CN107033189B - A kind of platinum (II) complex and its preparation method and application - Google Patents
A kind of platinum (II) complex and its preparation method and application Download PDFInfo
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- CN107033189B CN107033189B CN201710306666.3A CN201710306666A CN107033189B CN 107033189 B CN107033189 B CN 107033189B CN 201710306666 A CN201710306666 A CN 201710306666A CN 107033189 B CN107033189 B CN 107033189B
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Abstract
The present invention provides an eka-platinium (II) complexs, have solid luminescence property, and luminescent color shows stronger anti-saturated absorption from yellow light to feux rouges at 532nm, and the lasing safety of 532nm can be realized using its optical limitation；Platinum (II) complex provided by the invention has piezallochromy property, under the effect of the pressure, it can clearly observe that complex solid luminescence color becomes red from yellow under 365nm ultraviolet lamp, emitting red light may be implemented in the case where methylene chloride steam is stifling simultaneously and revert to yellow, this property can be used in novel information anti-fake.
Description
Technical field
The present invention relates to organic photoelectric functional material field more particularly to a kind of platinum (II) complex and preparation method thereof and
Using.
Background technique
D with plane configuration8Platinum complex is since its excellent photophysical property is in Organic Light Emitting Diode, oxygen biography
Scientific research work has been obtained in the potential using value in the fields such as sense, solar battery, photocatalysis, molecular probe and lasing safety
The extensive concern of author.
Since the new century, as laser weapon gos deep into diversified development in military field, lasing safety is had become
Human eye, camera, photoelectric sensing are protected in confrontation laser hot destruction for a key areas of photoelectronic warfare in modern war
The protection requirements of device and optical system etc. are particularly evident.Pt (II) complex of plane quadrilateral structure all has preferably
Thermal stability, pass through efficiency and triplet quantum yield between higher gap, and be easy to change molecule knot by chemical modification
Structure reaches the regulation to its HOMO and LUMO, to effectively adjust the optical property of material, can be used as efficient optical Limiting material
Material.
Sun seminar in 2011 reports by the D- π-A type platinum complex of fluorenes biphenylyl amine and terpyridyl building, grinds
Both study carefully influence of the different connecting modes to two-photon absorption, the results showed that by the complexs 2 of three key connectings than singly-bound and double
The complex of key possesses bigger two photon absorption cross section (Chem.Eur.J.2011,17,2479-2491).The subsequent seminar
Reported a kind of terpyridyl platinum complex of fluorenes biphenyl benzothiazolyl group again in 2013, research finds its wide Excited-state Absorption
Including visible light and near infrared region, wherein the visible light part anti-saturated absorption strong derived from the complex, near infrared region are
Because there is big photon induced Excited-state Absorption in complex.Pass through three key connecting fluorenes biphenyl benzothiazolyls group and three pyrroles
The complex 2 of piperidinyl group possesses bigger σex/σ0, while such complex has significantly 532nm pulse laser (4.1ns)
Optical limiting properties can be used as potential optical limiting materials (ACS Appl.Mater.Interfaces 2013,5,565-572).
In short, bipyridyl platinum complex has as optical limiting materials, nonlinear optical coefficients are big, laser damage threshold is high, optic response
Time is short, structure is easily modified, photophysical property is controllable and can carry out hybrid combination with other materials, has wide application
Prospect.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of platinum (II) with optical limitation and piezallochromy property
Complex.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of platinum (II) complex has structure shown in Formulas I:
R is one of following radicals in Formulas I:
The present invention also provides the preparation methods of platinum described in above-mentioned technical proposal (II) complex, comprising the following steps:
(1) under the conditions of anhydrous and oxygen-free, 1,3- bipyridyl -5- bromobenzene and connection boric acid pinacol ester are urged in organic palladium class
Agent and the lower progress cross-coupling reaction of alkaline matter catalysis, obtain 1,3- bipyridyl -5- borate ester；
(2) in the absence of oxygen, 1, the 3- bipyridyl -5- borate ester and bromo fluorenes step (1) obtained
Derivative carries out in mixed solution of the toluene with second alcohol and water under tetra-triphenylphosphine palladium and inorganic base substance catalysis
Suzuki coupling reaction obtains joining the ligand that 1,3- bipyridyl benzene is core with fluorenes,
The bromo fluorene derivative is one of following structures:
(3) under anaerobic, by the step (2) obtain with fluorenes connection 1,3- bipyridyl benzene be core ligand with
Dichloro two (dimethyl sulfoxide) platinum carries out coordination substitution in acetic acid solution, obtains the platinum (II) with structure shown in Formulas I
Complex.
Preferably, palladium class catalyst includes [1,1'- bis- (diphenylphosphine) ferrocene] palladium chloride in the step (1)
And/or triphenylphosphine palladium.
Preferably, the molar ratio of 1,3- bipyridyl -5- bromobenzene and connection boric acid pinacol ester is 1:1 in the step (1)
~4.
Preferably, in the step (1) cross-coupling reaction temperature be 70~90 DEG C, the cross-coupling reaction when
Between be 4~10h.
Preferably, the molar ratio of 1,3- bipyridyl -5- borate ester and bromo fluorene derivative is 1 in the step (2):
1~2.
Preferably, the molar ratio of 1,3- bipyridyl -5- borate ester and tetra-triphenylphosphine palladium is 1 in the step (2):
0.05~0.20.
