CN114752070B - Photoresponse intelligent material and preparation method thereof - Google Patents
Photoresponse intelligent material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a photoresponse intelligent material and a preparation method thereof. The material is [ Cd (BCM) 0.5 (4,4′‑bipy) 0.5 ]Belong toThe orthorhombic Pnna space group whose asymmetric units comprise one crystallographically independent divalent Cd, half of a perfluorodithienyl vinyl formate anion and half of a 4,4' -bipyridine molecule. Is prepared by taking perfluor bithienyl vinyl formic acid and 4,4' -bipyridine as mixed ligands. Photo-responsive smart material [ Cd (BCM) ] 0.5 (4,4′‑bipy) 0.5 ]Compared with perfluoro dithienyl vinyl formic acid, the color generation process and the color fading process have better speed, thermal stability and fatigue resistance, and larger application prospect; the distance is significantly minimized and the cyclization and decyclization rates are maximized compared to the same class of complexes. The photoresponse intelligent material can be switched between two discrete states during irradiation, pure white or blue crystals can be selected according to requirements to be presented, and natural blue spar can be well replaced.
Description
Technical Field
The invention belongs to the field of photoresponse metal organic framework compounds, and particularly relates to a photoresponse intelligent material and a preparation method thereof.
Background
The blue natural spar has special magic power and is popular among a plurality of amateurs. First, blue represents a precious color, such as alexandrite, sea vein stone, sea sapphire, etc., which are all valuable. Blue crystals with colors from sky blue to dark blue are coated in pure white crystals, and the crystals are beautiful and rare; secondly, blue is a curing color system, and blue crystallization is used for the adjuvant treatment of depression and insomnia in foreign countries; thus, sapphire is also known as a healed gemstone. The yield of blue-hair crystals is very rare, only brazil is found with such a field, and the exploitation of this ore is very difficult, because of the beautiful shape and magical efficacy of this stone, its popularity is increasing and the demand is also increasing.
Disclosure of Invention
Aiming at the problems of high price, small quantity, difficult exploitation and the like of blue natural spar, the most fundamental way for solving the shortage of supply is replacement, and a cadmium metal organic framework compound constructed on the basis of a mixed ligand of perfluorodithienyl vinyl formic acid and 4,4' -bipyridine is provided and is a photochromic intelligent material. Compared with diarylene or other published similar complexes, the coordinated cadmium metal organic framework complex has better effect or performance in the aspects of the speed of a color generation process and a fading process, thermal stability, fatigue resistance and the like. Attempts to incorporate the photoresponsive material into processes such as necklaces, earrings, brooches have resulted in both increased product aesthetics and a solution to the problem of energy consumption. The crystal can be switched between two discrete states during irradiation, which indicates that the photophysical properties of the material can be adjusted according to the excitation wavelength, and pure white or blue crystals can be selected to be presented according to requirements. For example, it appears pure white in the absence of light or darkness and blue in the sun. The development of stimuli-responsive materials that undergo changes in their physicochemical properties upon exposure to external light stimuli covers the next generation of advances in the art.
The following technical scheme is adopted specifically:
a photoresponsive smart material, said material being [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]Belonging to the orthorhombic Pnna space group, the asymmetric unit of which comprises a crystallographically independent divalent Cd, half of a perfluorodithienyl vinyl formate anion and half of a 4,4' -bipyridine molecule; in a coordination environment, divalent Cd presents a four-corner bipyramid coordination geometric structure, the vertex is respectively provided by nitrogen atoms of two 4,4' -bipyridyl ligands, the basal plane is formed by four oxygen atoms of four perfluoro-dithienyl vinyl formic acid ligands, wherein the distance of Cd-O bonds is
Distance of Cd-N bond of
The coordination mode of the perfluoro-dithienyl vinyl formic acid ligand is a bidentate bridgeBi [ mu ] 4-eta 1: eta 1, the structure of the perfluorodithienyl vinyl formic acid is arranged in an antiparallel conformation with the distance between two activated carbon atoms
(less than
Indication [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]Optically active); the material is a 3-node 2,8-c connection network, and the topological sign of the material is {4 } 2 .6 10 .8 10 .10 6 }{4} 2 {6} 2 。
Among them, there are not few reports of 4,4 '-bipyridyl cobalt, copper, zinc complexes, and perfluoro-dithienyl vinyl formate cobalt, copper, zinc complexes, but a complex formed by assembling perfluoro-dithienyl vinyl formate and 4,4' -bipyridine as ligands and cadmium as metal ions has not been found so far.
