CN106519250A - Preparation method of one-dimensional chain copper coordination polymers with nitrogen-containing small-molecular organic ligand for adjusting fluorescence emission properties - Google Patents
Preparation method of one-dimensional chain copper coordination polymers with nitrogen-containing small-molecular organic ligand for adjusting fluorescence emission properties Download PDFInfo
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- CN106519250A CN106519250A CN201610858979.5A CN201610858979A CN106519250A CN 106519250 A CN106519250 A CN 106519250A CN 201610858979 A CN201610858979 A CN 201610858979A CN 106519250 A CN106519250 A CN 106519250A
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Abstract
The invention relates to a preparation method of one-dimensional chain copper coordination polymers with a nitrogen-containing small-molecular organic ligand for adjusting fluorescence emission properties, wherein the method comprises the following steps: dissolving a small-molecular nitrogen-containing heterocyclic organic ligand, a copper metal salt and a sulfonic ligand in water, carrying out heating reflux for 1 h, and cooling and filtering; and under a condition of room temperature, naturally volatilizing the filtrate, to obtain a blue single crystal. The fluorescence properties of the complexes can be adjusted and controlled by changing the nitrogen-containing ligand; the fluorescence emission effect of the complexes 1-3 has significant change compared with the ligand and compared with each other; the synthetic method of the complexes is simple and has fewer synthesis steps, and is low in synthesis cost and cheap in raw materials.
Description
Technical field
A kind of a kind of the present invention relates to preparation method of fluorescent polymer, more particularly to nitrogenous small molecule organic ligand regulation
The preparation method of the one-dimensional chain copper coordination polymer of fluorescent emission property.
Background technology
The fluorescent emission property of existing research coordination compound is concentrated mainly on the conjugated system for increasing coordination compound changing cooperation
The electric charge transfer of thing, so that change photoluminescent property.The emphasis of research is the photoluminescent property of single coordination compound.Its fluorescent emission machine
Reason includes that metal-ligand charge is shifted, electric charge transfer between part etc..The metal ion selected during its research is more with rare earth unit
Based on element.The research of this aspect is commonplace.Also, it is few for the report of the regulation and control of the photoluminescent property of coordination compound
See.
Existing fluorescent material species is various, including（1）Nitrogen heterocyclic ring and aromatic rings equiconjugate organic compound, the material
It is not coordination compound, is the aromatic of macromole.The synthesis step of such compound is more, synthesizes costly；（2）
Coordination compound containing conjugation aromatic rings.But, for the fluorescent emission property of these fluorescent materials influence factor and regulation and control because
It is little that element is studied.
The content of the invention
The purpose of the present invention is to set up to match somebody with somebody by cheap nitrogenous small molecule is organic based on a kind of of complex fluorescent property
The difference of body is adjusting the fluorescent emission property of coordination compound.Expand the influence factor for adjusting complex fluorescent emission characteristic.Purpose
It is adjusting the photoluminescent property of coordination compound by simply means.Characterization result shows that the coordination compound that the method is prepared can
With by the fluorescent emission property for changing and then adjusting coordination compound of containing n-donor ligand.
The preparation method of the present invention comprises the steps：
Small molecule nitrogen heterocyclic ring organic ligand is soluble in water with copper metal salt, sulfonic acid ylidene ligands, it is heated to reflux cooled after 1 h
Filter；
At ambient temperature, filtrate is volatilized naturally, obtains blue monocrystalline.
Described small molecule nitrogen heterocyclic ring includes 2,2 '-bipyridyl and pyridine.
Described copper metal salt is Cu (NO3)2·3H2O。
Described sulfonic acid ylidene ligands include 1,5- naphthalene disulfonates and 1,6- naphthalene disulfonates.