It preferably, is ligand and dichloro two (the dimethyl Asia of core with fluorenes connection 1,3- bipyridyl benzene in the step (3)
Sulfone) platinum molar ratio be 1:1~2.5.
Preferably, dichloro two (dimethyl sulfoxide) platinum replaces with tetrachloro and closes sub- potassium platinate in the step (3).
The present invention also provides preparation methods described in (II) complex of platinum described in above-mentioned technical proposal or above-mentioned technical proposal
Application of obtained platinum (II) complex in optical limitation or information anti-fake.
Preferably, application of platinum (II) complex in optical limitation includes being used for lasing safety field.
The present invention provides a kind of platinum (II) complex, there is certain solid emissive, luminescent color from yellow light to feux rouges,
And stronger anti-saturated absorption is presented at 532nm, it can be very good the laser of protection 532nm wavelength, can be applied to light limit
In width effect, as being applied in lasing safety field；Platinum (II) complex provided by the invention has piezallochromy property, is pressing
Under the action of power, it can clearly observe that solid luminescence color becomes red from yellow under 365nm ultraviolet lamp, while
Emitting red light may be implemented under methylene chloride steam is stifling and revert to yellow, this property can be used for novel information anti-fake
In.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is uv-visible absorption spectra of the complex Pt-1~Pt-5 of the present invention in dichloromethane solution；
Fig. 2 is phosphorescence emission spectra of the complex Pt-1~Pt-5 of the present invention in dichloromethane solution；
Fig. 3 is complex Pt-1 transient absorption spectra in acetonitrile solution of the present invention；
Fig. 4 is complex Pt-2 transient absorption spectra in acetonitrile solution of the present invention；
Fig. 5 is complex Pt-3 transient absorption spectra in acetonitrile solution of the present invention；
Fig. 6 is complex Pt-4 transient absorption spectra in acetonitrile solution of the present invention；
Fig. 7 is complex Pt-5 transient absorption spectra in acetonitrile solution of the present invention；
Fig. 8 is that complex Pt-1~Pt-5 of the present invention measures optical Limiting curve in acetonitrile solution under 532nm；
Fig. 9 is complex Pt-1~Pt-5 solid phosphor launching light spectrogram of the present invention；
Figure 10 is complex Pt-4 of the present invention in pressure effect and the stifling front and back launching light spectrogram of solvent.
Specific embodiment
The present invention provides a kind of platinum (II) complexs, have structure shown in Formulas I:
R is one of following radicals in Formulas I:
The present invention also provides the preparation methods of platinum described in above-mentioned technical proposal (II) complex, comprising the following steps:
(1) under the conditions of anhydrous and oxygen-free, 1,3- bipyridyl -5- bromobenzene and connection boric acid pinacol ester are urged in organic palladium class
Agent and the lower progress cross-coupling reaction of alkaline matter catalysis, obtain 1,3- bipyridyl -5- borate ester；
(2) in the absence of oxygen, 1, the 3- bipyridyl -5- borate ester and bromo fluorenes step (1) obtained
Derivative carries out in mixed solution of the toluene with second alcohol and water under tetra-triphenylphosphine palladium and inorganic base substance catalysis
Suzuki coupling reaction obtains joining the ligand that 1,3- bipyridyl benzene is core with fluorenes,
The bromo fluorene derivative is one of following structures:
(3) under anaerobic, by the step (2) obtain with fluorenes connection 1,3- bipyridyl benzene be core ligand with
Dichloro two (dimethyl sulfoxide) platinum coordination substitution in acetic acid solution obtains the cooperation of the platinum (II) with structure shown in Formulas I
Object.
The present invention is under the conditions of anhydrous and oxygen-free, by 1,3- bipyridyl -5- bromobenzene and connection boric acid pinacol ester in organic palladium
Class catalyst and the lower progress cross-coupling reaction of alkaline matter catalysis, obtain 1,3- bipyridyl -5- borate ester.In the present invention
In, the palladium class catalyst preferably includes [1,1'- bis- (diphenylphosphine) ferrocene] palladium chloride and/or triphenylphosphine dichloride
Palladium；When the palladium class catalyst is mixing for [bis- (diphenylphosphine) ferrocene of 1,1'-] palladium chloride and triphenylphosphine palladium
When closing object, the present invention is to [1,1'- bis- (diphenylphosphine) ferrocene] palladium chloride and triphenylphosphine dichloride in the mixture
The mass ratio of palladium does not have special restriction, using any mass ratio [1,1'- bis- (diphenylphosphine) ferrocene] palladium chloride and
The mixture of triphenylphosphine palladium.In embodiments of the present invention, described [1,1'- bis- (diphenylphosphine) ferrocene] two
The mass ratio of palladium chloride and triphenylphosphine palladium is preferably 1~5:1, more preferably 3:1.
In the present invention, the molar ratio of 1, the 3- bipyridyl -5- bromobenzene and connection boric acid pinacol ester be preferably 1:1~
4, more preferably 1:2~2.5.
In the present invention, the temperature of the cross-coupling reaction is preferably 70~90 DEG C, and more preferably 75~85 DEG C；It is described
The time of cross-coupling reaction is preferably 4~10h, more preferably 6~8h.
In the present invention, the alkaline matter includes one of potassium acetate, sodium carbonate, potassium carbonate, preferably potassium acetate.
In the present invention, the organic solvent includes 4- dioxane and/or dimethyl sulfoxide.
In the present invention, the molar ratio of 1, the 3- bipyridyl -5- bromobenzene and alkaline matter is preferably 1:2~6, more excellent
It is selected as 1:2.5~4.