The 4,4' -bipyridine is a linear double-base rigid ligand, has no branched chain, less steric hindrance and better bridging effect. The coordination ability of the transition metal ions and the ammonia atom of the 4,4' -bipyridyl is stronger, and the coordination complexes with various spatial structures can be formed. Mainly comprises a linear shape, a zigzag shape, a step shape, a brick wall shape, a square net, a honeycomb shape, a diamond shape and an octahedron shape. The two pyridine rings can rotate around the carbon-carbon single bond between the two pyridine rings at will, so that the diversity of the space structure of the bridged complex is increased. Due to different structures of the complexes, different complex properties are obtained, and the different complex properties inevitably cause different purposes in application. The photochromism of diarylethene derivatives in the single crystalline phase is controlled by the molecular conformation in the crystal. In the perfluoro-dithienyl vinyl formic acid crystal, two isomers with different photoactivity in an antiparallel conformation and a parallel conformation exist at the same time. In the antiparallel conformation, the distance between the activated carbon atoms C1 and C10 is
Enough to cause photocyclization reaction in the crystal. In the photo-inactive parallel conformation, the distance between the activated carbon atoms C18 and C27 is
The ratio of the antiparallel and parallel conformations is 1, so that only 50% of the diarylethene molecules in the crystal can undergo photochromic reactions.
And [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]In the single crystal, the distance between two activated carbon atoms is
The distance between two activated carbon atoms is reduced compared to perfluorodithienyl vinyl formic acid single crystals
And 100% of diarylethene molecules in the crystal can undergo photochromic reaction.
We handle [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]The photoisomerization rates were compared with two other similar complexes. The cyclization rate constants of the three species are obtained, in order of magnitude [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ](8.89×10 -3 mol·L -1 ·s -1 )，[Zn(BCM) 2 (bpfb)](8.37×10 -3 mol·L -1 ·s -1 ),[Zn 2 (BCM) 2 (4,4′-bipy)](8.07×10 -3 mol·L -1 ·s -1 ). Log (A) under visible light irradiation during the decyclization process 1 ) Shows a good linear relation with the irradiation time, and indicates that the decyclization process belongs to a first-order reaction, and the reaction rate constants of the decyclization process are [ Cd (BCM) from large to small 0.5 (4,4′-bipy) 0.5 ](6.20×10 -2 s -1 )，[Zn(BCM) 2 (bpfb)](4.19×10 -2 s -1 )，[Zn 2 (BCM) 2 (4,4′-bipy)](4.99×10 -2 s -1 ). Of the three materials, [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]The cyclization reaction rate of (a) is maximal, and the decyclization reaction rate is also maximal, possibly with crystals thereofThe distance between the two activated carbon atoms of the perfluorodithienylvinylformic acid ligand in the bulk structure is related, compared to the other two materials, [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]Is significantly minimized.
The invention also provides a preparation method of the photoresponse intelligent material, which comprises the following steps:
perfluorodithienyl vinyl formic acid, 4' -bipyridine and Cd (NO) 3 ) 2 ·4H 2 O is dispersed in a dimethylformamide/ethanol/deionized water solution at a molar ratio of 1. Preferably, the transparent bulk crystal is rinsed 3 times with dimethylformamide and ethanol.
