CN102516270B - Metallic silver coordination polymer with two-dimensional lamellar structure, and preparation and application thereof - Google Patents
Metallic silver coordination polymer with two-dimensional lamellar structure, and preparation and application thereof Download PDFInfo
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- SCOHYGRXXPIVSX-UHFFFAOYSA-N c1cc(-c2nnc(-c3ccccn3)[n]2-c2ccncc2)ncc1 Chemical compound c1cc(-c2nnc(-c3ccccn3)[n]2-c2ccncc2)ncc1 SCOHYGRXXPIVSX-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention relates to a 3,5-di(2-pyridyl)-4-(4-pyridyl)-1,2,4-triazolyl-silver (I) coordination polymer, and a preparation and application thereof. The compound is synthesized by the following steps: under normal temperature and pressure, mixing AgNO2 acetonitrile solution and ligand L chloroform solution, and keeping stirring for half an hour, and standing in a dark place to volatilize for about one week, thereby obtaining the colorless lumpy monocrystal product. The invention has the advantages of simple preparation technique, short reaction time, easy after-treatment and high yield. The experiment proves that nitrite ions in the material can selectively react with tetrafluoroborate ions, hexafluorosilicate ions, nitrate ions and perchlorate in an anion exchange mode, and benzoate ions and acetate ions can not perform similar anion exchange reaction. The material overcomes the limitation to the existing anion exchange material, the exchange process is simple and easy to implement, and thus, the invention is hopeful to practical application in the field of ion exchange materials.
Description
Technical field
The invention belongs to synthetic, structure and the performance technologies field of novel inorganic-organic Hybrid Materials, specially refer to a kind of preparation of the coordination polymer material with two-dimensional layered structure, say more specifically 3, two (2-the pyridyl)-4-(4-pyridyl)-1 of 5-, 2,4-triazole-Ag coordinated polymer and preparation thereof and the application aspect chosen anion exchange.
Background technology
Along with the development of coordination chemistry, the concept of crystal engineering be incorporated in the middle of the design of coordination supramolecular structure and extended an important subject branch-ligand polymer (Coordination Polymer).It is defined as: between ligand molecular or ion and metal ion, assemble by coordinate bond the crystalloid material with highly regular infinite network structure and specific physical chemical property forming.Multiple ambits such as inorganic chemistry, organic chemistry, physical chemistry, coordination chemistry, supramolecular chemistry, materials chemistry, crystal engineering and topology have been crossed in the research of ligand polymer, become one of current chemical research field heat subject (S. R. Batten, R. Robson
angew. Chem., Int. Ed. 1998,
37, 14601494; M. Eddaoudi, D. B. Moler, H. Li, B. Chen, T. Reineke, M. O ' Keeffe, O. M. Yaghi,
acc. Chem. Res. 2001,
34, 319 1 330).According to the difference of metal ion and part mode of connection, obtain miscellaneous one-dimensional chain compound, two-dimension netted compound and three-dimensional frame structure compound.Along with scientific and technical development and people are for the going deep into of ligand polymer functional study, synthesized the ligand polymer that there is in a large number novel topological framework and there is premium properties at aspects such as optical, electrical, magnetic, separation, catalysis and absorption (G. F é rey,
chem. Soc. Rev. 2008,
37, 191 – 214; M. Du, X.-H. Bu,
bull. Chem. Soc. Jpn. 2009,
82, 539 – 554; A. Corma, H. Carc í a, F. X. Llabr é s i Xamena,
chem. Rev. 2010,
110, 4606 – 4655).
In general, ligand polymer has the adjustable cavity of microcosmic of some scale, higher thermostability and be insoluble to the good material properties such as common organic solvent, can hold some object components (as negatively charged ion and solvent molecule etc.) in its open pore passage structure.Especially negatively charged ion, on the one hand negatively charged ion, in the situation that not participating in coordination, often occupies with the cavity of supporting network structure and plays the effect of balancing charge as object template; The mode of connection that negatively charged ion can change part and metal ion by coordination on the other hand causes forming different network structures.These features above, all make ligand polymer can be used as a kind of potential novel ion-exchange material, can use widely the determination of trace at metal ion, the aspect such as the quantitative analysis of pollutent and isotope geochemistry research in environment.But the known ligand polymer with anionresin function often embodies certain limitation at present.The most important is exactly, and its ion-exchange performance betides between the object negatively charged ion with similar volume and identical valence state conventionally, and it is also very rare to have the coordination polymer material of selectivity switching performance for the negatively charged ion that participates in coordination.
