as
" crystallization sponge " or " crystal sponge " [8].The seminar has been described that crystallization sponge method is determining small molecule structure, metabolome
Point, the broad application prospect in reaction intermediate type and absolute configuration distribution.
Structure elucidation is the highly important part in chemical research, for the structure for quick and precisely determining testing molecule, mesh
Preceding common method mainly has NMR spectrum (NMR), and mass spectrum (MS), infrared spectroscopy (IR) etc., they can provide related function
Group, key connection property, molecular formula, the molecular structure information of spatial chemistry and conformation.But strictly speaking, they can only provide supposition
Molecular structure, and X-ray single crystal diffraction (XSCD) is to directly obtain the most reliable method of atomic structure information, including absolute stereo
Chemical [9].
There are the limitations of some keys by XSCD: it is required that sample is crystal, noncrystalline compound such as liquid or amorphous solid
Body is not suitable for such analysis, and which has limited the piths of molecular structure；Secondly, before measuring, sample cannot
It automates and preparation process needs to expend time [9].
Bibliography
[1] R.Mejia-Ariza, J.Huskens, The effect of PEG length onthe size and
4 (2016) 1108-1115. of guest uptake of PEG-capped MIL-88A particles, J.Mater.Chem.B
[2] C.Wang, T.Zhang, W.Lin, Rational synthesis of noncentrosymmetric
Metalorganic frameworks for second-order nonlinear optics, Chem.Rev.112 (2012)
1084-1104.
[3] Q.G.Meng, X.L.Xin, L.L.Zhang, F.N.Dai, R.M.Wang, D.F.Sun, A
multifunctional Eu MOF as a fluorescent pH sensor and exhibiting highly
Solvent-dependent adsorption and degradation of rhodamine B, J.Mater.Chem.A 3
(2015)24016-24021.
[4] J.Xu, W.Xing, H.Wang, W.Xu, Q.Ding, L.Zhao, W.Guo, Z.Yan, Monte Carlo
Simulation study of the halogenated MIL-47 (V) frameworks:influence of
Functionalization on H2S adsorption and separation properties, J.Mater.Sci.51
(2015)2307-2319.
[5] J.An, N.L.Rosi, Tuning, M.O.F.CO2, adsorption properties via cation
Exchange, J.Am. Chem.Soc.132 (2010) 5578-5579.
[6] R.Kaur, K.Vellingiri, K.H.Kim, A.K.Paul, A.Deep, Efficient
photocatalytic degradation of rhodamine 6G with a quantum dot-metal organic
154 (2016) 620-627. of framework nanocomposite, Chemosphere
[7] X.Kuang, Y.Ma, H.Su, J.Zhang, Y.B.Dong, B.Tang, High-performance liquid
chromatographic enantioseparation of racemic drugs based on homochiral
Metalorganic framework, Anal.Chem.86 (2014) 1277-1281.
[8] Y.Inokuma, S.Yoshioka, J.Ariyoshi, T.Arai, M.Fujita, Preparation and
guest-uptake protocol for a porous complex useful for′crystal-free′
Crystallography, Nature protocols, 9 (2014) 246-52.
[9] G.W.Waldhart, N.P.Mankad, B.D.Santarsiero, Improvements to the
Practical Usability of the″Crystalline Sponge″Method for Organic Structure
Determination, Organic letters, 18 (2016) 6112-6115.
Summary of the invention
Object of the present invention is to solve metal organic framework [(ZnI2)3(TPT)2] n (solvent) x Opacity in lens process is multiple
Miscellaneous, time-consuming, low yield, and the unstable problem of synthetic crystal provides a kind of simplicity, efficiently synthesizes stable metal organic backbone
The method of crystal, this approach avoid solution to be slowly mixed together, and time-consuming, low output and it is unstable the disadvantages of, shortened by temperature control
Generated time simplifies synthesis process.Method is easy, and quickly, gained crystal yield is high, more stable.