Described preparation method specifically includes following step：
Coordination compound 1：By 0.24 g Cu (NO3)2·3H2O（1mmol）, 0.332 g 1,5- naphthalene disulfonates（1mmol）With 0.16
2,2 '-bipyridyls of g（1mmol）20mL water is dissolved in, while stirring with 1 mol L-1It is 4-5 that NaOH solution adjusts pH value,
Cold filtration after 1 h is heated to reflux, at ambient temperature, filtrate is volatilized naturally, after five days, obtains blue monocrystalline, yield is 67%.
Coordination compound 2：By 0.24 g Cu (NO3)2·3H2O（1mmol）, 0.332 g 1,6- naphthalene disulfonates（1mmol）With
1mL pyridines are dissolved in 20mL water, are added dropwise over 1 mol L while stirring-1NaOH solution, the pH value for adjusting reaction system are 5-6,
Cold filtration after 1 h is heated to reflux, at ambient temperature, filtrate is volatilized naturally, after three days, obtains blue monocrystalline, yield is 50%.
Coordination compound 3：10mL Cu (the NO that 0.5mL pyridines are slowly added to be stirred continuously3)2·3H2O（1mmol）Aqueous solution
In, wherein Cu (NO3)2·3H2The quality of O is 0.242 g, adds 0.332 g 1,5- naphthalene disulfonates（1mmol）, will be molten
Liquid is heated to reflux cold filtration after 1 h, and at ambient temperature, filtrate is volatilized naturally, obtains blue monocrystalline after 14 days, and yield is
68.6%。
Advantages of the present invention and effect：
The present invention is, using containing cheap small molecule nitrogen heterocyclic ring organic ligand, to form one-dimensional with copper metal salt, sulfonic acid ylidene ligands
Chain
Coordination polymer, by the change of nitrogenous small molecule organic ligand, reach the purpose of the photoluminescent property of regulation and control coordination compound,
Realize the controllability of fluorescent emission property.
Compared with other fluorescent materials, the complex material of the present invention is the characteristics of have following prominent：(1) its cooperation
Thing it is glimmering
Light emission characteristic can be regulated and controled by changing containing n-donor ligand；(2) the fluorescent emission effect of coordination compound 1-3 with match somebody with somebody body phase
Than and compare each other, change obvious；(3) synthetic method of the coordination compound is simple, and synthesis step is few, and synthesis cost is just
Preferably, it is raw materials used cheap.
Description of the drawings
The molecular structure of Fig. 1 coordination compounds 1.
The one-dimensional catenary structure figure of Fig. 2 coordination compounds 1.
The fluorescence spectrum of Fig. 3 coordination compounds 1.
The molecular structure of Fig. 4 coordination compounds 2.
The one-dimensional catenary structure figure of Fig. 5 coordination compounds 2.
The fluorescence spectrum of Fig. 6 coordination compounds 2.
The molecular structure of Fig. 7 coordination compounds 3.
The one-dimensional catenary structure figure of Fig. 8 coordination compounds 3.
The fluorescence spectrum of Fig. 9 coordination compounds 3.
Specific embodiment
Embodiment 1
Coordination compound 1：By 0.24 g Cu (NO3)2·3H2O（1mmol）, 0.332 g 1,5- naphthalene disulfonates（1mmol）With 0.16
2,2 '-bipyridyls of g（1mmol）20mL water is dissolved in, while stirring with 1 mol L-1It is 4-5 that NaOH solution adjusts pH value,
Cold filtration after 1 h is heated to reflux, at ambient temperature, filtrate is volatilized naturally, after five days, obtains blue monocrystalline, yield is 67%.
Embodiment 2
Coordination compound 2：By 0.24 g Cu (NO3)2·3H2O（1mmol）, 0.332 g 1,6- naphthalene disulfonates（1mmol）And 1mL
Pyridine is dissolved in 20mL water, is added dropwise over 1 mol L while stirring-1NaOH solution, the pH value for adjusting reaction system are 5-6, are heated
Flow back cold filtration after 1 h, and at ambient temperature, filtrate is volatilized naturally, obtains blue monocrystalline after three days, and yield is 50%.
