CN104610296A - Zinc triiodo phenylamine phthalic acid complex used as potential fluorescent material and preparation method thereof - Google Patents

Zinc triiodo phenylamine phthalic acid complex used as potential fluorescent material and preparation method thereof Download PDF

Info

Publication number
CN104610296A
CN104610296A CN201510088016.7A CN201510088016A CN104610296A CN 104610296 A CN104610296 A CN 104610296A CN 201510088016 A CN201510088016 A CN 201510088016A CN 104610296 A CN104610296 A CN 104610296A
Authority
CN
China
Prior art keywords
pta
phthalic acid
amine
triazole
phenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510088016.7A
Other languages
Chinese (zh)
Inventor
王英
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin Normal University
Original Assignee
Tianjin Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin Normal University filed Critical Tianjin Normal University
Priority to CN201510088016.7A priority Critical patent/CN104610296A/en
Publication of CN104610296A publication Critical patent/CN104610296A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18Metal complexes
    • C09K2211/188Metal complexes of other metals not provided for in one of the previous groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention discloses a zinc triiodo phenylamine phthalic acid complex used as a potential fluorescent material and a preparation method thereof, wherein the structural motif of the zinc triiodo phenylamine phthalic acid complex {[Zn(L)2(pta).(H2O)0.5} (1) is as shown in the figure 1. The invention further discloses the preparation method of {[Zn(L)2(pta).(H2O)0.5} (1) (L=tri(4-triazolephenyl) amine, pta= phthalic acid). According to a solvothermal method, L, Zn(Ac)2.2H2O, pta and water react for three days at 140 DEG C and then the reaction product is slowly cooled to room temperature to obtain yellow rodlike crystals suitable for X-ray single crystal diffraction. The invention further discloses an application of the zinc triiodo phenylamine phthalic acid complex {[Zn(L)2(pta).(H2O)0.5} (1) (L= tri(4-triazolephenyl) amine, pta= phthalic acid) as a potential fluorescent material.