After the completion of the cross-coupling reaction, the present invention preferably post-processes cross-coupling reaction product, obtains 1,
3- bipyridyl -5- borate ester.In the present invention, the post-processing preferably includes following steps:
Cross-coupling reaction product is successively carried out to cooling, is washed, organic layer is obtained；
The organic layer is successively dried, removes solvent, purifying, obtains 1,3- bipyridyl -5- borate ester.
The present invention does not have special restriction to the mode of the cooling, preferably natural at room temperature in embodiments of the present invention
It is cooling.
The present invention does not have special restriction to the mode of the drying, in embodiments of the present invention preferably with anhydrous MgSO4
Dry organic layer.
The present invention does not have special restriction to the mode of the removal solvent, in embodiments of the present invention preferably with depressurizing
The mode of filter removes organic solvent.
The present invention does not have special restriction to the column chromatography eluting method of 1, the 3- bipyridyl -5- borate ester,
Using column chromatography purification process well known to those skilled in the art.In embodiments of the present invention, described column chromatography eluting
The eluant, eluent used is preferably the mixed solution of petroleum ether and ethyl acetate, petroleum ether and ethyl acetate in the mixed solution
Volume ratio is preferably 3:1.
The present invention is to the 1,3- bipyridyl -5- bromobenzene, connection boric acid pinacol ester, organic palladium class catalyst, basic species
The order by merging of matter, organic solvent does not have any special limitation, using mixing charging sequence well known to those skilled in the art
?.Preferably sequentially add in embodiments of the present invention 1,3- bipyridyl -5- bromobenzene, alkaline matter, connection boric acid pinacol ester,
Organic palladium class catalyst, organic solvent.
The present invention does not have any special restriction to the device of the cross-coupling reaction, ripe using those skilled in the art
The reaction unit known.It is preferably carried out in two mouthfuls of flasks in embodiments of the present invention.
The present invention does not have any special restriction to the mixed mode, using mixing well known to those skilled in the art
Mode.It preferably being carried out by the way of stirring in embodiments of the present invention, the revolving speed of the stirring is preferably 100~
300rpm, more preferably 150~200rpm, the time of the stirring are preferably 4~10h, more preferably 6~8h.
Present invention preferably employs be passed through nitrogen to reach the oxygen free condition.
After obtaining 1,3- bipyridyl -5- borate ester, the present invention in the absence of oxygen, by 1,3-, bis- pyridine
Base -5- borate ester and bromo fluorene derivative under tetra-triphenylphosphine palladium and inorganic base substance catalysis, in toluene and ethyl alcohol and
Suzuki coupling reaction is carried out in the mixed solution of water, obtains joining the ligand that 1,3- bipyridyl benzene is core, the bromine with fluorenes
It is one of following structures for fluorene derivative:
In the present invention, the molar ratio of 1, the 3- bipyridyl -5- borate ester and bromo fluorene derivative is preferably 1:1
~2, more preferably 1:1.2~1.5.
In the present invention, the molar ratio of 1, the 3- bipyridyl -5- borate ester and tetra-triphenylphosphine palladium is preferably 1:
0.05~0.2, more preferably 1:0.08~0.15.
In the present invention, the inorganic base substance preferably includes sodium carbonate, potassium phosphate, cesium carbonate, sodium bicarbonate or hydrogen
Sodium oxide molybdena.
In the present invention, the molar ratio of 1, the 3- bipyridyl -5- borate ester and inorganic base substance is preferably 1:2
~6, more preferably 1:2.5~5.
In the present invention, the volume ratio of the toluene and toluene and second alcohol and water in the mixed solution of second alcohol and water is preferably
2~6:2~5:1, more preferably 4:4:1.
In the present invention, the temperature of the Suzuki coupling reaction is preferably 75~90 DEG C, and more preferably 80~85 DEG C；Institute
The time for stating Suzuki coupling reaction is preferably 8~for 24 hours, more preferably 10~16h.
After the completion of the Suzuki coupling reaction, the present invention preferably post-processes Suzuki coupling reaction product, obtains
To using fluorenes connection 1,3- bipyridyl benzene as the ligand of core.In the present invention, the post-processing preferably includes following steps:
Suzuki coupling reaction reaction product is successively carried out to cooling, is washed, organic layer is obtained；
The organic layer is successively dried, removes solvent, purifying, obtains joining with fluorenes 1,3- bipyridyl benzene as core
Ligand.
The present invention does not have special restriction to the mode of the cooling, preferably natural at room temperature in embodiments of the present invention
It is cooling.
The present invention does not have special restriction to the mode of the drying, in embodiments of the present invention preferably with anhydrous MgSO4
Dry organic layer.
The present invention does not have special restriction to the mode of the removal solvent, in embodiments of the present invention preferably with depressurizing
The mode of filter removes organic solvent.
The present invention to it is described using fluorenes connection 1,3- bipyridyl benzene be the column chromatography eluting method of the ligand of core without spy
Different restriction, using column chromatography purification process well known to those skilled in the art.In embodiments of the present invention, the column color
The eluant, eluent that spectrometry purifying uses is preferably the mixed solution of petroleum ether and ethyl acetate, petroleum ether and second in the mixed solution
The volume ratio of acetoacetic ester is preferably 3:1.