Technical proposal that the invention solves the above-mentioned problems is:
A kind of simplicity efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2] n (solvent) x side
Method, it is characterised in that the method can be simple, and quickly and high yield synthesizes stable metal organic framework crystal [(ZnI2)3
(TPT)2] n (solvent) x zinc coordination polymer, the chemical formula [(ZnI2)3(TPT)2] in n (solvent) x
TPT be 2,4,6- tri- (4- pyridyl group) -1,3,5-triazines ligands, solvent is solvent molecule, is in the present invention acetonitrile
(CH3CN), nitrobenzene (PhNO2), it is solution solvent molecule to be measured, the [(ZnI in solution to be measured2)3(TPT)2]n·
(solvent) x is three-D space structure, belongs to monoclinic crystal, space group C2/c, cell parameter is respectively α=90 °, β=102.527 (2) °, γ=90 ° are infrared
Data (KBr) are as follows: 3065 (s), 3013 (m), 2930 (w), 2855 (w), 1614 (vs), 1521 (s), 1347 (m), 1063
(m), 1012 (m), 800 (s), 704 (s), 603 (s), 512 (m) cm-1。
Synthesis step is as follows:
One, by ZnI2It is placed in CH3In CN (molar ratio 3: 10~20), under conditions of 30~100kHz of ultrasound handle 10~
20min；
Two, a certain amount of TPT is placed in PhNO2With CH3In the mixed solution of OH (molar ratio 2: 20~40: 12.5~25),
30~60min is stirred at room temperature；
Three, material mixing in step 1 and two is placed in 30~60 DEG C of baking oven, mixture passes through 3h in an oven
~3 d crystallization form rhabdolith, after cooling take out reaction flask；
Four, the ZnI2With the molar ratio 1: 0.5~3 of TPT.
Further preferably, the processing time of ultrasound condition described in step 1 is 10min, the ZnI2With CH3The molar ratio of CN
It is 3: 19.2.
Further preferably, it is 30min, the TPT, PhNO that the time is stirred at room temperature described in step 22With CH3OH's rubs
You are than being 2: 39.2: 25.
Further preferably, described in step 3 material mixing is placed in 40 DEG C of baking oven in the step of one and two, mixing
Object passes through 5h crystallization in an oven.
Further preferably, ZnI described in step 42With the molar ratio 1.5: 1 of TPT.
Advantages of the present invention:
One, process of the present invention: synthesis process only needs to stand in baking oven without slowly chromatography.
Two, cleverly using high temperature promote crystal growth feature, shorten crystallization the time required to (< 3d), it is most short can be extremely
3 h。
Three, synthetic method can high yield obtain stable rhabdolith and in data determination without nitrogen (N2) and low temperature
Protection, yield is up to 95%.
The present invention efficiently synthesizes stable metal organic backbone crystal [(ZnI for simplicity2)3(TPT)2]n·(solvent)
X (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines).
Detailed description of the invention
Fig. 1 is that embodiment one synthesizes gained crystal [(ZnI2)3(TPT)2] n (solvent) x optical microscopy under shape
Looks figure.
Fig. 2 is that embodiment one synthesizes gained crystal [(ZnI2)3(TPT)2] n (solvent) x infrared spectrogram, Yi Jishi
Apply the infrared spectrogram comparison of crystal after two exchange of solvent of example.
Fig. 3 is that embodiment one synthesizes gained crystal [(ZnI2)3(TPT)2] n (solvent) x and crystal solvent evaporation after
The comparison diagram of crystal.
Fig. 4 is [(ZnI2)3[TPT)2] (DIPA) 2x ligand environment and steric configuration figure.
Specific embodiment
Above content of the present invention is described in further details by the following examples, but this hair should not be interpreted as through this
The range of bright aforementioned body is only limitted to following embodiment, and all contents realized based on above content of the present invention belong to of the invention
Range.