Description

Phenyl triiodide amine phthalic acid Zn complex with potential fluorescent material and preparation method thereof
The present invention obtains state natural sciences fund general project (21471113), young top-notch personnel's support plan, Tianjin Education Commission general project (20140506), Tianjin Normal University Middl-age and youth faculty Academic innovations advance planning item (52XC1401), the subsidy of Tianjin State Scientific and Technological Commission general project (11JCYBJC03600) and Tianjin innovation team of institution of higher education training plan (TD12-5038).
Technical field
The invention belongs to organic and Inorganic synthese technical field, relate to phenyl triiodide amine three triazole phthalic acid Zn complex { [Zn (L) (pta)] (H 2o) 0.5( 1) preparation method of (L=tri-(4-triazole phenyl) amine, pta=phthalic acid) and the application as potential fluorescent material.
Background technology
1,2,4-triazole and derivative thereof have the coordination feature of pyrazoles and imidazoles concurrently, are the bridgingligands that coordination ability is stronger, have synthesized at present and have characterized a large amount of monokaryons, multinuclear and multidimensional compound.These parts can with 1, nitrogen-atoms on 2 and metallic ion coordination form N1, N2-bridging pattern, for 4 unsubstituted 1,2,4-triazole derivative is by 2, nitrogen-atoms on 4 forms N2, N4-bridging pattern, this N2, N4-bridging pattern is with the N1 of imidazoles in metalloenzyme, and N3-bridging mode class seemingly.Special purpose for triazole class compounds also shows in the design of molecular device, and the metal complexes that synthesis has different dimension has been the vital step of device.
The present invention adopts " solvent-thermal method ", i.e. L, Zn (Ac) 22H 2o, pta and water are 140 ounder C, reaction is slowly down to room temperature in three days afterwards, obtains yellow rhabdolith { [Zn (L) (pta)] (H of applicable X-ray single crystal diffraction after driving still 2o) 0.5( 1) (L=tri-(4-triazole phenyl) amine, pta=phthalic acid).This title complex also can be used as potential fluorescent material aspect and is applied.
Summary of the invention
Another object of the present invention is to provide a kind of phenyl triiodide amine three triazole phthalic acid Zn complex { [Zn (L) (pta)] (H 2o) 0.5( 1) (L=tri-(4-triazole phenyl) amine, pta=phthalic acid) monocrystalline and preparation method thereof.
Current inventor provides following technical scheme for this reason:
Phenyl triiodide amine three triazole phthalic acid Zn complex { [Zn (L) (pta)] (H 2o) 0.5( 1) (L=tri-(4-triazole phenyl) amine, pta=phthalic acid) structural motif as shown in Figure 1.
The present invention further discloses phenyl triiodide amine three triazole phthalic acid Zn complex { [Zn (L) (pta)] (H 2o) 0.5( 1) (L=tri-(4-triazole phenyl) amine, pta=phthalic acid) monocrystalline, it is characterized in that this single crystal structure adopts APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (λ=0.71073) be incident radiation, with ω-2 θscan mode collects point diffraction, obtains unit cell parameters, utilize SHELXL-97 direct method to solve single crystal data from difference Fourier electron density map through least-squares refinement:
Table 1. title complex 1crystallographic data
Phenyl triiodide amine three triazole phthalic acid Zn complex { [Zn (L) (pta)] (H of the present invention 2o) 0.5( 1) preparation method of (L=tri-(4-triazole phenyl) amine, pta=phthalic acid) monocrystalline, its feature adopts " solvent-thermal method ", i.e. L, Zn (Ac) in employing 22H 2o, pta and water are 140 ounder C, reaction is slowly down to room temperature in three days, afterwards to prepare this title complex after driving still
L pta。
The present invention's preferred example:
Three (4-triazole phenyl) amine) preparation of (L)
Adopt " one kettle way " at polar solvent, three (4-phenyl-iodide) amine, 1H-1,2,4-triazole, salt of wormwood and cupric oxide are prepared in a heated condition; Wherein three (4-phenyl-iodide) amine: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:15:30:1;
three (4-phenyl-iodide) amine 1H-1,2,4-triazole
The present invention is three (4-phenyl-iodide) amine: 1H-1,2,4-triazole preferably: salt of wormwood: the mol ratio of cupric oxide is 2:15:30:1; Temperature of reaction 80-200 DEG C, reaction times 12-120 hour.In polar solvent, adopt " one kettle way ", three (4-phenyl-iodide) amine, 1H-1,2,4-triazole, salt of wormwood and cupric oxide are prepared this organic compound in a heated condition;
Another preferred embodiment of the present invention
Three (4-triazole phenyl) amine) (L) (0.1 mmol), Zn (Ac) 22H 2o (0.2 mmol), pta (0.1 mmol) and H 2o (10 mL), is put in 23 mL water heating kettles, and 140 oc heats and is slowly down to room temperature afterwards in three days, obtains the yellow rhabdolith of applicable X-ray single crystal diffraction after driving still.Productive rate: 20%.Ultimate analysis (C 32h 23n 10o 4.5zn) theoretical value (%): C, 56.11; H, 3.38; N, 20.45.Measured value: C, 56.19; H, 3.39; N, 20.49.
The present invention further discloses phenyl triiodide amine three triazole phthalic acid Zn complex { [Zn (L) (pta)] (H 2o) 0.5( 1) (L=tri-(4-triazole phenyl) amine, pta=phthalic acid) can be used as potential fluorescent material aspect and applied.
A kind of phenyl triiodide amine three triazole phthalic acid Zn complex { [Zn (L) (pta)] (H disclosed by the invention 2o) 0.5( 1) advantage and disadvantage that has of (L=tri-(4-triazole phenyl) amine, pta=phthalic acid) monocrystalline is:
(1) operation is simple and easy to do.
(2) reaction yield is high, and the purity of products obtained therefrom is high.
(3) { [Zn (L) (pta)] (H prepared by the present invention 2o) 0.5( 1) (L=tri-(4-triazole phenyl) amine, pta=phthalic acid) production cost is low, method is easy, is applicable to scale operation.