Summary of the invention
One object of the present invention has been to provide a kind of ligand polymer with two-dimensional layered structure and preparation method thereof.
Another object of the present invention has been to provide prepares required precursor compound of the ligand polymer of two-dimensional layered structure and preparation method thereof.
A further object of the present invention has been to provide the crystal with two-dimensional layered structure ligand polymer.
The application of the ligand polymer that a further object of the present invention has been to provide two-dimensional layered structure aspect selective ion exchange.
For achieving the above object, openly following technology contents of the present invention:
There is the ligand polymer of two-dimensional layered structure: chemical formula is [Ag
2l (NO
2)
2], wherein the structural formula of L is as follows:
The preparation method of ligand polymer of the present invention, is characterized in that: at normal temperatures and pressures, and by 0.1 ~ 0.5 mmol AgNO
2acetonitrile solution mix with the chloroform soln of 0.1 ~ 0.3 mmol ligand L, and keep stirring half an hour, under lucifuge condition, leave standstill volatilization and within 5 ~ 7 days, obtain colourless bulk-shaped monocrystal product.
Many Pyridine Bridges based on 1,2,4-triazole of the present invention are associated with machine ligand L, have following structural formula:
L room temperature existence form is white solid.This organic application is the stable ligand polymer of preparation, and this compound, as the polydentate ligand that contains multi-functional group, can be taked different coordination modes when from metallic ion coordination.Its preparation method is undertaken by following concrete steps:
N-(4-pyridyl)-2-pyridine-thioamides and 2-pyridine formyl hydrazine are dissolved with propyl carbinol, and reflux stops heating after 34 ~ 40 hours, be cooled to room temperature, and decompress filter obtains light yellow solid with after washing with alcohol three times; Wherein N-(4-pyridyl)-2-pyridine-thioamides: the mol ratio of 2-pyridine formyl hydrazine is 1:1 ~ 1.5.With ethyl alcohol recrystallization, obtain white solid product.
More concrete step of the present invention is as follows:
Building-up process: by N-(4-pyridyl)-2-pyridine-thioamides (21.5 g, 0.1 mol) and 2-pyridine formyl hydrazine (13.7 g, 0.1 mol) with 200 mL propyl carbinols dissolve, reflux stops heating after 36 hours, be cooled to room temperature, decompress filter, obtains light yellow solid with after washing with alcohol three times.With ethyl alcohol recrystallization, obtain white powder solid phase prod.Accurately weigh with analytical balance, calculating productive rate is 66%.
The present invention further discloses the ligand polymer crystal with two-dimensional layered structure, it is characterized in that described ligand polymer crystal belongs to tetragonal system, its Advances in crystal X-ray diffraction structure determination is carried out on Bruker Apex II CCD diffractometer.Under 296 (2) K, to use through the Mo of graphite monochromatization K alpha-ray (λ=0.71073) and collect point diffraction with ω scan mode, the data of collection are also carried out semiempirical absorption correction by SADABS method by SAINT programe reduction.Structure elucidation and refine adopt respectively the SHELXS of SHELXTL program and SHELXL to complete, by complete matrix least square method pair
f 2revise the coordinate and the anisotropic parameters that obtain whole non-hydrogen atoms.Infrared spectra is by AVATAR-370(Nicolet) spectrophotometer, KBr compressing tablet, collects 400-4000 cm
– 1interval censored data; Ultimate analysis is by CE-440(Leemanlabs) elemental analyser mensuration; X-ray powdery diffractometry (XRPD) style is measured by Bruker D8 Advance diffractometer, Cu target (λ=1.5406), and 0.2 °/min of scanning speed, its crystal parameters is as follows:
Molecular formula C
17h
12ag
2n
8o
4
Molecular weight 608.09
Crystallographic system Tetragonal
Spacer
p4
32
12
Unit cell parameters (,
o)
a 7.239(4)
b 7.239(4)
c 36.32(2)
α 90
β 90
γ 90
Unit cell volume (
3) 1903.3 (18)
Z 4
Crystalline density calculated value (g/cm
3) 2.122
Crystal linear absorption coefficient (mm
– 1) 2.104
Crystalline size (mm) 0.28 × 0.22 × 0.20
Number of electrons 3925 in unit cell
Diffraction index Fan Wei – 8/4 ， – 8/8 ， – 43/42
Participate in the diffraction number 1687 of refine
How much limiting parameter number/participation number of parameters 0/142
Equivalency point standard error of mean 0.0376
Diffraction experiment temperature (K) 296 (2)
Goodness of fit value 1.138
Observable point diffraction
r 1 aaMP.AMp.Amp
wR 2 b[
i>2
σ(
i)] value 0.0375 & 0.0871
All point diffractions
r 1 aaMP.AMp.Amp
wR 2 bbe worth 0.0395 & 0.0879
The results are shown in Figure 3..