The present invention is to the 1,3- bipyridyl -5- bromobenzene, bromo fluorene derivative, tetra-triphenylphosphine palladium, inorganic alkaline object
The order by merging of the mixed solution of matter, toluene and second alcohol and water does not have any special limitation, ripe using those skilled in the art
The mixing charging sequence known.1,3- bipyridyl -5- bromobenzene is preferably sequentially added in embodiments of the present invention, bromo fluorenes spreads out
Biology, tetra-triphenylphosphine palladium, inorganic base substance, toluene, ethyl alcohol, water.
Present invention preferably employs be passed through nitrogen to reach the oxygen free condition.
It obtains after joining the ligand that 1,3- bipyridyl benzene is core with fluorenes, the present invention under anaerobic, will be described with fluorenes
Join the ligand and dichloro two (dimethyl sulfoxide) platinum coordination substitution in acetic acid solution that 1,3- bipyridyl benzene is core, obtains
To platinum (II) complex with structure shown in Formulas I.
In the present invention, described to join the ligand and dichloro two (dimethyl sulfoxide) platinum that 1,3- bipyridyl benzene is core with fluorenes
Molar ratio be preferably 1:1~2.5, more preferably 1:1.2~1.5.
In the present invention, the temperature of the coordination substitution is preferably 105~125 DEG C, and more preferably 110~115 DEG C；
The time of the coordination substitution is preferably 24~72h, more preferably 36~48h.
After the completion of the coordination substitution, the present invention preferably post-processes coordination substitution product, is had
There is platinum (II) complex of structure shown in Formulas I.In the present invention, the post-processing preferably includes following steps:
Coordination substitution product is successively carried out to cooling, is washed, crude product is obtained；
The crude product is purified, platinum (II) complex with structure shown in Formulas I is obtained.
The present invention does not have special restriction to the mode of the cooling, preferably natural at room temperature in embodiments of the present invention
It is cooling.
The present invention does not have special restriction to the step of washing, using mode of washing well known to those skilled in the art
, water, ethanol washing are successively used in embodiments of the present invention.
The present invention is preferably column chromatography eluting method or recrystallization method to the mode of the purifying.The present invention is to the tool
Having the column chromatography eluting method of platinum (II) complex of structure shown in Formulas I does not have special restriction, using those skilled in the art
Column chromatography purification process known to member.In the present invention, the solvent that the recrystallization method uses be preferably methylene chloride and
The mixed solution of hexane, the volume ratio of methylene chloride and hexane is preferably 1:3 in the mixed solution.
The present invention is to described using fluorenes connection 1,3- bipyridyl benzene as the ligand of core, dichloro two (dimethyl sulfoxide) platinum, second
The order by merging of acid solution does not have any special limitation, using mixing charging sequence well known to those skilled in the art.
Acetic acid is preferably sequentially added in embodiments of the present invention, using fluorenes connection 1,3- bipyridyl benzene as the ligand of core, two (diformazan of dichloro
Base sulfoxide) platinum.
Present invention preferably employs be passed through nitrogen to reach the oxygen free condition.
In the present invention, dichloro two (dimethyl sulfoxide) platinum replaces with tetrachloro and closes sub- potassium platinate.In the present invention, will
Dichloro two (dimethyl sulfoxide) platinum replace with tetrachloro close the operation after sub- potassium platinate can be specifically according to above-mentioned technical proposal institute
The operation stated carries out, and is no longer repeated herein.
The present invention also provides preparation methods described in (II) complex of platinum described in above-mentioned technical proposal or above-mentioned technical proposal
Application of obtained platinum (II) complex in optical limitation and information anti-fake.
In the present invention, application of platinum (II) complex in optical limitation includes being used for lasing safety field,
More preferably it is applied in lasing safety device.
The present invention provides a kind of platinum (II) complex, there is certain solid emissive, luminescent color from yellow light to feux rouges,
And stronger anti-saturated absorption is presented at 532nm, it can be very good the laser of protection 532nm wavelength, can be applied to light limit
In width effect, in lasing safety field；Platinum (II) complex provided by the invention has piezallochromy property, in the work of pressure
Under, it can clearly observe that solid luminescence color becomes red from yellow under 365nm ultraviolet lamp, while in dichloromethane
Emitting red light may be implemented under alkane steam is stifling and revert to yellow, this property can be used in novel information anti-fake.
Platinum provided by the invention (II) complex and its preparation method and application is carried out below with reference to embodiment detailed
Illustrate, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The synthesis of bipyridyl borate ester
Be added 1,3- bipyridyl -5- bromobenzene 0.31g, potassium acetate 0.294g in bis- mouthfuls of flasks of 100mL, connection boric acid frequency that
Alcohol ester 0.508g and [1,1- bis- (diphenylphosphino) ferrocene] palladium chloride 0.082g and anhydrous Isosorbide-5-Nitrae-dioxane 25mL,
Lower 80 DEG C of nitrogen protection are heated 6 hours.After being cooled to room temperature, solution is washed with water (3 × 20mL).By organic layer with anhydrous
MgSO4It dries, filters and solvent is removed under reduced pressure.Purified by column chromatography (eluant, eluent: petrol ether/ethyl acetate=3:
1) faint yellow product, yield 83% are obtained.1HNMR(400MHz,CDCl3): δ 8.78 (t, J=2Hz, 1H), 8.71-8.73
(m, 2H), 8.465 (d, J=2,2H), 7.89 (d, J=4,2H), 7.74-7.78 (m, 2H), 7.22-7.25 (m, 2H), 1.38
(s,12H)。13C NMR(100MHz,CDCl3):δ157.3,149.5,139.3,136.8,133.82,128.7,122.2,
121.1,84.04,83.5,82.81,75.06,24.9.ESI-HRMS:m/z 358.Anal.calcd (%) for
C22H23BN2O2:C,73.76；H,6.47；N,7.82；Found:C,73.71；H,6.51；N,7.85.