Embodiment 3
Coordination compound 3：10mL Cu (the NO that 0.5mL pyridines are slowly added to be stirred continuously3)2·3H2O（1mmol）In aqueous solution, its
Middle Cu (NO3)2·3H2The quality of O is 0.242 g, adds 0.332 g 1,5- naphthalene disulfonates（1mmol）, solution is heated
Flow back cold filtration after 1 h, and at ambient temperature, filtrate is volatilized naturally, obtains blue monocrystalline after 14 days, and yield is 68.6%.
Coordination compound 1 and coordination compound 3 adopt 1,5- naphthalene disulfonates for the first part, and coordination compound 2 adopts 1,6- naphthalenes, two sulphur
Sour sodium is the first part.Coordination compound 1 adopts 2, and 2 '-bipyridyl is Ligands, coordination compound 2 and coordination compound 3 adopt pyridine for
Ligands.Coordination compound 1, coordination compound 2 and coordination compound 3 adopt Cu2+Ion centered on ion, three are respectively formed one-dimensional chain knot
Structure.Cu2+Ion is hexa-coordinate, the nitrogen-atoms with the sulfonic group oxygen atom ligand and nitrogenous Ligands of the first part
Coordination, remaining coordination site are occupied by hydrone.
Under 315 nm wavelength shooting conditions, 1,5- naphthalene disulfonate and 2, the major fluorescent emission peak point of 2 '-bipyridyl
Not in 379 nm and 251 nm.The major fluorescent emission peak of 1,6- naphthalene disulfonates and pyridine is respectively in 401 nm and 354 nm.
The major fluorescent emission peak of 1,5- naphthalene disulfonates is in 379 nm.
Under 315 nm wavelength shooting conditions, the maximum emission peak of coordination compound 1, coordination compound 2 and coordination compound 3 is respectively 368
Nm, 462 nm and 392 nm.Relative to the main part containing sulfonic group, their maximum emission peak there occurs respectively blue shift, red shift and
Red shift.The central ion of coordination compound 1, coordination compound 2 and coordination compound 3 is Cu2+Ion, which has the 3d for being not completely filled with electronics
Track, the delocalized electron of containing n-donor ligand can be transferred to Cu2+The 3d tracks of ion, form the electric charge transfer of ligand metal, and which is
The main cause of coordination compound 1,3 fluorescent emission of coordination compound 2 and coordination compound.But, the quantity of containing n-donor ligand, weak work each other
Impact can be produced on fluorescent emission with, size of π keys etc..To coordination compound 1, only one of which containing n-donor ligand molecule 2,2 '-connection pyrrole
Pyridine and Cu2+Ion coordination, although π keys are larger, but without weak effect each other between containing n-donor ligand；For coordination compound 2,
There are four containing n-donor ligand molecule pyridines and Cu2+Ion coordination, is acted on weaker pi-pi accumulation to each other；For coordination compound 3,
There are two containing n-donor ligand molecule pyridines and Cu2+Ion coordination, the aromatic rings containing sulfonic acid ylidene ligands have π-π heaps with containing n-donor ligand pyridine
Product effect.Coordination compound 2 and coordination compound 3 and Cu2+The containing n-donor ligand molecular amounts of ion coordination are more than or equal to coordination compound 1 and Cu2+
The containing n-donor ligand molecular amounts of ion coordination；Coordination compound 2 and coordination compound 3 have pi-pi accumulation to act on, and coordination compound 1 does not have.Cause
This, compared with part, the fluorescence emission peak of coordination compound 1 there occurs blue shift, and the fluorescence emission peak of coordination compound 2 and coordination compound 3 is sent out
Red shift is given birth to.
Claims (7)
1. nitrogenous small molecule organic ligand adjusts the preparation method of the one-dimensional chain copper coordination polymer of fluorescent emission property, and which is special
Levy is to comprise the steps：
Small molecule nitrogen heterocyclic ring organic ligand is soluble in water with copper metal salt, sulfonic acid ylidene ligands, it is heated to reflux cooled after 1 h
Filter；
At ambient temperature, filtrate is volatilized naturally, obtains blue monocrystalline.