The invention has the beneficial effects that:
(1) Photo-responsive smart material [ Cd (BCM) ] 0.5 (4,4′-bipy) 0.5 ]Compared with perfluoro-dithienyl vinyl formic acid, the cadmium metal organic framework compound after coordination has better speed, thermal stability (the thermal stability is still kept at the high temperature of 350 ℃) and fatigue resistance (the absorption strength is basically not influenced after continuous 25 reversible cycles) in the color generation process and the color fading process, and has larger application prospect.
(2) Photo-responsive smart material [ Cd (BCM) ] 0.5 (4,4′-bipy) 0.5 ]The structure of perfluorodithienylethenecarboxylic acid in (1) is arranged in an antiparallel conformation, and the distance between two activated carbon atoms is less than
The distance between two activated carbon atoms is reduced compared to perfluorodithienylvinylformic acid single crystals
And 100% of diarylethene molecules in the crystal can have photochromic reaction; compared with the same complex, [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]Is obviously minimized and the cyclization reaction rate is maximized, as well asThe rate of the decyclization reaction is also maximal.
(3) Photo-responsive smart material [ Cd (BCM) ] 0.5 (4,4′-bipy) 0.5 ]The crystal can be switched between two discrete states during irradiation, the photophysical properties of the material can be adjusted according to the excitation wavelength, pure white or blue crystal can be selected according to requirements to be presented, and natural blue spar can be well replaced.
Drawings
FIG. 1 is a diagram showing the synthetic scheme of ligand perfluorodithienyl vinyl formate;
FIG. 2 shows [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]A synthetic scheme for crystalline materials;
FIG. 3 shows [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]The crystal structure of (1);
FIG. 4 shows [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]Thermogram of (a);
FIG. 5 shows [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]An infrared spectrum of (1);
FIG. 6 shows [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]Powder X-ray diffraction pattern of (a);
FIG. 7 shows [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]And a solid photochromic plot of a perfluorodithienyl vinyl formate ligand;
FIG. 8 shows [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]And a photochromic pattern of a perfluorodithienyl vinyl formate ligand in methanol solution;
FIG. 9 shows [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]And photoisomerization rate profile of the same complex in methanol saturated solution.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments and the accompanying drawings to fully understand the objects, aspects and effects of the present invention.
Example 1:
(1) Synthesis of ligand perfluorodithienyl vinyl formic acid
The synthetic route is shown in figure 1. Accurately weighed 1 (15.13g, 120mmol) was placed in a 250mL single-neck flask, 120.0mL of glacial acetic acid was added and stirred, and Br was measured in a measuring cylinder 2 (9.0 mL, 132mmol) was added slowly dropwise over a constant pressure titration funnel in an ice bath for about 2h with complete Br addition 2 Then keeping the reaction for 12h, adding a proper amount of water to stop the reaction after the reaction is finished, and passing through Na 2 CO 3 Adjusting the reaction liquid to be neutral, adding 120.0mL of multiplied by 3 dichloromethane for extraction, combining organic phases, washing with supersaturated salt water, drying with anhydrous sodium sulfate, carrying out reduced pressure rotary evaporation, removing the solvent, and carrying out silica gel column chromatography, wherein an eluent is pure petroleum ether for separation, and a product 2 is a light yellow solid (13.02 g, yield: 53.57%), and structural analysis of a target product is as follows: 1 H NMR(400MHz，DMSO-d 6 )δ(ppm)：9.81(s，1H)，8.01(s，1H)，2.47(s，3H)。
accurately weighing 2 (3.06g, 15mmol) and adding into a 250.0mL single-neck bottle, 3.0mL ethylene glycol, p-toluenesulfonic acid (0.056g, 0.03mmol) as a catalyst, toluene as a solvent, raising the temperature to 130 ℃, keeping the temperature, and separating H generated in the process by a water separator 2 O is separated out and 3.0mL of H is produced by 10mmol of material 2 The general rule of O is to judge whether the reaction is complete, 3 is an intermediate product, the aldehyde group protection stability is poor, the process is not further purified, and the next reaction is directly carried out after the reaction is finished.