Accompanying drawing explanation
Fig. 1: title complex 1crystalline structure primitive figure;
Fig. 2: title complex 1two-dimensional layered structure figure.
Embodiment
Below in conjunction with embodiment, the present invention is described further, and embodiment is only indicative, never means that it limits the scope of the invention by any way.Raw materials used three (4-phenyl-iodide) amine, 1H-1,2,4-triazole, salt of wormwood and cupric oxide etc. all have commercially available.All raw materials are all buy from chemical reagents corporation both domestic and external, through continuation purify but directly use.
Embodiment 1
Three (4-phenyl-iodide) amine: 1H-1,2,4-triazole: salt of wormwood: the mol ratio of cupric oxide is 2:15:30:1
CuO (0.5 mmol), salt of wormwood (15 mmol), 1H-1 is added respectively in 50 mL, tri-mouthfuls of round-bottomed flasks that magneton, reflux exchanger and thermometer are housed, 2,4-triazole (5 mmol), three (4-phenyl-iodide) amine (1 mmol) and 20 mL DMF.Start and be stirred in 150 oc, reacts 60 hours.After reaction terminates, reaction solution is down to room temperature, filter, filtrate adds 100 mL water, separates out and precipitates in a large number, suction filtration, collects filter cake, three (4-triazole phenyl) amine (L).Yield 78.3%.
Embodiment 2
Three (4-triazole phenyl) amine) (L) (0.1 mmol), Zn (Ac) 22H 2o (0.2 mmol), pta (0.1 mmol) and H 2o (10 mL), is put in 23 mL water heating kettles, and 140 oc heats and is slowly down to room temperature afterwards in three days, obtains the yellow rhabdolith of applicable X-ray single crystal diffraction after driving still.Productive rate: 20%.Ultimate analysis (C 32h 23n 10o 4.5zn) theoretical value (%): C, 56.11; H, 3.38; N, 20.45.Measured value: C, 56.19; H, 3.39; N, 20.49.
Embodiment 3
Crystal structure determination adopts APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (λ=0.71073) be incident radiation, with ω-2 θscan mode collects point diffraction, obtains unit cell parameters, utilize software to solve crystalline structure from difference Fourier electron density map through least-squares refinement, and through Lorentz lorentz and polarizing effect correction.All H atom are synthesized by difference Fourier and are determined through desirable position calculation.Detailed axonometry data are in table 1.Structural motif is shown in Fig. 1, and two-dimensional layered structure is shown in Fig. 2.
Table 1. title complex 1crystallographic data
Embodiment 4
The concrete instance that dyestuff or luminous agent use
Method: PARSTAT 2273 electrochemical workstation of differentiated pulse volt-ampere (DPV) the curve negotiating Princeton Applied Research Laboratory development of dye solution is measured.The DPV test of solution adopts three-electrode system, and glass-carbon electrode is working electrode, and supporting electrode is platinum plate electrode, homemade Ag/AgNO 3electrode is reference electrode; Electrolytic solution is the acetonitrile solution of 0.1molL-1TBAP.Reduce reversible point to for interior mark with Oxidation of Ferrocene, obtains the correction value between test system and standard hydrogen electrode system.
Monochromatic incident light photoelectric transformation efficiency (IPCE) describes the photoelectric transformation efficiency of DSCs under monochromatic ray effect, is transfer to the electronic number of external circuit and the ratio of incident light subnumber.During measurement, use 500 W xenon lamps as light source, the monochromatic ray of incident light under the multifunctional assembled grating spectrograph of WDS-5 type obtains different wave length λ; Monochromatic light exposure, in the light anode of battery, reads current value I by Keithley2400 digital sourcemeter.Monochromatic good fortune illumination is measured by USB4000 plug-and-play Miniature optical linear light spectrometer.
Step: in order to definitely understand dyestuff at TiO 2adsorptive capacity on film, by dye sensitization TiO 2(geometric area is about 1 cm to nanometer crystal film 2) be immersed in 10 mL 0.01 molL -1sodium hydroxide methanol solution in spend the night, treat that the absorbancy of attached mensuration solution separated completely by dyestuff.Wash one's face and rinse one's mouth according to absorbancy and molar absorptivity and can calculate the adsorptive capacity of dyestuff on unit surface nanometer crystal film.The adsorptive capacity of this title complex is 5.9 × 10 -4mol/cm 2.
Result: compared with the methanol solution of dyestuff, dyestuff is at TiO 2absorption spectrum on film all obviously broadens and red shift.This shows that dye molecule is at TiO 2define the J-aggregate of first also tail.From the principle of work of DSCs, the spectrum broadening that dye aggregation causes and red shift are very favourable for the widening of photoelectric response scope of dyestuff.But meanwhile, dye aggregation cognition reduces its electron injection efficiency greatly, thus causes the degraded performance of DSCs.So, in dye solution, usually add coadsorbent to suppress the gathering of dyestuff.This title complex is in methanol solution and at TiO 2the fluorometric investigation of the purple solution on membrane electrode adopts 2.5 × 10 -5the methanol solution of mol/L, maximum emission wavelength is positioned at 575 nm.
After the preferred embodiment described in detail, be familiar with this technology personage can be well understood to, do not departing under above-mentioned claim and spirit and can carry out various change and amendment, all above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all belong to the scope of technical solution of the present invention.And the present invention is not also by the restriction of example embodiment in specification sheets.

