CN101830934A - Synthesis and structure of cobaltic biligand coordination polymer - Google Patents
Synthesis and structure of cobaltic biligand coordination polymer Download PDFInfo
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- CN101830934A CN101830934A CN200910079468A CN200910079468A CN101830934A CN 101830934 A CN101830934 A CN 101830934A CN 200910079468 A CN200910079468 A CN 200910079468A CN 200910079468 A CN200910079468 A CN 200910079468A CN 101830934 A CN101830934 A CN 101830934A
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- bpp
- nds
- propane
- disulfonic acid
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Abstract
The invention provides a cobaltic inorganic-organic coordination polymer crystal structure with 1, 3-bis (4-pyridyl)propane (bpp) and 1,6-naphthtalenedisulfonic acid (nds) biligand. The synthesis method of the coordination polymer is a hydrothermal synthesis method, and the molecular formula is [Co(bpp)2(H2O)2]n.n(1,6-nds).7nH2O [bpp=1,3-bis(4-pyridyl)propane, nds= naphthtalenedisulfonic acid]. In the unit structure, 1,6-naphthtalenedisulfonic acid is taken as counter ion, Co<2+> adopts an octahedral coordination mode, and the coordination atoms are four N atoms respectively provided by four independent bpps and O atoms provided by two water molecules; in addition, seven crystalline water molecules exist.
Description
Technical field
The invention belongs to the synthetic field of the metal inorganic-organic coordination polymer of two parts, be specifically related to the preparation and the constitutional features of the inorganic-organic coordination polymer of a kind of transition metal and two kinds of parts.
Technical background
Ligand polymer is formed by self-assembly by metal ion and organic ligand, it combines the characteristics of organic ligand and metal ion, people can be by selecting suitable organic ligand and metal ion or metal cluster, control influences the various delicate factor of self-assembly, designs the compound that has unique texture and function.Ligand polymer not only has multifarious structure, also have in fields such as light, electricity, magnetic and catalysis good application prospects (Hong Maochun, Chen Rong, the inorganic chemistry [M] in flat .21 century of Liang Wen. the .2005 of Beijing Science Press).At present, the quantity that contains sulfonic acid class ligand polymer of known references report is few, the ligand polymer quantity that particularly contains neutral ligand still less, therefore, the novel metal ligand polymer that contains the two parts of naphthalene disulfonic acid and neutral ligand has more potential application foreground.
By neutral ligand and transition metal ion coordination, the naphthalene disulfonic acid part forms novel texture by hydrogen bond connection, self-assembly again as counter ion.This novel system structure not only can be enriched the synthetic chemistry theory, also will provide new approaches with cutting out property for the design of novel molecular base inorganic-organic hybridization material.
Before present patent application work, still there is not bpp=1,3-two (4-pyridine) propane, 1,6-nds=1, the patent documentation of the ligand polymer aspect that 6-naphthalene disulfonic acid and two water cobaltous perchlorate self-assemblies form or scientific paper report.
Summary of the invention
The purpose of this invention is to provide a kind of 1 of cobalt that contains, 3-two (4-pyridine) propane (bpp) and 1, the inorganic-organic coordination polymer crystalline structure of the two parts of 6-naphthalene disulfonic acid (nds), in this structure, 1, the 6-naphthalene disulfonic acid is as counter ion, Co
2+Adopt the octahedral coordination pattern, ligating atom is four independently four N atoms and two two O atoms that water molecules provides of providing respectively of bpp, the N atom of each bpp respectively with two contiguous Co
2+Coordination.In addition, remain in each asymmetric unit at seven crystal water molecules, accompanying drawing 1 is seen in the asymmetric unit of its crystalline structure.
In this structure, Co constitutes the 1D duplex structure by going up the N Atomic coordinate with bpp, and its duplex structure is seen accompanying drawing 2, in this structure, and aspect of the double-stranded formation of 1D, around naphthalene disulfonic acid and water molecules were distributed in, its deck structure was seen accompanying drawing 3.
In this structure, 1, the 6-naphthalene disulfonic acid is interspersed between the double-stranded plane that constitutes as counter ion, forms the 3D structure by hydrogen bond between layer and the layer, and this 3D accumulation graph is seen accompanying drawing 4.
Technical scheme of the present invention is as follows:
A kind of ligand polymer crystalline structure that contains two parts is characterized in that this ligand polymer is by 1,3-two (4-pyridine) propane (bpp), 1, and the ligand polymer crystal that 6-naphthalene disulfonic acid (nds) and two water cobaltous perchlorate self-assemblies form, molecular formula is:
[Co(bpp)
2(H
2O)
2]
n·n(1，6-nds)·7nH
2O
The synthetic ligand polymer of hydrothermal method is adopted in this experiment: with ligand 1,3-two (4-pyridine) propane (bpp), 1,6-naphthalene disulfonic acid (nds), two water cobaltous perchlorates are raw material, with water as solvent, put into the teflon-lined stainless steel cauldron after the mixing, isothermal reaction 24h under 160 ℃ of conditions reduces to room temperature with the cooling rate of 3 ℃/h, obtains ligand polymer crystal [Co (bpp)
2(H
2O)
2]
nN (1,6-nds) 7nH
2O.