Embodiment 2
The synthesis of ligand 4a
Borate 0.716g, bromo fluorenes 2mmol, Na are added in bis- mouthfuls of flasks of 10mL2CO30.846g, Pd (PPh3)40.23g, adds toluene 40mL, and the mixed liquor of ethyl alcohol 40mL and water 10mL flow back 12 hours under nitrogen protection.It is cooled to
After room temperature, solution is washed with water (3 × 20mL).By organic layer with anhydrous MgSO4It dries, filters and solvent is removed under reduced pressure.Pass through
Column chromatography is purified (eluant, eluent: petrol ether/ethyl acetate=3:1) and obtains white solid, yield are as follows: 63%.1H NMR
(CDCl3, 400MHz): 8.77 (d, J=2Hz, 2H), 8.55 (s, 1H), 8.35 (s, 2H), 7.93 (d, J=4Hz, 2H),
7.79-7.84(m,3H),7.71(s,1H),7.28-7.37(m,5H),2.03-2.06(m,4H),1.07-1.12(m,4H),
0.67-0.70(m,10H)。13C NMR(100MHz,CDCl3):δ206.9,157.4,151.4,151,149.7,143.1,
140.7,140.5,139.8,136.8,127.1,126.7,126.5,126.3,124.7,122.9,122.4,121.7,
121.1,119.9,119.7,55.2,40.2,30.9,29.7,26,23.1,13.8。ESI-HRMS:m/z calc.for
[C37H36N2+H]+:509.29513,found 509.29514。Elemental analysis calculated for
C37H36N2:C,87.36；H,7.13；N,5.51.Found:C,81.27；H,8.07；N,5.80.
Embodiment 3
The synthesis of ligand 4b
Process is same as embodiment 2, and reactant bromo fluorenes is only changed to bromo fluorenes dinaphthalene acid imide, chromatographs to obtain by column
Greenish yellow solid, yield are as follows: 45%.1HNMR(CDCl3, 400MHz): 8.78 (d, J=2Hz, 2H), 8.67 (q, 2H), 8.56
(s, 1H), 8.34-8.39 (m, 3H), 7.90-7.96 (m, 4H), 7.78-7.88 (m, 5H), 7.70 (t, J=8Hz, 1H), 7.52
(d, J=4Hz, 2H), 7.32 (t, J=4Hz, 2H), 4.24 (t, J=8Hz, 2H), 2.09-2.13 (m, 4H), 1.75-1.78
(m, 2H), 1.46-1.51 (m, 2H), 1.10-1.16 (m, 4H), 1.01 (t, J=8Hz, 3H), 0.67-0.79 (m, 10H).13C
NMR(100MHz,CDCl3):δ164.4,164.2,157.3,151.7,149.7,147.5,142.8,141.3,140.5,
139.87,137.4,136.9,132.7,131.1,130.9,130.2,128.9,128.8,127.8,126.7,124.6,
122.4,121.1,120.4,58.45,55.49,40.31,40.12,30.27,29.7,26.2,23,20.4,18.4。ESI-
HRMS:m/z calc.for[C53H49N3O2+H]+:760.38975,found 760.38898.Elemental analysis
calculated for C53H49N3O2:C,83.76；H,6.50；N,5.53；.Found:C,83.67；H,6.52；N,5.59.
Embodiment 4
The synthesis of ligand 4c
Process is same as embodiment 2, and reactant is only changed to bromo fluorenes connection benzothiazole, chromatographs to obtain by column faint yellow
Solid, yield are as follows: 53%.1H NMR(CDCl3, 400MHz): 8.77 (d, J=2Hz, 2H), 8.57 (s, 1H), 8.37 (s,
2H), 8.15 (s, 1H), 8.06-8.12 (m, 2H), 7.94 (d, J=2Hz, 3H), 7.85 (d, J=4Hz, 3H), 7.79 (d, J=
4,2H), 7.75 (s, 1H), 7.51 (t, J=8Hz, 1H), 7.39 (t, J=8Hz, 1H), 7.31 (t, J=8Hz, 2H), 2.12-
2.16(m,4H),1.09-1.13(m,4H),0.67-0.70(m,10H)。13C NMR(100MHz,CDCl3):168.8,157.3,
154.2,152.2,151.9,149.8,143.9,142.8,140.8,140.6,139.7,136.8,135.0,133.7,
132.3,127.1,126.6,126.4,125.0,124.6,122.9,122.3,121.8,121.6,121.5,121,120.8,
120.2,55.6,40.23,26.1,23.1,13.8。ESI-HRMS:m/z calc.for[C44H39N3S+H]+:642.29375,
found 642.29376。Elemental analysis calculated for C44H39N3S:C,82.33；H,6.12；N,
6.55.Found:C,82.27；H,6.07；N,6.57.