Embodiment one
1, easy, efficiently synthesize stable metal organic backbone crystal [(ZnI2)3(TPT)2] n (solvent) x (TPT=
2,4,6- tri- (4- pyridyl group) -1,3,5-triazines) method, synthesis step the following steps are included:
One, by ZnI2(9.60mg, 0.03mmol) is placed in 1mL CH3In CN, handled under conditions of ultrasonic 50kHz
10min；
Two, TPT (6.30mg, 0.02mmol) is placed in 4mL PhNO2With 1mL CH3In the mixed solution of OH, it is stirred at room temperature
30min；
Three, material mixing in step 1 and two being placed in 40 DEG C of baking oven, mixture passes through 5h crystallization in an oven,
Rhabdolith is formed, after cooling takes out reaction flask.
2, easy, efficiently synthesize stable metal organic backbone crystal [(ZnI2)3(TPT)2] n (solvent) x (TPT=
2,4,6- tri- (4- pyridyl group) -1,3,5-triazines) Structural Identification:
Analyzing faint yellow nearly clear crystal obtained by above-mentioned steps 1 by following infrared spectroscopies and X-ray single crystal diffraction is
Simplicity of the present invention, stable metal organic framework crystal [(ZnI quickly and obtained by high yield synthesis2)3(TPT)2]n·
(solvent) x (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines).
(1) infrared spectroscopy (KBr pellet, cm-1): 3065 (s), 3013 (m), 2930 (w), 2855 (w), 1614 (vs),
1521 (s), 1347 (m), 1063 (m), 1012 (m), 800 (s), 704 (s), 603 (s), 512 (m) cm-1。
(2) X-ray single crystal diffraction is the result shows that above-mentioned [(ZnI2)3(TPT)2] n (solvent) x specification be 0.230x
0.220x 0.200mm3, it is at normal temperature faint yellow nearly colourless monoclinic crystal, asymmetric cell contains 3 Zn2+, 2 TPT
Ligand.Wherein Znl be four-coordination structure, respectively in 2 TPT ligands 2 pyridyl nitrogen atoms and two I atoms match
Position, using metal as vertex, the angle of two ligands is V-type, Zn2, Zn3 coordination configuration having the same, generally dual interpenetrating
Three-dimensional structure.
Fig. 3 is that embodiment one synthesizes gained crystal [(ZnI2)3(TPT)2] n (solvent) x and crystal solvent evaporation after
The comparison diagram of crystal.
Table 1 is the resulting [(ZnI of embodiment one2)3(TPT)2] n (solvent) x crystallographic parameter.
Embodiment two
Stable metal organic framework the crystal [(ZnI that the present embodiment uses embodiment one to obtain2)3(TPT)2]n·
(solvent) x (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines) measures the knot of 2,6-DIPA (DIPA)
Structure, measurement the following steps are included:
1, exchange of solvent:
One, easy in embodiment one, efficiently synthesize stable metal organic backbone crystal [(ZnI2)3(TPT)2]n·
(solvent) after reaction, bottle is taken out from baking oven by x (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines),
Most of surplus solution is removed with glass pipette, then 2mL cyclohexane solvent is added in bottle；Removal is most of molten again
Liquid to remove nitrobenzene as much as possible；The new cyclohexane solvent of 2mL is added in bottle, crystal is then placed in room temperature
Under.It takes out and supplements solvent 1 time in bottle daily.
Two, solvent exchange procedure monitors: monitoring the time of exchange of solvent, using infrared spectroscopy whether to confirm nitrobenzene
It is removed from crystal completely.Above-mentioned simplicity efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2]n·
(solvent) x is in 1344cm-1There is a N-O to stretch peak, repeats solvent exchange procedure until peak completely disappears.Experiments have shown that this
Process removes all PhNO2Solvent needs 6d.
Fig. 1 is simplicity, efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2] n (solvent) x with it is molten
The infrared spectrogram of crystal after agent exchanges.
2, the infiltration of DIPA:
One, the preparation of DIPA solution: use methylene chloride dilution DIPA solution to 1mg/mL as object solution.
Two, in embodiment two after solution exchange, remaining solution is removed with pipette, crystal is moved into a system one by one respectively
It arranges in 2mL bottle.