The application of the ligand polymer that the present invention further discloses two-dimensional layered structure aspect selective ion exchange.Wherein said selective ion exchange refers to: the exchange of tetrafluoroborate ion, hexafluorosilicic acid radical ion, nitrate ion and perchlorate.
The ligand polymer with two-dimensional layered structure disclosed by the invention is compared with current known material of the same type, and tool has the following advantages:
(1) this ion-exchange material only has selectivity function of exchange for tetrafluoroborate, hexafluorosilicic acid root, nitrate radical and perchlorate's negatively charged ion, does not have this feature for other negatively charged ion.
(2) preparation of this material is simple, and the reaction times is short, and aftertreatment is easy and productive rate is higher.And conventionally known this type of material prepare that productive rate is lower and aftertreatment is cumbersome.
(3) this material is irreversible for the permutoid reaction of tetrafluoroborate, hexafluorosilicic acid root, nitrate radical and perchlorate, can avoid the generation of side reaction in exchange process, has higher exchange efficiency.
The present invention has prepared one and has had special optionally coordination polymer type ion exchange material for tetrafluoroborate, hexafluorosilicic acid root, nitrate radical and perchlorate's negatively charged ion, have synthetic simple, easy to operate, good stability, productive rate height and ion-exchanging efficiency advantages of higher.The present invention has wide significance and important using value at aspects such as coordination chemistry, Supramolecular Assembling, solid state chemistry, mineral crystal engineering and materials chemistries.
accompanying drawing explanation:
fig. 1.ag in this material
ithe coordination environment figure of ion;
fig. 2.the two-dimensional layered structure figure of this material;
fig. 3.the experiment of this material powder X-ray diffraction (XPRD) style and theoretical contrast figure;
fig. 4.infrared (FT-IR) spectral comparison figure before and after this material generation ion-exchange.
Embodiment
Below in conjunction with embodiment, the present invention is described, the scheme of embodiment described here, do not limit the present invention, one of skill in the art can make improvements and change according to spirit of the present invention, these described improvement and variation all should be considered as within the scope of the invention, and scope of the present invention and essence are limited by claim.Wherein N-(4-pyridyl)-2-pyridine-thioamides is saturating, and 2-pyridine formyl hydrazine all has commercially available.
Embodiment 1:
The many Pyridine Bridges that contain 1,2,4-triazole are associated with preparation and the discussion of results of machine ligand L
1. compound experiment and aftertreatment:
By N-(4-pyridyl)-2-pyridine-thioamides (21.5 g, 0.1 mol) and 2-pyridine formyl hydrazine (13.7 g, 0.1 mol) with 200 mL propyl carbinols dissolve, reflux stops heating after 36 hours, be cooled to room temperature, decompress filter, obtains light yellow solid with after washing with alcohol three times.With ethyl alcohol recrystallization, obtain white powder product.Accurately weigh with analytical balance, calculating productive rate is 66%.
2. result and discussion:
Analytical and testing instrument:
Ultimate analysis, C, H, N assay use CE-440 (Leemanlabs) type elemental analyser
Infrared spectra, AVATAR-370 (Nicolet) Fourier infrared spectrograph
Ultimate analysis: theoretical value (C
17h
12n
6, Mr=300.3): C, 67.99; H, 4.03; N, 27.98%. actual value: C, 67.90; H, 3.99; N, 27.95%.