Embodiment 5
The synthesis of ligand 4d
Process is same as embodiment 2, and reactant is only changed to bromo fluorenes connection phenthazine, chromatographs to obtain pale yellow colored solid by column
Body, yield 41%.1H NMR(CDCl3, 400MHz): 8.77 (d, J=2Hz, 2H), 8.57 (s, 1H), 8.39 (s, 2H),
7.95 (t, J=8Hz, 3H), 7.80-7.86 (m, 4H), 7.76 (s, 1H), 7.38 (t, J=8Hz, 2H), 7.30 (t, J=
8Hz, 2H), 7.02 (t, J=4Hz, 2H), 6.78-6.84 (m, 4H), 6.23 (d, J=4Hz, 2H), 2.01-2.11 (m, 4H),
1.07-1.14(m,4H),0.68-0.78(m,10H)。13C NMR(100MHz,CDCl3):157.3,154.5,151.9,
149.7,144.6,142.8,141.0,140.6,139.7,136.8,129.6,126.8,126.7,126.5,126.0,
124.6,122.4,122.3,121.9,121.8,119.5,115.6,55.6,40,26.2,22.9,13.9.ESI-HRMS:m/z
calc.for[C49H43N3S+H]+:706.32505,found 706.32397。Elemental analysis calculated
for C49H43N3S:C,83.37；H,6.14；N,5.95.Found:C,83.27；H,6.09；N,5.90.
Embodiment 6
The synthesis of ligand 4e
Process is same as embodiment 2, and reactant is only changed to bromo fluorenes connection tert-butyl carbazole, chromatographs to obtain white by column
Solid, yield 59%.1H NMR(CDCl3, 400MHz): 8.77 (d, J=2Hz, 2H), 8.58 (s, 1H), 8.39 (s, 2H),
8.18 (s, 2H), 7.93 (t, J=8Hz, 3H), 7.77-7.87 (m, 5H), 7.56 (d, J=4Hz, 2H), 7.49 (d, J=4Hz,
2H), 7.41 (d, J=4Hz, 2H), 7.30 (t, J=4Hz, 2H), 2.05-2.11 (m, 4H), 1.49 (s, 18H), 1.13-1.18
(m,4H),0.74-0.79(m,10H)。13C NMR(100MHz,CDCl3):157.4,152.8,151.7,149.8,142.9,
142.8,140.8,140.6,139.6,139.4,136.8,126.6,125.0,124.5,123.8,123.4,122.4,
121.3,121.0,120.8,120.4,120.1,116.3,109.2,55.6,40.2,34.8,32.1,26.2,23.1,13.9。
ESI-HRMS:m/z calc.for[C57H59N3+H]+:786.47818,found 786.47736。Elemental analysis
calculated for C57H59N3:C,87.09；H,7.57；N,5.35.Found:C,87.07；H,7.51；N,5.43.
Embodiment 7
The synthesis of complex Pt-1
By 4a 0.4mmol, Pt (DMSO)2Cl2The mixture of 0.4mmol and acetic acid 20mL flow back 24 hours under a nitrogen.
After being cooled to room temperature, reaction mixture is filtered.With water, ethyl alcohol and ether washing precipitating, crude product pass through in dichloromethane/hexane
Middle recrystallization is further purified to obtain yellow powder, yield are as follows: 35%.1H NMR(CDCl3,400MHz):δ9.28(dd,J1=
16Hz,J2=2Hz, 2H), 7.93 (t, J=8Hz, 2H), 7.77 (t, J=8Hz, 4H), 7.60 (d, J=4Hz, 4H) .7.36
(m, d, J=4Hz, 3H), 7.22 (s, 2H), 2.00-2.06 (m, 4H), 1.10-1.15 (m, 4H), 0.69-0.73 (m, 10H)
.13C NMR(100MHz,CDCl3):δ206.9,167.1,152.2,151.6,150.8,141.1,140.7,140.6,140.3,
138.8,137.1,127.1,126.8,125.8,123.3,123.1,122.9,121.1,120.1,119.7,119.3,55.2,
40.2,30.9,26,23.1,13.8.HRMS(MALDI-TOF),m/z calcd for[C37H35ClN2Pt+H]+:738.2209,
found 738.2169.Anal.Calcd.for C37H35ClN2Pt:C,60.20；H,4.78；N,3.79.Found:C,60.26；
H,4.81；N,3.78.
Embodiment 8
The synthesis of complex Pt-2
Reaction process is same as embodiment 7, and reactant 4a is only changed to compound 4b, and product passes through column layer after reaction
Analysis obtains yellow powder, yield 41%.1H NMR(CDCl3, 400MHz): δ 9.39 (dd, J1=16Hz, J2=2Hz, 2H),
8.65-8.71 (m, 2H), 8.35 (d, J=4Hz, 1H), 8.0 (t, J=4Hz, 2H), 7.88-7.94 (m, 2H), 7.82 (t, J=
8Hz, 3H), 7.64-7.73 (m, 6H), 7.53 (d, J=4Hz, 2H), 7.33 (t, J=4Hz, 2H), 4.24 (t, J=8Hz,
2H),2.10-2.14(m,4H),1.75-1.78(m,2H),1.48-1.52(m,2H),1.15-1.19(m,4H),1.01(t,J
=8Hz, 3H), 0.75-0.82 (m, 10H).HRMS(MALDI-TOF),m/z calcd for[C53H48ClN3O2Pt+H]+:
989.3156,found 989.3186.Anal.Calcd.for C53H48ClN3O2Pt:C,64.33；H,4.89；N,4.25；
.Found:C,64.30；H,4.85；N,4.29.