3 was dissolved in 120.0mL of purified anhydrous tetrahydrofuran under an argon atmosphere at a low temperature of-78 ℃ and placed in a 250.0mL three-necked flask. Injecting n-butyllithium (7.0mL and 169mol) through a syringe, continuously adding liquid nitrogen during the reaction process to keep reacting at a low temperature for 0.75h, weighing perfluorocyclopentene (1.2mL and 9mmol) to be dissolved in 15.0mL refined tetrahydrofuran, dropwise adding the solution into a reaction system through a constant-pressure titration funnel to react for 3h, detecting and tracking the reaction through TLC (thin-layer chromatography), adding a proper amount of deionized water to terminate the reaction after the reaction is completed, carrying out reduced-pressure rotary evaporation, adding 120.0mL of multiplied by 3 dichloromethane to extract, combining organic phases, washing with supersaturated saline water, drying with anhydrous sodium sulfate, carrying out reduced-pressure rotary evaporation, taking petroleum ether and ethyl acetate (v: v = 20)Body 1.55g, yield: 20.23 percent. 1 HNMR(400MHz，DMSO-d 6 )δ(ppm)：6.79(s，2H)，6.07(s，2H)，3.85(d，4H)，3.75(d，4H)，2.36(s，6H)。
Taking 4 (1.5g, 3mmol) to 250.0mL of a single-neck flask, dissolving in 120.0mL of acetone and 30.0mL of water, using p-toluenesulfonic acid (1.66g, 8.7mmol) as a catalyst, heating to 80 ℃, stirring and refluxing, reacting for 12h, tracing the reaction by TLC detection, after the reaction is completed, carrying out reduced pressure rotary evaporation, adding 120.0mL × 3 dichloromethane for extraction, combining organic phases, washing with supersaturated saline, drying with anhydrous sodium sulfate, carrying out reduced pressure rotary evaporation, using petroleum ether and ethyl acetate (v: v = 20) as eluents, carrying out separation and purification by silica gel column, and yielding 1.12g of 5 blue solid matter, yield: 88.21 percent. 1 HNMR(400MHz，DMSO-d 6 )δ(ppm)：9.90(s，1H)，8.12(s，1H)，2.03(s，3H)。
Accurately weighing a compound 5 (1.12g, 2.64mmol), dissolving in acetone, pouring into a single-neck flask, stirring in an ice-water bath environment, gradually dropping a Jones reagent, changing the solution from blue to orange, then changing the solution to green, detecting and tracking the reaction by TLC, after the reaction is finished, carrying out reduced pressure rotary evaporation, adding trichloromethane and a water solution, carrying out suction filtration, and drying in an oven for 5 hours to obtain 1.13g of 6 light-green solid powder, wherein the yield is 91.17%. 1 H NMR(400MHz，DMSO-d 6 )，δ(ppm)：13.45(s，1H)，7.69(s，1H)，1.97(s，3H)。 13 C NMR(DMSO-d 6 ，100MHz)，161.85，148.64，135.80，133.16，132.18，124.41。
(2)[Cd(BCM) 0.5 (4,4′-bipy) 0.5 ]Preparation of crystalline materials
The synthetic route is shown in FIG. 2, and the 4,4-bipyridine ligand is purchased from Tech technologies, inc. of Yinakai, beijing. Fluorodithienylvinylformic acid (9.13mg, 0.02mmol), 4-bipyridine (3.12mg, 0.02mmol) and Cd (NO) 3 ) 2 ·4H 2 O (6.20mg, 0.02mmol) was dispersed in a 2.0mL solution of dimethylformamide/ethanol/deionized water (v: v: v = 1.5. Filtering to obtain colorless transparent block crystals, and adding dimethyl formamideThe amide and ethanol were washed 3 times, yield 87.0%. Calcd: c 27 H 16 CdF 6 N 2 O 4 S 2 。C，45.00；H，2.10；N，3.90％。found：C，44.85；H，2.09；N，3.87％。
Example 2:
[Cd(BCM) 0.5 (4,4′-bipy) 0.5 ]experimental profile analysis of crystalline material:
(1) The single crystal data were measured at room temperature using a Bruker SMART APEX II single crystal diffractometer. And refined by SHELX-2014 program and full matrix least square method, and all non-hydrogen atoms are refined anisotropically. During refinement, disordered guest molecules were removed by using the SQUEEZE program in PLATON.