In the above-mentioned synthetic method, reaction solvent is a water, and preferred temperature is 160 ℃, and the preferred reaction time is 36h, and preferred cooling rate is 3 ℃/h.
Advantage of the present invention and positively effect: ligand polymer of the present invention is easy to preparation, and the part cost of material is cheap, and productive rate is quite high.
Description of drawings:
Accompanying drawing 1 is the asymmetric unit figure of crystalline structure.
Accompanying drawing 2 is the double-stranded figure of 1D.
Accompanying drawing 3 is deck structure figure.
Accompanying drawing 4 is this crystalline 3D structure accumulation graphs.
Embodiment:
The specific embodiment of the invention is not limited to following embodiment.Embodiments of the invention can make the professional and technical personnel more fully understand the present invention.
Embodiment one:
Press Co (ClO
4)
2.2H
2O: bpp: 1,6-nds=2: 2: 1 ratio weighing medicines, the medicine and the 10ml deionized water that weigh up are mixed, stir, put into 20ml and contain the teflon-lined stainless steel cauldron, be heated to 160 ℃, constant temperature 36h, cooling rate with 2 ℃/h is reduced to room temperature, gets less orange crystal after two weeks.
Embodiment two:
Press Co (ClO
4)
2.2H
2O: bpp: 1,6-nds=2: 2: 1 ratio weighing medicines, the medicine and the 10ml deionized water that weigh up are mixed, stir, put into 20ml and contain the teflon-lined stainless steel cauldron, be heated to 160 ℃, constant temperature 36h, cooling rate with 4 ℃/h is reduced to room temperature, gets the pillar-shaped crystal of orange after three weeks.
Embodiment three:
Press Co (ClO
4)
2.2H
2O: bpp: 1,6-nds=2: 2: 1 ratio weighing medicines, the medicine and the 10ml deionized water that weigh up are mixed, stir, put into 20ml and contain the teflon-lined stainless steel cauldron, be heated to 150 ℃, constant temperature 36h, cooling rate with 3 ℃/h is reduced to room temperature, gets the little pillar-shaped crystal of orange after two weeks.
Embodiment four:
Press Co (ClO
4)
2.2H
2O: bpp: 1,6-nds=2: 2: 1 ratio weighing medicines, the medicine and the 10ml deionized water that weigh up are mixed, stir, put into 20ml and contain the teflon-lined stainless steel cauldron, be heated to 170 ℃, constant temperature 36h, cooling rate with 3 ℃/h is reduced to room temperature, gets the pillar-shaped crystal of orange after three weeks.
Embodiment five:
Press Co (ClO
4)
2.2H
2O: bpp: 1,6-nds=2: 2: 1 ratio weighing medicines, the medicine and the 10ml deionized water that weigh up are mixed, stir, put into 20ml and contain the teflon-lined stainless steel cauldron, be heated to 160 ℃, constant temperature 24h, cooling rate with 3 ℃/h is reduced to room temperature, gets the pillar-shaped crystal of orange after three weeks.
Embodiment six:
Press Co (ClO
4)
2.2H
2O: bpp: 1,6-nds=2: 2: 1 ratio weighing medicines, the medicine and the 10ml deionized water that weigh up are mixed, stir, put into 20ml and contain the teflon-lined stainless steel cauldron, be heated to 160 ℃, constant temperature 48h, cooling rate with 3 ℃/h is reduced to room temperature, after all around the pillar-shaped crystal of orange.
Claims (4)
1. one kind contains 1 of cobalt, 3-two (4-pyridine) propane (bpp) and 1, and the inorganic-organic coordination polymer of the two parts of 6-naphthalene disulfonic acid (nds), its molecular formula is [Co (bpp)
2(H
2O)
2]
nN (1,6-nds) 7nH
2O[n is polymerization degree n=1,2,3...].
2. ligand polymer as claimed in claim 1, Co
2+Adopt the octahedral coordination pattern, ligating atom is four independently four N atoms and two two O atoms that water molecules provides of providing respectively of bpp, in addition, remains at seven crystal water molecules.
3. ligand polymer as claimed in claim 1, Co
2+Constitute the 1D duplex structure by going up the N Atomic coordinate with bpp, 1, the 6-naphthalene disulfonic acid interts between the plane that two strands constitutes jointly as counter ion and water molecules, forms the 3D structure by hydrogen bond between layer and the layer.