Embodiment 9
The synthesis of complex Pt-3
Reaction process is same as embodiment 7, and reactant 4a is only changed to compound 4c, obtains yellow powder, and yield is
29%.1H NMR(CDCl3,400MHz):δ9.34(dd,J1=16Hz, J2=2Hz, 2H), 8.17 (s, 1H), 8.08-8.13
(m, 2H), 7.94-7.99 (m, 3H), 7.85 (d, J=4Hz, 2H), 7.80 (d, J=4Hz, 2H), 7.67 (d, J=4Hz, 3H),
7.63 (s, 1H), 7.52 (t, J=8Hz, 1H), 7.40 (t, J=4Hz, 1H), 7.29 (d, J=4Hz, 2H), 2.13-2.19 (m,
4H),1.12-1.17(m,4H),0.69-0.73(m,10H).HRMS(MALDI-TOF),m/z calcd for
[C44H38ClN3PtS+H]+:871.2196,found 871.2191.Anal.Calcd.for C44H38ClN3PtS:C,60.65；
H,4.40；N,4.82.Found:C,60.60；H,4.33；N,4.78.
Embodiment 10
The synthesis of complex Pt-4
Reaction process is same as embodiment 7, and reactant 4a is only changed to 4d, obtains yellow powder, yield 32%.1H
NMR(CDCl3,400MHz):δ9.38(dd,J1=16Hz, J2=2Hz, 2H), 7.97-8.02 (m, 3H), 7.84 (t, J=8Hz,
3H), 7.67-7.72 (m, 3H), 7.63 (s, 1H), 7.39 (t, J=8Hz, 2H), 7.32 (t, J=4Hz, 2H), 7.03 (t, J=
4Hz,2H),6.81-6.83(m,4H),6.24-6.27(m,2H),2.06-2.11(m,4H),1.10-1.17(m,4H),0.70-
0.76(m,10H)。HRMS(MALDI-TOF),m/z calcd for[C49H42ClN3PtS+H]+935.2509,found
935.2507.Anal.Calcd.for C49H42ClN3PtS:C,62.91；H,4.53；N,4.49.Found:C,62.99；H,
4.58；N,4.54.
Embodiment 11
The synthesis of complex Pt-5
Reaction process is same as embodiment 7, and reactant 4a is only changed to 4e, obtains yellow powder, yield 19%.1H
NMR(CDCl3,400MHz):δ9.38(dd,J1=16Hz, J2=2Hz, 2H), 8.18 (s, 2H), 8.00 (t, J=8Hz, 2H),
7.94 (d, J=4Hz, 1H), 7.84 (t, J=8Hz, 3H), 7.72 (s, 1H), 7.68 (d, J=4Hz, 1H), 7.63 (s, 1H),
7.58 (s, 2H), 7.50 (d, J=4Hz, 2H), 7.42 (d, J=8Hz, 2H), 7.32 (d, J=4Hz, 2H), 2.07-2.14 (m,
4H),1.49(s,18H),1.15-1.19(m,4H),0.75-0.81(m,10H)。HRMS(MALDI-TOF),m/z calcd
for[C57H58ClN3Pt+H]+:1015.4040,found 1015.4023.Anal.Calcd.for C57H58ClN3Pt:C,
67.41；H,5.76；N,4.14.Found:C,67.52；H,5.81；N,4.19.
Embodiment 12
The test of complex Pt-1~Pt-5 uv-visible absorption spectra
Using methylene chloride as solvent, it is 1 × 10 that compound Pt-1~Pt-5 is made into concentration respectively-5The solution of mol/L.?
Under room temperature, using 8453 type ultraviolet-visible photometer of Agilent, with the quartz colorimetric utensil of 1cm, in 200-600nm wave
The scanning of Duan Jinhang ultra-violet absorption spectrum measures ultraviolet-ray visible absorbing light of the compound Pt-1~Pt-5 in dichloromethane solution
Spectrum, test result are shown in Fig. 1.The dichloromethane solution of these platinum complexes all shows stronger absorption in ultraviolet-visible light area.
Other than Pt-3, strong absorption of other complexs before 350nm can be attributed to match intracorporal1π, π * transition, and 350-
The absorption of 455nm can be attributed to1MLCT/1ILCT transition.The absorption spectrum of Pt-3 is mainly shown as a strong absworption peak, can belong to
For1π,π*/1MLCT/1ILCT transition.
Embodiment 13
The test of complex Pt-1~Pt-5 phosphorescence emission spectra
Using methylene chloride as solvent, it is 1 × 10 that compound Pt-1~Pt-5, which is made into concentration,-5The solution of mol/L.In room temperature
Under the conditions of, after maintaining nitrogen purge 30 minutes, with the quartz colorimetric utensil of 1cm, slit width Iex/Iem=10nm/5nm, uses day
Vertical emission spectrum of the F-4600 fluorescence spectrophotometer measurement compound Pt-1~Pt-5 in dichloromethane solution, test result
See Fig. 2.The transmitting of all platinum complexes is respectively positioned on green-yellow light region.The emission spectrum of wherein Pt-1, Pt-4, Pt-5 are similar, are in
Reveal certain fine structure and relatively narrow peak type, can be attributed to3π, π * excitation state.And the emission peak of Pt-3 is with respect to red shift, knot
Negative solvation effect is closed, can be emitted and be attributed to3π,π*/3MLCT excitation state.The emission spectrum of Pt-2 shows as wide hair
Peak is penetrated, is derived from1ILCT excitation state.
Embodiment 14
The test of complex Pt-1~Pt-5 transient absorption spectra
Using acetonitrile as solvent, compound Pt-1~Pt-5 is made into the concentration solution that absorbance is 0.4 at 355nm.?