Three, the object solution (DIPA solution) of 50 μ L is added in each 2mL bottle, and by bottle in baking oven (50 DEG C)
Stand 5h.During this, DIPA molecule, which enters, to be infiltrated through in crystal hole, and crystal has apparent color change, becomes orange.
Three, crystal is taken out using needle and Paratone oil, and they is put on a glass slide, selected by microscope
It is transparent and be used for the structure determination of X-ray single crystal diffraction without crackle and the crystal of deformation.
X-ray single crystal diffraction is the result shows that two gained [(ZnI of embodiment2)3[TPT)2] (DIPA) crystal is at normal temperature
Faint yellow nearly colourless monoclinic crystal, asymmetric cell contain 3 Zn2+, 2 TPT ligands, 1 guest molecule (DIPA).Wherein
Zn1 be four-coordination structure, respectively with 2 pyridyl nitrogen atoms and two I Atomic coordinates in 2 TPT ligands, with metal
For vertex, the angle of two ligands is V-type, Zn2, Zn3 coordination configuration having the same, generally dual interpenetrating three-dimensional structure.
Table 2 is the resulting [(ZnI of embodiment two2)3[TPT)2] (DIPA) crystallographic parameter and bibliography [0015]
[8] synthesis gained crystallographic parameter.
Fig. 4 is [(ZnI2)3[TPT)2] (DIPA) ligand environment and steric configuration.
Table 3 is resulting [(ZnI2) 3 [TPT) 2] (DIPA) (TPT=2,4,6- tri- (4- after two DIPA of embodiment infiltration
Pyridyl group) -1,3,5-triazines) part bond distance's bond angle data.
| Zn(1)-N(2) | 2.049(5) | Zn(2)-I(3) | 2.5458(11) |
| Zn(1)-N(1) | 2.056(5) | Zn(2)-I(4) | 2.5465(10) |
| Zn(1)-I(1) | 2.5147(11) | Zn(3)-N(5) | 2.072(5) |
| Zn(1)-I(2) | 2.5451(10) | Zn(3)-N(6) | 2.097(5) |
| Zn(2)-N(4) | 2.057(6) | Zn(3)-I(5) | 2.5221(10) |
| Zn(2)-N(3) | 2.072(5) | Zn(3)-I(6) | 2.5275(10) |
Claims (14)
1. a kind of simplicity efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2] n (solvent) x (TPT=
2,4,6- tri- (4- pyridyl group) -1,3,5-triazines) method.It is characterized in that the method can be easy, stabilization is efficiently synthesized
Metal organic framework crystal [(ZnI2)3(TPT)2] n (solvent) x zinc coordination polymer, the chemical formula [(ZnI2)3
(TPT)2] TPT in n (solvent) x is 2,4,6- tri- (4- pyridyl group) -1,3,5-triazines ligands, solvent is solvent
Molecule is in the present invention acetonitrile (CH3CN), nitrobenzene (PhNO2), it is solution solvent molecule to be measured in solution to be measured；It is described
[(ZnI2)3(TPT)2] n (solvent) x be three-D space structure, belong to monoclinic crystal, space group C2/c, structure cell
Parameter is respectivelyα=90 °, β=102.527 (2) °, γ
=90 °, infrared data (KBr) are as follows: 3065 (s), 3013 (m), 2930 (w), 2855 (w), 1614 (vs), 1521 (s), 1347
(m), 1063 (m), 1012 (m), 800 (s), 704 (s), 603 (s), 512 (m) cm-1。
2. stable metal organic backbone crystal [(ZnI according to claim 12)3(TPT)2]n·(solvent)x(TPT
=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines) simple, efficient synthetic method, which is characterized in that the method includes
Following steps:
One, by ZnI2It is placed in CH3In CN (molar ratio 3: 10~20), under conditions of 30~100kHz of ultrasound handle 10~
20min；
Two, a certain amount of TPT is placed in PhNO2With CH3In the mixed solution of OH (molar ratio 2: 20~40: 12.5~25), room temperature
Stir 30~60min；
Three, material mixing in step 1 and two is placed in 30~60 DEG C of baking oven, mixture passes through 3h~3d in an oven
Crystallization forms rhabdolith, after cooling takes out reaction flask；
Four, the ZnI2With the molar ratio 1: 0.5~3 of TPT.