Claims (4)

1. phenyl triiodide amine three triazole phthalic acid Zn complex { [Zn (L) (pta)] (H 2o) 0.5( 1) structural motif as shown in Figure 1:
L=tri-(4-triazole phenyl) amine, pta=phthalic acid.
2. the monocrystalline of phenyl triiodide amine three triazole phthalic acid Zn complex described in claim 1, it is characterized in that this single crystal structure adopts APEX II CCD single crystal diffractometer, use through graphite monochromatised Mok alpha-ray (λ=0.71073) be incident radiation, with ω-2 θscan mode collects point diffraction, obtains unit cell parameters, utilize software to solve single crystal data from difference Fourier electron density map through least-squares refinement:
Table 1. title complex 1crystallographic data
3. phenyl triiodide amine three triazole phthalic acid Zn complex { [Zn (L) (pta)] (H described in claim 1 2o) 0.5( 1) preparation method of (L=tri-(4-triazole phenyl) amine, pta=phthalic acid), it is characterized in that it adopts " solvent-thermal method ", i.e. L, Zn (Ac) 22H 2o, pta and water are 140 ounder C, reaction is slowly down to room temperature in three days afterwards, drives still to prepare this title complex
L pta。
4. phenyl triiodide amine three triazole phthalic acid Zn complex { [Zn (L) (pta)] (H described in claim 1 2o) 0.5( 1) (L=tri-(4-triazole phenyl) amine, pta=phthalic acid) as the application of potential fluorescent material aspect.
CN201510088016.7A 2015-02-26 2015-02-26 Zinc triiodo phenylamine phthalic acid complex used as potential fluorescent material and preparation method thereof Pending CN104610296A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510088016.7A CN104610296A (en) 2015-02-26 2015-02-26 Zinc triiodo phenylamine phthalic acid complex used as potential fluorescent material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510088016.7A CN104610296A (en) 2015-02-26 2015-02-26 Zinc triiodo phenylamine phthalic acid complex used as potential fluorescent material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN104610296A true CN104610296A (en) 2015-05-13

Family

ID=53144974

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510088016.7A Pending CN104610296A (en) 2015-02-26 2015-02-26 Zinc triiodo phenylamine phthalic acid complex used as potential fluorescent material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104610296A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106124466A (en) * 2016-06-16 2016-11-16 陕西师范大学 The application in detection aniline of the p-phthalic acid europium fluorescent probe containing 1 ethyl 3 Methylimidazole.

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102276658A (en) * 2011-06-13 2011-12-14 天津师范大学 Mixed ligand cobalt (II) coordination compound as well as preparation method and application thereof
CN104193691A (en) * 2014-09-11 2014-12-10 南京农业大学 Synthesis methods of tri-(4-triazolyl phenyl) amine and tri-(4-triazolyl phenyl)amine cadmium complex

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102276658A (en) * 2011-06-13 2011-12-14 天津师范大学 Mixed ligand cobalt (II) coordination compound as well as preparation method and application thereof
CN104193691A (en) * 2014-09-11 2014-12-10 南京农业大学 Synthesis methods of tri-(4-triazolyl phenyl) amine and tri-(4-triazolyl phenyl)amine cadmium complex

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
苗少斌: "基于1,2,4-三氮唑配体的配位聚合物的合成、结构和性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106124466A (en) * 2016-06-16 2016-11-16 陕西师范大学 The application in detection aniline of the p-phthalic acid europium fluorescent probe containing 1 ethyl 3 Methylimidazole.