As shown in FIG. 3, it can be seen that [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]Belonging to the orthorhombic Pnna space group, the asymmetric unit of which comprises a crystallographically independent Cd (II), half of a perfluorodithienyl vinyl formate anion and half of a 4, 4-bipyridine molecule. In a coordination environment, cd (II) presents a tetragonal bipyramidal coordination geometry structure, vertexes are respectively provided by nitrogen atoms of two 4, 4-bipyridyl ligands, a basal plane is formed by four oxygen atoms of four perfluoro-dithienyl vinyl formic acid ligands, and the distance of Cd-O bonds is within the range of
Range, distance of Cd-N bond
The perfluorodithienyl vinyl formate ligand only adopts one coordination mode: the bidentate bridge is mu 4-eta 1: eta 1. The structure of perfluorodithienylvinylformic acid is arranged in an antiparallel conformation with the distance between two activated carbon atoms being
Is less than
Indication [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]Has optical activity.
(2) The thermal stability was analyzed using a Netzsch STA 449C thermal analyzer heated from room temperature to 800 ℃ using a heating rate of 20 ℃/min in an air atmosphere. Approximately 4mg of the solid sample was weighed into a ceramic crucible for testing. Specific results are shown in FIG. 4, and experiments show that [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]The thermogravimetric curve of (a) shows a weight loss of 8.73% before 330 ℃, mainly due to the loss of free solvent molecules in the channels, with the breakdown of the ligands as the temperature increases, the framework structure of the crystals begins to collapse and eventually breaks down into the metal oxide CdO.
(3) Tabletting with dried KBr and recording of perfluorodithienylvinylformic acid and [ Cd (BCM) on a Bruker Vertex-70 Fourier transform Infrared spectrometer 0.5 (4,4′-bipy) 0.5 ]Wave number range of 4000-400cm -1 An infrared spectrum of (1). As shown in FIG. 5, at a wave number of 3438cm -1 And 1686cm -1 The strong absorption peak can be attributed to upsilon of perfluoro-dithienyl vinyl formic acid ligand O-H And upsilon C＝O And (5) stretching and vibrating. Due to the presence of [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]In the method, the perfluoro-dithienyl vinyl formic acid adopts a bidentate bridging coordination mode, so that the concentration of the perfluoro-dithienyl vinyl formic acid is 1680cm -1 No v was observed in the vicinity C＝O A stretching vibration peak.
(4) Powder X-ray diffraction (PXRD) characterization was performed on a Shimadzu Lab Xrd-6100X-ray diffractometer using Cu radiation at room temperature in the 2 θ range of 5-60 ℃ to determine the purity of the sample and whether the crystal structure was altered. [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]PXRD results of (5) shows the spectrum of the experimental synthetic sample [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]-o (red), [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]The agreement between-c (black) and PXRD pattern (blue) simulated by Mercury single crystal data (as shown in FIG. 6) is good, which indicates that the synthesized crystal [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]Has high phase purity, although 2 theta is between 15-17 deg.C, [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]-o and [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]C there is a difference in diffraction peak height, which is suspected to be related to a slight change in the crystallographic plane between open and closed rings. However, the diffraction peak positions were substantially the same, and [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]The optical cyclization from open to closed loop still maintains its structural integrity.