Infrared spectra: IR (pressing potassium bromide troche, cm
-1): 1592vs, 1509s, 1465vs, 1429vs, 1249w, 1221w, 1174m, 1148m, 1088m, 1045w, 1018w, 992m, 844s, 791s, 743s, 717s, 685m, 637m, 606m, 503w..
embodiment 2:
The many Pyridine Bridges that contain 1,2,4-triazole are associated with preparation and the discussion of results of machine ligand L
1. compound experiment and aftertreatment:
By N-(4-pyridyl)-2-pyridine-thioamides (21.5 g, 0.1 mol) and 2-pyridine formyl hydrazine (17.8 g, 0.13 mol) with 200 mL propyl carbinols dissolve, reflux stops heating after 40 hours, be cooled to room temperature, decompress filter, obtains light yellow solid with after washing with alcohol three times.With ethyl alcohol recrystallization, obtain white powder product.Accurately weigh with analytical balance, calculating productive rate is 70%.
2. result and discussion:
Analytical and testing instrument:
Ultimate analysis, C, H, N assay use CE-440 (Leemanlabs) type elemental analyser
Infrared spectra, AVATAR-370 (Nicolet) Fourier infrared spectrograph
Ultimate analysis: theoretical value (C
17h
12n
6, Mr=300.3): C, 67.99; H, 4.03; N, 27.98%. actual value: C, 67.89; H, 4.05; N, 27.90%.
Infrared spectra: IR (pressing potassium bromide troche, cm
-1): 1594vs, 1509s, 1465vs, 1430vs, 1249w, 1220w, 1175m, 1147m, 1088m, 1045w, 1018w, 991m, 843s, 791s, 743s, 716s, 685m, 636m, 606m, 504w..
embodiment 3:
The many Pyridine Bridges that contain 1,2,4-triazole are associated with preparation and the discussion of results of machine ligand L
1. compound experiment and aftertreatment:
By N-(4-pyridyl)-2-pyridine-thioamides (21.5 g, 0.1 mol) and 2-pyridine formyl hydrazine (20.5 g, 0.15 mol) with 200 mL propyl carbinols dissolve, reflux stops heating after 38 hours, be cooled to room temperature, decompress filter, obtains light yellow solid with after washing with alcohol three times.With ethyl alcohol recrystallization, obtain white powder product.Accurately weigh with analytical balance, calculating productive rate is 73%.
2. result and discussion:
Analytical and testing instrument:
Ultimate analysis, C, H, N assay use CE-440 (Leemanlabs) type elemental analyser
Infrared spectra, AVATAR-370 (Nicolet) Fourier infrared spectrograph
Ultimate analysis: theoretical value (C
17h
12n
6, Mr=300.3): C, 67.99; H, 4.03; N, 27.98%. actual value: C, 67.92; H, 4.09; N, 27.91%.
Infrared spectra: IR (pressing potassium bromide troche, cm
-1): 1593vs, 1510s, 1463vs, 1432vs, 1248w, 1221w, 1174m, 1146m, 1089m, 1044w, 1017w, 991m, 844s, 791s, 743s, 716s, 685m, 635m, 605m, 504w.
embodiment 4:
Ligand polymer crystal of the present invention belongs to tetragonal system, and spacer is
p4
32
12, unit cell parameters is
a=
b=7.239 (4),
c=36.32 (2), α=
β=γ=90
o,
v=1903.3 (18)
3.Basic structure is a two-dimensional layered structure, has a kind of Ag
icoordination environment, Ag
ifor the pentacoordinate configuration of distortion, the results are shown in Figure 3..
Coordination polymer material [Ag
2l (NO
2)
2] preparation and discussion of results
1.[Ag
2l (NO
2)
2] preparation
By 0.1 mmol AgNO
2acetonitrile solution mix with the chloroform soln of 0.1 mmol ligand L, and keep stirring half an hour, under lucifuge condition, leave standstill volatilization and within 5 days, obtain colourless bulk-shaped monocrystal product.Filter, wash then vacuum-drying.Productive rate: 76%.