Similar Documents

Publication Publication Date Title
CN104610302A (en) Antharcycline bis-triazole terephthalic acid zinc complex with potential fluorescent material and preparation method of antharcycline bis-triazole terephthalic acid zinc complex
CN104592267A (en) Cadmium naphthalene bis(triazolyl) isophthalate complex used as potential fluorescent material and preparation method of cadmium naphthalene bis(triazolyl) isophthalate complex
CN104592262A (en) Zinc anthracene cyclo-bis(triazolyl) isophthalate complex used as potential fluorescent material and preparation method of zinc anthracene cyclo-bis(triazolyl) isophthalate complex
CN104610315A (en) Cadmium oxyether bistriazol isophthalate complex with potential fluorescent material and preparation method of complex
CN104610320A (en) Fluorescent material containing tetraphenylethylene-4-triazole three-dimensional cadmium complex and preparation method thereof
CN104557991A (en) Oxyether bistriazole zinc chloride complex with potential fluorescent material and preparation method thereof
CN104610287B (en) Two triazole one-dimensional copper title complex of oxygen ether with potential fluorescent material and preparation method thereof
CN104610299A (en) Zinc naphthalene bistriazole terephthalic acid complex used as potential fluorescent material and preparation method thereof
CN104557992A (en) Naphthalene bistriazole trimesinic acid cadmium complex with potential fluorescent material and preparation method thereof
CN104592270A (en) Cadmium isophthalate anthracene cyclo-bis(triazolyl) nitrate complex used as potential fluorescent material and preparation method of cadmium isophthalate anthracene cyclo-bis(triazolyl) nitrate complex
CN104610321A (en) Tetraphenyl ethylene four triazole terephthalic acid cadmium complex with potential fluorescent material and preparation method thereof
CN104610322A (en) Tetraphenyl ethylene tetratriazolyl cadmium acetate complex with potential fluorescent material and preparation method thereof
CN104610313A (en) Oxy-ether-bis(triazole) cadmium complex with potential fluorescent materials and preparation method thereof
CN104592266B (en) Two triazole cadmium nitrate title complex of oxygen ether with potential fluorescent material and preparation method thereof
CN104592265A (en) Cadmium phthalate anthracene cyclo-bis(triazolyl) complex used as potential fluorescent material and preparation method of cadmium phthalate anthracene cyclo-bis(triazolyl) complex
CN104592272A (en) Cadmium tetraphenyl ethylene-tetra(triazolyl) bromide complex used as potential fluorescent material and preparation method of cadmium tetraphenyl ethylene-tetra(triazolyl) bromide complex
CN104610307A (en) Zinc oxyether bistriazol acetate complex with potential fluorescent material and preparation method of complex
CN104610319A (en) Tetraphenylethylene 4-triazole cadmium perchlorate complex with potential fluorescence material and preparation method of tetraphenylethylene 4-triazole cadmium perchlorate complex
CN104610298B (en) Two triazole zinc nitrate title complex of oxygen ether with potential fluorescent material and preparation method thereof
CN104610296A (en) Zinc triiodo phenylamine phthalic acid complex used as potential fluorescent material and preparation method thereof
CN104610303A (en) Zinc triiodo phenylamine tri-triazole terephthalic acid complex used as potential fluorescent material and preparation method thereof
CN104610301A (en) Naphthaline bis-triazole m-phthalic acid zinc complex serving as potential fluorescent material and preparation method of naphthaline bis-triazole m-phthalic acid zinc complex
CN104610344A (en) Oxygen ether bitriazol lead complex with potential fluorescent material and preparation method of complex
CN104592269A (en) Cadmium oxyether-bis(triazolyl) iodide complex used as potential fluorescent material and preparation method of cadmium oxyether-bis(triazolyl) iodide complex
CN104592273A (en) Cadmium oxyether-bis(triazolyl) acetate complex used as potential fluorescent material and preparation method of cadmium oxyether-bis(triazolyl) acetate complex

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20150513