Under room temperature, after maintaining nitrogen purge 30 minutes, with the transient absorption spectra of transient state absorption spectrometer test compound.Pt-1,
Pt-4, Pt-5 have strong and negative absorption band in 490nm to 680nm, this is because three complexs have at that wavelength
Caused by stronger phosphorescent emissions.In addition Pt-2 and Pt-3 has stronger positive absorption peak after 400nm, illustrates that the two are matched
It closes excited-state absorption cross section of the object in this wave-length coverage and is greater than ground state absorption cross section.Test result is shown in Fig. 3~7.
Embodiment 15
The test of complex Pt-1-Pt-5 optical Limiting
Using acetonitrile as solvent, compound Pt-1~Pt-5 is made into reach at 532nm 95% linear transmittance it is molten
Liquid makes complex Pt-1~Pt-5 optical Limiting curve by changing laser energy.With gradually increasing for incident optical density, thoroughly
The energy for crossing sample has certain downward trend, and wherein the degree of Pt-2 and Pt-3 decline is larger, illustrates that the two compounds have
There is good anti-saturated absorption property, can be used as laser protective material.Test result is shown in Fig. 8.
Embodiment 16
Complex Pt-1~Pt-5 solid phosphor emission spectrum
At room temperature, complex Pt-1~Pt-5 solid powder is added in solid sample slot, is swashed with 450nm wavelength
The solid emissive spectrum of hair test complex, test result are shown in Fig. 9.The transmitting of all platinum complexes is located at yellow green to red color area
Domain.The emission spectrum of wherein Pt-1, Pt-4, Pt-5 are similar, and the emission peak with fine structure is presented in 530nm or so,
The transmitting of Pt-3 shows two emission peaks with respect to red shift, one in 550nm, another is in 610nm.Pt-2 is in 650nm
There is a wide emission peak.
Embodiment 17
Complex Pt-4 is in pressure effect and the stifling front and back emission spectrum of solvent
Complex Pt-4 is shown in Figure 10 in pressure effect and the stifling front and back emission spectrum of solvent, and compound Pt-4 is placed in agate
In mortar, solid is firmly ground, until luminescent color becomes red under 365nm ultraviolet lamp for it, by the solid sample after grinding
Collection is added in solid sample slot, solid emissive spectrum after test grinding, it can be found that the solid emissive peak position after grinding
It is converted near 670nm by original 530nm.Then the solid sample after grinding is put into the steam atmosphere of methylene chloride,
It observes after its color is restored to initial conditions and tests its solid emissive spectrum, solid emissive peak position is attached by 670nm as the result is shown
It is close to be restored to 530nm again.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of platinum (II) complex has structure shown in Formulas I:
R is one of following radicals in Formulas I:
The preparation method of platinum described in claim 1 2. (II) complex, comprising the following steps:
(1) under the conditions of anhydrous and oxygen-free, by 1,3- bipyridyl -5- bromobenzene and connection boric acid pinacol ester in organic palladium class catalyst
It is catalyzed lower progress cross-coupling reaction with alkaline matter, obtains 1,3- bipyridyl -5- borate ester；
(2) in the absence of oxygen, 1, the 3- bipyridyl -5- borate ester and bromo fluorenes step (1) obtained is derivative
It is even to carry out Suzuki under tetra-triphenylphosphine palladium and inorganic base substance catalysis in the mixed solution of toluene and second alcohol and water for object
Connection reaction obtains joining the ligand that 1,3- bipyridyl benzene is core with fluorenes,
The bromo fluorene derivative is one of following structures:
(3) under anaerobic, the ligand and dichloro with fluorenes connection 1,3- bipyridyl benzene for the core step (2) obtained
Two (dimethyl sulfoxide) platinum carry out coordination substitution in acetic acid solution, obtain the cooperation of the platinum (II) with structure shown in Formulas I
Object.
3. preparation method according to claim 2, which is characterized in that in the step (1) palladium class catalyst include [1,
Bis- (diphenylphosphine) ferrocene of 1'-] palladium chloride and/or triphenylphosphine palladium.
4. preparation method according to claim 2, which is characterized in that 1,3- bipyridyl -5- bromobenzene in the step (1)
Molar ratio with connection boric acid pinacol ester is 1:1~4.
5. preparation method according to claim 2, which is characterized in that the temperature of cross-coupling reaction in the step (1)
It is 70~90 DEG C, the time of the cross-coupling reaction is 4~10h.
6. preparation method according to claim 2, which is characterized in that 1,3- bipyridyl -5- benzene boron in the step (2)
The molar ratio of acid esters and bromo fluorene derivative is 1:1~2.
7. preparation method according to claim 2, which is characterized in that 1,3- bipyridyl -5- benzene boron in the step (2)
The molar ratio of acid esters and tetra-triphenylphosphine palladium is 1:0.05~0.20.
8. preparation method according to claim 2, which is characterized in that join 1,3- bipyridyl in the step (3) with fluorenes
Benzene is the ligand of core and the molar ratio of dichloro two (dimethyl sulfoxide) platinum is 1:1~2.5.
9. the preparation method according to claim 2 or 8, which is characterized in that (dimethyl is sub- for dichloro two in the step (3)
Sulfone) platinum replaces with tetrachloro and closes sub- potassium platinate.
What 10. preparation method described in platinum (II) complex described in claim 1 or claim 2~9 any one obtained
Application of platinum (II) complex in optical limitation or information anti-fake.
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