2. result and discussion:
Analytical and testing instrument:
Ultimate analysis, C, H, N assay use CE-440 (Leemanlabs) type elemental analyser
Infrared spectra, AVATAR-370 (Nicolet) Fourier infrared spectrograph
Powder x-ray diffraction instrument, Bruker D8 Advance diffractometer, the results are shown in Figure 3..
Ultimate analysis: theoretical value: C, 33.58; H, 1.99; N, 18.43.Experimental value: C, 33.65; H, 2.06; N, 18.49%.
Infrared spectra: IR (pressing potassium bromide troche, cm
-1): 1596s, 1587s, 1508s, 1465s, 1446m, 1432s, 1241m, 1270vs, 1176w, 1151w, 1088w, 1077w, 1045w, 1020w, 990m, 967w, 845m, 832m, 792s, 744s, 728m, 715s, 686m, 637m, 607s, 615m, 607s, 526w, 504w.
embodiment 5:
Coordination polymer material [Ag
2l (NO
2)
2] preparation and discussion of results
1.[Ag
2l (NO
2)
2] preparation
By 0.1 mmol AgNO
2acetonitrile solution mix with the chloroform soln of 0.3 mmol ligand L, and keep stirring half an hour, under lucifuge condition, leave standstill volatilization and within 7 days, obtain colourless bulk-shaped monocrystal product.Filter, wash then vacuum-drying.Productive rate: 77%.
2. result and discussion:
Analytical and testing instrument:
Ultimate analysis, C, H, N assay use CE-440 (Leemanlabs) type elemental analyser
Infrared spectra, AVATAR-370 (Nicolet) Fourier infrared spectrograph
Powder x-ray diffraction instrument, Bruker D8 Advance diffractometer, the results are shown in Figure 3..
Ultimate analysis: theoretical value: C, 33.58; H, 1.99; N, 18.43.Experimental value: C, 33.50; H, 2.07; N, 18.50%.
Infrared spectra: IR (pressing potassium bromide troche, cm
-1): 1595s, 1586s, 1508s, 1464s, 1445m, 1431s, 1241m, 1271vs, 1177w, 1153w, 1086w, 1076w, 1044w, 1020w, 991m, 966w, 845m, 834m, 792s, 745s, 728m, 716s, 686m, 636m, 605s, 614m, 607s, 525w, 504w.
embodiment 6:
Coordination polymer material [Ag
2l (NO
2)
2] preparation and discussion of results
1.[Ag
2l (NO
2)
2] preparation
By 0.5 mmol AgNO
2acetonitrile solution mix with the chloroform soln of 0.3 mmol ligand L, and keep stirring half an hour, under lucifuge condition, leave standstill volatilization and within 5 days, obtain colourless bulk-shaped monocrystal product.Filter, wash then vacuum-drying, productive rate: 74%.
2. result and discussion:
Analytical and testing instrument:
Ultimate analysis, C, H, N assay use CE-440 (Leemanlabs) type elemental analyser
Infrared spectra, AVATAR-370 (Nicolet) Fourier infrared spectrograph
Powder x-ray diffraction instrument, Bruker D8 Advance diffractometer, the results are shown in Figure 3..
Ultimate analysis: theoretical value: C, 33.58; H, 1.99; N, 18.43.Experimental value: C, 33.66; H, 1.85; N, 18.38%.
Infrared spectra: IR (pressing potassium bromide troche, cm
-1): 1598s, 1587s, 1510s, 1466s, 1447m, 1431s, 1421m, 1269vs, 1175w, 1150w, 1089w, 1077w, 1046w, 1021w, 991m, 966w, 843m, 832m, 792s, 744s, 728m, 715s, 682m, 632m, 608s, 614m, 605s, 526w, 504w.