(5) Using Agilent 8453 for [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ](FIG. 7 a) and perfluorodithienylvinylcarboxylic acid (FIG. 7 b) by irradiation with SHG-200 UV lamp and BMH-250 visible lamp. The UV power was set to 1.604X 10 by filtering with a 313nm filter -4 W, visible light power is set to 1.975X 10 - 4 W. Perfluorodithienylvinylformic acid and [ Cd (BCM) were performed at room temperature 0.5 (4,4′-bipy) 0.5 ]Testing photochromic behavior in solid state. First, [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]O A distinct absorption peak at 320nm, and a broad and flat absorption peak at 700nm, which is not characteristic of the ring-opened isomers of diarylethene molecules, was observed, as evidenced by its photochromic behavior in methanol solution. After 313nm ultraviolet irradiation, a new absorption peak appears at 600nm, the absorption peak at 600nm gradually rises with the prolonging of the irradiation time, and finally reaches saturation, and the color changes from original colorless to blue, which is attributed to the occurrence of photocyclization reaction and ring-opening isomer [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]O becomes a closed ring isomer [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]-c is the structure of. After saturation, visible light (lambda) passes through>500 nm) was irradiated, the absorption peak and the color were restored to the initial values, indicating that [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]Has good photochromic property.
As shown in FIG. 7b, the absorption maximum of the ring-opened isomer (perfluorodithienylvinylformic acid-o) occurs at 320nm. Under 297nm, a new visible absorption band appeared at 615nm, changing the color from colorless to blue, due to photoisomerization of the ring-opened isomer (perfluorodithienylethenecarboxylic acid-o) to the ring-closed isomer (perfluorodithienylethenecarboxylic acid-c). The absorption spectrum and the color are recovered after the irradiation of visible light (lambda is more than 500 nm), which shows that the perfluoro dithienyl vinyl formic acid-c is photoisomerized back to the perfluoro dithienyl vinyl formic acid-o, and an equal absorption point is observed at 350 nm.
(6) Using Agilent 8453 for [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ](FIG. 8 a) and perfluorodithienylethenecarboxylic acid (FIG. 8 b) in methanol solution. The concentration of perfluorodithienyl vinyl formic acid is 2X 10 - 5 mol/L，[Cd(BCM) 0.5 (4,4′-bipy) 0.5 ]Is the saturation concentration. The light irradiation was carried out using an SHG-200 ultraviolet lamp and a BMH-250 visible lamp. The UV power was set to 1.604X 10 with 297nm filter -4 W, visible light power is set to 1.975X 10 -4 W is added. The UV absorption band of perfluorodithienylvinylcarboxylic acid-o (20. Mu.M) appears clearly at 250nm, which is attributable to the π - π transition. Then, under 297nm ultraviolet irradiation, the absorption spectrum of perfluorodithienylethenecarboxylic acid changed significantly. A new absorption peak appeared at 581nm, changing the color from colorless to blue, indicating that the ring-opened isomer perfluorodithienylethenecarboxylic acid-o underwent cyclization to form the ring-closed isomer perfluorodithienylethenecarboxylic acid-c structure (FIG. 8 b). Similarly, [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]A clear absorption band at 250nm in methanol solution was shown. Under 297nm uv irradiation, a new absorption band appears at 580nm and the colorless solution turns blue (fig. 8 a). Accordingly, when perfluorodithienylethenecarboxylic acids-c and [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]C visible light (lambda) for the solution>500 nm), their absorption spectra and colors can be restored to the original state. [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]The wavelength of maximum absorption in methanol solution is different from that of solid, which may be due to solvent effect or crystal stacking. The above experimental phenomena clearly show that the compounds perfluorodithienylethenecarboxylic acid and [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]Has reversible and consistent photochromic characteristics. More evidence [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]Photochromic of (2)Derived from a perfluorodithienyl vinyl formate ligand.