2. the one-dimensional chain cupric coordination of nitrogenous small molecule organic ligand regulation fluorescent emission property according to claim 1 gathers
Compound
Preparation method, it is characterised in that described small molecule nitrogen heterocyclic ring includes 2,2 '-bipyridyl and pyridine.
3. the one-dimensional chain cupric coordination of nitrogenous small molecule organic ligand regulation fluorescent emission property according to claim 1 gathers
Compound
Preparation method, it is characterised in that described copper metal salt be Cu (NO3)2·3H2O。
4. the one-dimensional chain cupric coordination of nitrogenous small molecule organic ligand regulation fluorescent emission property according to claim 1 gathers
Compound
Preparation method, it is characterised in that described sulfonic acid ylidene ligands include 1,5- naphthalene disulfonates and 1,6- naphthalene disulfonate.
5. the one-dimensional chain cupric coordination of nitrogenous small molecule organic ligand regulation fluorescent emission property according to claim 1 gathers
Compound
Preparation method, it is characterised in that specifically include following step：
Coordination compound 1：By 0.24 g Cu (NO3)2·3H2O（1mmol）, 0.332 g 1,5- naphthalene disulfonates（1mmol）With 0.16
2,2 '-bipyridyls of g（1mmol）20mL water is dissolved in, while stirring with 1 mol L-1It is 4-5 that NaOH solution adjusts pH value,
Cold filtration after 1 h is heated to reflux, at ambient temperature, filtrate is volatilized naturally, after five days, obtains blue monocrystalline, yield is 67%.
6. the one-dimensional chain cupric coordination of nitrogenous small molecule organic ligand regulation fluorescent emission property according to claim 1 gathers
Compound
Preparation method, it is characterised in that specifically include following step：
Coordination compound 2：By 0.24 g Cu (NO3)2·3H2O（1mmol）, 0.332 g 1,6- naphthalene disulfonates（1mmol）And 1mL
Pyridine is dissolved in 20mL water, is added dropwise over 1 mol L while stirring-1NaOH solution, the pH value for adjusting reaction system are 5-6, are heated
Flow back cold filtration after 1 h, and at ambient temperature, filtrate is volatilized naturally, obtains blue monocrystalline after three days, and yield is 50%.
7. the one-dimensional chain cupric coordination of nitrogenous small molecule organic ligand regulation fluorescent emission property according to claim 1 gathers
Compound
Preparation method, it is characterised in that specifically include following step：
Coordination compound 3：10mL Cu (the NO that 0.5mL pyridines are slowly added to be stirred continuously3)2·3H2O（1mmol）In aqueous solution, its
Middle Cu (NO3)2·3H2The quality of O is 0.242 g, adds 0.332 g 1,5- naphthalene disulfonates（1mmol）, solution is heated
Flow back cold filtration after 1 h, and at ambient temperature, filtrate is volatilized naturally, obtains blue monocrystalline after 14 days, and yield is 68.6%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108795417A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex yellow green phosphor material of chain structure |
| CN112552320A (en) * | 2020-12-02 | 2021-03-26 | 辽宁石油化工大学 | One-step in-situ synthesis method of copper-catalyzed N-alkylated benzimidazole derivative and complex |
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| CN101687815A (en) * | 2007-06-26 | 2010-03-31 | 塞诺菲-安万特股份有限公司 | The regioselective copper catalyzed of benzoglyoxaline and azepine benzoglyoxaline synthesized |
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| CN104892518A (en) * | 2014-03-05 | 2015-09-09 | 中国科学院大连化学物理研究所 | Preparation method and application of porous nano metal organic framework material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108795417A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex yellow green phosphor material of chain structure |
| CN112552320A (en) * | 2020-12-02 | 2021-03-26 | 辽宁石油化工大学 | One-step in-situ synthesis method of copper-catalyzed N-alkylated benzimidazole derivative and complex |
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Application publication date: 20170322 |