Crystal data:
1: C
17h
12ag
2n
8o
4,
m=608.09, tetragonal, space group
p4
32
12,
a=
b=7.239 (4),
c=36.32 (2), α=
β=γ=90
o,
v=1903.3 (18)
3,
z=4,
u=2.104 mm cm
-1, GOF=1.138,
r int=0.0376, final
rindices [I > 2 σ (I)]
r 1=0.0375 and
wR 2=0.0871.
application Example 1:
Coordination polymer material [Ag
2l (NO
2)
2for BF
4 –the switching performance of ion:
The crystal prototype obtaining in embodiment 4 (0.1 mmol) is suspended in and contains NaBF
4in the aqueous solution of (0.15 mmol), stirring at room temperature.After 8 hours by be identified after products therefrom filtration, washing, vacuum-drying.Identification of means is infrared spectra.
The results of FT-IR: the infrared spectra of exchange product and former ligand polymer has obvious difference, at 1083 cm
– 1occurred the characteristic peak of tetrafluoroborate, and nitrite anions is at 1270 cm
– 1the characteristic peak at place disappears.
above result proves that this material can be used as the exchange material of tetrafluoroborate negatively charged ion,can be as the tetrafluoroborate analysis in drug testing.
Application Example 2:
Coordination polymer material [Ag
2l (NO
2)
2] for SiF
6 2 –the switching performance of ion:
The crystal prototype obtaining in embodiment 4 (0.1 mmol) is suspended in and contains Na
2siF
6in the aqueous solution of (0.15 mmol), stirring at room temperature.After 8 hours by be identified after products therefrom filtration, washing, vacuum-drying.Identification of means is infrared spectra.
The results of FT-IR: the infrared spectra of exchange product and former ligand polymer has obvious difference, at 737 cm
– 1occurred the characteristic peak of hexafluorosilicic acid root, and nitrite anions is at 1270 cm
– 1the characteristic peak at place disappears.
above result proves that this material can be used as the exchange material of hexafluorosilicic acid root negatively charged ion, can analyze as the hexafluorosilicic acid root in glasswork's waste water.
application Example 3:
Coordination polymer material [Ag
2l (NO
2)
2] for NO
3 –the switching performance of ion:
The crystal prototype obtaining in embodiment 4 (0.1 mmol) is suspended in and contains NaNO
3in the aqueous solution of (0.15 mmol), stirring at room temperature.After 8 hours by be identified after products therefrom filtration, washing, vacuum-drying.Identification of means is infrared spectra.
The results of FT-IR: the infrared spectra of exchange product and former ligand polymer has obvious difference, at 1383 cm
– 1occurred the characteristic peak of nitrate radical, and nitrite anions is at 1270 cm
– 1the characteristic peak at place disappears.
above result proves that this material can be used as the exchange material of nitrate anion, can be as the nitrate radical analysis in acid rain.
application Example 4:
Ligand polymer [Ag
2l (NO
2)
2] for ClO
4 –the switching performance of ion:
The crystal prototype obtaining in embodiment 4 (0.1 mmol) is suspended in and contains NaClO
4in the aqueous solution of (0.15 mmol), room temperature is stirred
mix.After 8 hours by be identified after products therefrom filtration, washing, vacuum-drying.Identification of means is infrared spectra.
the results of FT-IR: the infrared spectra of exchange product and former ligand polymer has obvious difference, has occurred perchlorate's characteristic peak at 1087 cm – 1, and nitrite anions disappears at the characteristic peak at 1270 cm – 1 places.
above result proves that this material can be used as the exchange material of perchlorate's negatively charged ion, can analyze as the perchlorate in tap water.
application Example 5:
Coordination polymer material [Ag
2l (NO
2)
2] switching performance to other negatively charged ion:
The crystal prototype obtaining in embodiment 4 (0.1 mmol) is suspended in respectively and contains NaC
6h
5cOO(0.15 mmol) or NaCH
3cOO(0.15 mmol) the aqueous solution in, stirring at room temperature.After 8 hours by be identified after products therefrom filtration, washing, vacuum-drying.Identification of means is infrared spectra.
(1) material [Ag
2l (NO
2)
2] and C
6h
5cOO
–the exchange result of ion:
The results of FT-IR: the infrared spectra of products therefrom and coordination polymer material [Ag after permutoid reaction
2l (NO
2)
2] infrared spectra in full accord.