4. prepare described a kind of 1 of the cobalt that contains of claim 1,3-two (4-pyridine) propane (bpp) and 1, the method for the inorganic-organic coordination polymer of 6-naphthalene disulfonic acid (nds) is characterized in that:
The preparation method is a hydrothermal synthesis method, with ligand 1, and 3-two (4-pyridine) propane (bpp), 1,6-naphthalene disulfonic acid (nds), two water cobaltous perchlorates are raw material, as solvent, react 36hs at 160 ℃ with water, reduce to room temperature with 3 ℃/h, obtain the inorganic-organic coordination polymer crystal.
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447851A (en) * | 2014-10-30 | 2015-03-25 | 辽宁师范大学 | Ultrathin layered material prepared by metal-organic coordination polymer and preparation method of ultrathin layered material |
| CN104892682A (en) * | 2015-07-02 | 2015-09-09 | 齐鲁工业大学 | Synthesis method of metal-coordination polymer containing sulfanilic acid and catalytic activity of metal-coordination polymer |
| CN105017333A (en) * | 2015-07-01 | 2015-11-04 | 齐鲁工业大学 | Catalyst catalyzed synthesis method for dihydropyrimidinone compounds |
| CN105061519A (en) * | 2015-09-08 | 2015-11-18 | 齐鲁工业大学 | Preparation method of metal coordination polymer with catalytic activity |
| CN105131046A (en) * | 2015-09-07 | 2015-12-09 | 齐鲁工业大学 | Synthetic method based on catalyst for catalysis of dihydropyrimidine ketone compounds |
| CN105153240A (en) * | 2015-10-08 | 2015-12-16 | 齐鲁工业大学 | Research of pyridine oxadiazole complex in catalyzing dihydropyrimidones |
| CN105175457A (en) * | 2015-10-09 | 2015-12-23 | 齐鲁工业大学 | Pyridine oxadiazole complex capable of catalyzing DHPMs (Dihydropyrimidinones) |
| CN105198936A (en) * | 2015-09-07 | 2015-12-30 | 齐鲁工业大学 | Preparation of metal coordination polymer containing benzenesulfonic acid cobalt and catalytic activity thereof |
| CN109320560A (en) * | 2018-08-27 | 2019-02-12 | 天津理工大学 | Functional complexes humidity-sensitive material containing cobalt ions and its preparation method and application |
| CN110903478A (en) * | 2019-12-13 | 2020-03-24 | 吉林大学 | Synthesis method of hydrogen bond covalent organic polymer material HCOP-7 |
-
2009
- 2009-03-12 CN CN200910079468A patent/CN101830934A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447851A (en) * | 2014-10-30 | 2015-03-25 | 辽宁师范大学 | Ultrathin layered material prepared by metal-organic coordination polymer and preparation method of ultrathin layered material |
| CN105017333A (en) * | 2015-07-01 | 2015-11-04 | 齐鲁工业大学 | Catalyst catalyzed synthesis method for dihydropyrimidinone compounds |
| CN104892682A (en) * | 2015-07-02 | 2015-09-09 | 齐鲁工业大学 | Synthesis method of metal-coordination polymer containing sulfanilic acid and catalytic activity of metal-coordination polymer |
| CN105131046A (en) * | 2015-09-07 | 2015-12-09 | 齐鲁工业大学 | Synthetic method based on catalyst for catalysis of dihydropyrimidine ketone compounds |
| CN105198936A (en) * | 2015-09-07 | 2015-12-30 | 齐鲁工业大学 | Preparation of metal coordination polymer containing benzenesulfonic acid cobalt and catalytic activity thereof |
| CN105061519A (en) * | 2015-09-08 | 2015-11-18 | 齐鲁工业大学 | Preparation method of metal coordination polymer with catalytic activity |
| CN105153240A (en) * | 2015-10-08 | 2015-12-16 | 齐鲁工业大学 | Research of pyridine oxadiazole complex in catalyzing dihydropyrimidones |
| CN105175457A (en) * | 2015-10-09 | 2015-12-23 | 齐鲁工业大学 | Pyridine oxadiazole complex capable of catalyzing DHPMs (Dihydropyrimidinones) |
| CN109320560A (en) * | 2018-08-27 | 2019-02-12 | 天津理工大学 | Functional complexes humidity-sensitive material containing cobalt ions and its preparation method and application |
| CN110903478A (en) * | 2019-12-13 | 2020-03-24 | 吉林大学 | Synthesis method of hydrogen bond covalent organic polymer material HCOP-7 |
| CN110903478B (en) * | 2019-12-13 | 2022-02-25 | 吉林大学 | Synthesis method of hydrogen bond covalent organic polymer material HCOP-7 |
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Application publication date: 20100915 |