3. simplicity according to claim 2 efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2]n·
(solvent) method of x (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines), it is characterised in that surpass described in step 1
Sound temperature is no more than 30 DEG C.
4. simplicity according to claim 2 efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2]n·
(solvent) method of x (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines), it is characterised in that surpass described in step 1
Sound condition handles the time as 10min.
5. simplicity according to claim 2 efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2]n·
(solvent) method of x (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines), it is characterised in that described in step 1
ZnI2With CH3The molar ratio of CN is 3: 19.2.
6. simplicity according to claim 2 efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2]n·
(solvent) method of x (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines), it is characterised in that described in step 2
TPT, PhNO2With CH3The molar ratio of OH is 2: 39.2: 25.
7. simplicity according to claim 2 efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2]n·
(solvent) method of x (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines), it is characterised in that described in step 2
It is 30min that the time, which is stirred at room temperature,.
8. simplicity according to claim 2 efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2]n·
(solvent) method of x (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines), it is characterised in that described in step 3
Material mixing is placed in 40 DEG C of baking oven in step 1 and two, and mixture passes through 3h crystallization in an oven.
9. simplicity according to claim 2 efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2]n·
(solvent) method of x (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines), it is characterised in that described in step 3
Material mixing is placed in 40 DEG C of baking oven in step 1 and two, and mixture passes through 5h crystallization in an oven.
10. simplicity according to claim 2 efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2]n·
(solvent) method of x (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines), it is characterised in that described in step 3
Material mixing is placed in 40 DEG C of baking oven in step 1 and two, and mixture passes through 1d crystallization in an oven.
11. simplicity according to claim 2 efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2]n·
(solvent) method of x (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines), it is characterised in that described in step 3
Material mixing is placed in 40 DEG C of baking oven in step 1 and two, and mixture passes through 3d crystallization in an oven.
12. simplicity according to claim 2 efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2]n·
(solvent) method of x (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines), it is characterised in that described in step 4
ZnI2With the molar ratio 1.5: 1 of TPT.
13. simplicity according to claim 2 efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2]n·
(solvent) method of x (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines), it is characterised in that described in step 4
ZnI2With the molar ratio 1: 2 of TPT.
14. simplicity according to claim 2 efficiently synthesizes stable metal organic backbone crystal [(ZnI2)3(TPT)2]n·
(solvent) method of x (TPT=2,4,6- tri- (4- pyridyl group) -1,3,5-triazines), it is characterised in that described in step 4
ZnI2With the molar ratio 1: 3 of TPT.
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| JP2021144045A (en) * | 2019-11-01 | 2021-09-24 | キリンホールディングス株式会社 | Method for determining structure of substance in multicomponent sample |
| EP4029869A1 (en) * | 2021-01-15 | 2022-07-20 | Merck Patent GmbH | Solvated crystalline polynuclear metal complex solvated with a mixture of non-polar and polar solvents, such solvated crystalline polynuclear metal complex including a guest compound analyte and its use in a method for determining molecular structure of the guest compound analyte |
| CN116333328A (en) * | 2023-02-23 | 2023-06-27 | 暨南大学 | Preparation method and application of novel copper-based pyridine fluorene crystal sponge |
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| JP2021144045A (en) * | 2019-11-01 | 2021-09-24 | キリンホールディングス株式会社 | Method for determining structure of substance in multicomponent sample |
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| WO2022152879A1 (en) * | 2021-01-15 | 2022-07-21 | Merck Patent Gmbh | Solvated crystalline polynuclear metal complex solvated with a mixture of non-polar and polar solvents, such solvated crystalline polynuclear metal complex including a guest compound analyte and its use in a method for determining molecular structure of the guest compound analyte |
| CN116333328A (en) * | 2023-02-23 | 2023-06-27 | 暨南大学 | Preparation method and application of novel copper-based pyridine fluorene crystal sponge |
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