(2) material [Ag
2l (NO
2)
2] and CH
3cOO
–the exchange result of ion:
The results of FT-IR: the infrared spectra of products therefrom and coordination polymer material [Ag after permutoid reaction
2l (NO
2)
2] infrared spectra in full accord.
above result proves that this material does not have ion-exchange performance for benzoate anion and acetate ion.
Claims (5)
1. there is the ligand polymer of two-dimensional layered structure: chemical formula is [Ag
2l (NO
2)
2], wherein the structural formula of L is as follows:
。
2. the preparation method of ligand polymer claimed in claim 1, is characterized in that: at normal temperatures and pressures, and by 0.1 ~ 0.5 mmol AgNO
2acetonitrile solution mix with the chloroform soln of 0.1 ~ 0.3 mmol ligand L, and keep stirring half an hour, under lucifuge condition, leave standstill volatilization and within 5 ~ 7 days, obtain colourless bulk-shaped monocrystal product.
3. there is the ligand polymer crystal of two-dimensional layered structure, it is characterized in that chemical formula is [Ag
2l (NO
2)
2], wherein the structural formula of L is as follows:
Described ligand polymer crystal belongs to tetragonal system, adopts X-ray powder diffraction pattern to be measured by Bruker D8 Advance diffractometer, Cu target λ=1.5406, and 0.2 °/min of scanning speed, its crystal parameters is as follows:
Molecular formula C
17h
12ag
2n
8o
4
Molecular weight 608.09
Crystallographic system Tetragonal
Spacer
p4
32
12
Unit cell parameters (,
o)
a 7.239(4)
b 7.239(4)
c 36.32(2)
α 90
β 90
γ 90
Unit cell volume (
3) 1903.3 (18)
Z 4
Crystalline density calculated value (g/cm
3) 2.122
Crystal linear absorption coefficient (mm
– 1) 2.104
Crystalline size (mm) 0.28 × 0.22 × 0.20
Number of electrons 3925 in unit cell
Diffraction index Fan Wei – 8/4 ， – 8/8 ， – 43/42
Participate in the diffraction number 1687 of refine
How much limiting parameter number/participation number of parameters 0/142
Equivalency point standard error of mean 0.0376
Diffraction experiment temperature (K) 296 (2)
Goodness of fit value 1.138
Observable point diffraction
r 1 aaMP.AMp.Amp
wR 2 b[
i>2
σ(
i)] value 0.0375 & 0.0871
All point diffractions
r 1 aaMP.AMp.Amp
wR 2 bbe worth 0.0395 & 0.0879
。
Described in claim 1 two-dimensional layered structure ligand polymer in the application of preparing in selective ion exchange polymer materials.
5. application described in claim 4, wherein said selective ion exchange refers to: the exchange of tetrafluoroborate ion, hexafluorosilicic acid radical ion, nitrate ion and perchlorate.
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| CN104892646B (en) * | 2015-04-27 | 2016-09-28 | 天津师范大学 | High-temperature solvent thermal synthesis based on picoline-triazole Ag (I) coordination compound and application |
| CN104844633A (en) * | 2015-04-27 | 2015-08-19 | 天津师范大学 | High-temperature solvothermal synthesis and application of tetranuclear Ag(I) cluster based on methylpyridine-triazole |
| CN105294742B (en) * | 2015-09-22 | 2017-05-17 | 南阳师范学院 | Bispyridine quinoxaline ligand silver metal complex and preparation method thereof |
| CN105541875A (en) * | 2016-01-08 | 2016-05-04 | 南阳师范学院 | Colorless silver metal complex with high light stability and preparation method thereof |
| CN105541888B (en) * | 2016-01-15 | 2017-10-13 | 天津师范大学 | It is a kind of to be directed to efficient absorption material of dichromate ion and preparation method and application in water |
| CN109081829B (en) * | 2017-06-13 | 2020-11-17 | 天津师范大学 | Ag (I) -organic framework material and preparation method and application thereof |
| CN109293636B (en) * | 2018-10-22 | 2020-05-05 | 山东师范大学 | One-pot synthesis of capsule coordination compound containing Schiff base structural unit, preparation method and application |
| CN111333669B (en) * | 2020-03-26 | 2021-05-18 | 中国原子能科学研究院 | Two-dimensional layered coordination compound and preparation method and application thereof |
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