(7) Using Agilent 8453 for [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]And ultraviolet-visible absorption spectrum of the same complex in methanol saturated solution. By alternately irradiating ultraviolet/visible light, the photoisomerization kinetic rates of the three materials in methanol saturated solution were studied. As shown in FIG. 9a, under 297nm of ultraviolet light irradiation, it can be clearly seen that the absorbance and the irradiation time show a better linear relationship, and the linear correction factors are all greater than 0.99, which indicates that the photochromic cyclization reaction of the three materials is a zero-order reaction, and the slope is a rate constant, according to the method, the cyclization rate constants of the three materials are obtained, and the sizes of the constants are [ Cd (BCM) in sequence) 0.5 (4,4′-bipy) 0.5 ](8.89×10 -3 mol·L -1 ·s -1 )，[Zn(BCM) 2 (bpfb)](8.37×10 - 3 mol·L -1 ·s -1 ),[Zn 2 (BCM) 2 (4,4′-bipy)](8.07×10 -3 mol·L -1 ·s -1 ). Under visible light irradiation during the deringing process, as shown in FIG. 9b, log (A) 1 ) Shows a good linear relation with the irradiation time, and indicates that the decyclization process belongs to a first-order reaction, and the reaction rate constants of the decyclization process are [ Cd (BCM) from large to small 0.5 (4,4′-bipy) 0.5 ](6.20×10 -2 s -1 )，[Zn(BCM) 2 (bpfb)](4.19×10 -2 s -1 )，[Zn 2 (BCM) 2 (4,4′-bipy)](4.99×10 -2 s -1 ). Of the three materials, [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]The cyclization reaction rate of (a) is maximized, while the decyclization reaction rate is maximized, possibly related to the distance between two activated carbon atoms of the perfluorodithienyl vinyl formate ligand in its crystal structure, compared to the other two materials, [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]Is significantly minimized.
The above description is only a preferred embodiment of the present invention, and the present invention is not limited to the above embodiment, and the present invention shall fall within the protection scope of the present invention as long as the technical effects of the present invention are achieved by the same means. The invention is capable of other modifications and variations in its technical solution and/or its implementation, within the scope of protection of the invention.
Claims (5)
1. A photo-responsive smart material, characterized in that said material is [ Cd (BCM) 0.5 (4,4′-bipy) 0.5 ]Belongs to an orthorhombic Pnna space group, and an asymmetric unit of the Pnna space group comprises a crystallographically independent divalent Cd, a half of perfluorodithienyl vinyl formate anion and a half of 4,4' -bipyridine molecule;
the preparation method of the photoresponse intelligent material comprises the following steps of:
perfluorodithienyl vinyl formic acid, 4' -bipyridine and Cd (NO) 3 ) 2 ·4H 2 O is dispersed in a dimethylformamide/ethanol/deionized water solution at a molar ratio of 1.
2. The photo-responsive smart material of claim 1 wherein in a coordination environment, divalent Cd assumes a four-corner bipyramidal coordination geometry with vertices provided by nitrogen atoms of two 4,4' -bipyridyl ligands, respectively, and basal planes consisting of four oxygen atoms of four perfluorodithienyl vinyl formate ligands.
3. The photo-responsive smart material of claim 2, wherein the distance of Cd-O bonds is 2.267-2.286 a, the distance of Cd-N bonds is 2.325 a, the coordination mode of the perfluorodithienyl vinyl formate ligand is bidentate bridging μ 4-414a 1: 414, the structure of the perfluorodithienyl vinyl formate is arranged in a antiparallel conformation, the distance between two active carbon atoms is 3.490 a.
4. The optically responsive smart material of claim 1 wherein the material is a 3-node 2,8-c connected network having a topological sign of {4 } ™ 2 .6 10 .8 10 .10 6 }{4} 2 {6} 2 。
5. The photo-responsive smart material of claim 1 wherein the transparent bulk crystal is rinsed 3 times with dimethylformamide and ethanol.
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