CN102993196B - Triazole derivative, preparation method thereof, nano particles thereof and application of nano particles - Google Patents

Triazole derivative, preparation method thereof, nano particles thereof and application of nano particles Download PDF

Info

Publication number
CN102993196B
CN102993196B CN201210560226.8A CN201210560226A CN102993196B CN 102993196 B CN102993196 B CN 102993196B CN 201210560226 A CN201210560226 A CN 201210560226A CN 102993196 B CN102993196 B CN 102993196B
Authority
CN
China
Prior art keywords
nano particle
compound
lifepo
preparation
nano particles
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.)
Expired - Fee Related
Application number
CN201210560226.8A
Other languages
Chinese (zh)
Other versions
CN102993196A (en
Inventor
李立东
徐新军
***
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.)
University of Science and Technology Beijing USTB
Original Assignee
University of Science and Technology Beijing USTB
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 University of Science and Technology Beijing USTB filed Critical University of Science and Technology Beijing USTB
Priority to CN201210560226.8A priority Critical patent/CN102993196B/en
Publication of CN102993196A publication Critical patent/CN102993196A/en
Application granted granted Critical
Publication of CN102993196B publication Critical patent/CN102993196B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The invention relates to synthesis of a dendritic molecule taking a 1,2,4-triazole derivative as a kernel and a benzothiophene or pyridinothiazole derivative as an arm, a preparation method of the derivative and detection of ferric ions in a lithium iron phosphate anode material by the nano particles of the compound. The triazole derivative is shown by formula 1; the fluorescence emission of the compound can be quenched by the ferric ions without suffering influence of other ions; and when measuring ferric ions in the lithium iron phosphate anode material, the triazole derivative has the advantages of high sensitivity, high speed, accuracy and simplicity and convenience in operation.

Description

The application of triazole derivative, its preparation method and nanoparticle thereof and nanoparticle
Technical field
The present invention relates to a class 1,2,4-triazole derivative is core, and thionaphthene or Kui Linpyrimido quinoline thiazole derivative are the synthesis of the dendrimer of arm, and the preparation method of this derivative, and such compound nano particle is to the detection of ferric ion in ferrous phosphate doping lithium anode material.
Background technology
LiFePO 4 (LiFePO 4) battery material be in the news first from 1997 since (A.K.Padhi, K.S.Nanjundaswamy, J.B.Goodenough, J.Electrochem.Soc.1997,144,1188), caused enough attention.Relative to traditional positive electrode material as LiCoO 2, LiNiO 2and LiMn 2o 4, LiFePO 4have many advantages, such as its theoretical capacity is 170mAhg -1, lithium ion is deviate from and embedded voltage is 3.5V, good cyclical stability and thermostability (K.Tang, J.Sun, X.Yu, H.Li, X.Huang, Electrochimica Acta.2009,54,6565).In addition, LiFePO is prepared 4low in raw material price, nontoxic, environmental friendliness, thus make LiFePO 4one of material power lithium-ion battery positive electrode material of new generation becoming most development and application potentiality.
LiFePO is prepared at present at use ferrous iron, ferric iron source 4time, the ferric iron introducing impurity is difficult to avoid.Ferric existence can make ferrous phosphate doping lithium anode material self-discharge become large, and ratio capacitance declines, so the content of ferric ion judges LiFePO 4an important indicator of positive electrode material quality quality.But at present for LiFePO 4the content detection of ferric ion in positive electrode material, not effective especially detection means and method, general sensitivity is lower and detection method complicated.
Disclosed about detection LiFePO at present 4the document of ferric ion content has CN102323228, CN101470078, and method includes volumetry and spectrophotometer method.Volumetry can not the content of direct-detection ferric ion, and detection sensitivity is not high, and error is comparatively large, and in titration process, use potassium bichromate can to environment.Spectrophotometry operates complexity, and detection sensitivity is not high yet.
Summary of the invention
An object of the present invention is to provide a kind of triazole species derivative compound and synthetic method thereof, preferably, the invention still further relates to the triazole derivative detected for ferric ion.In the present invention, if without specified otherwise, when inconsistent situation appears in the chemical name of compound and structural formula, be as the criterion with the compound representated by structural formula, and applicant retains the right according to structural formula amendment compound chemistry name.
Another object of the present invention be openly the nanoparticle prepared of a kind of triazole derivative to the detection effect of ferric ion.This detection has directly, highly sensitive, and quick and precisely, the advantage such as easy and simple to handle, can detect LiFePO 4the content of ferric ion in positive electrode material.
Triazole derivative shown in a kind of formula 1 of the present invention:
Formula 1
Wherein Ar is selected from hexa-atomic aromatic ring and/or hexa-atomic hetero-aromatic ring, R 10, R 11, R 12, R 13independently be selected from hydrogen, straight chained alkyl or branched-chain alkyl, amino, nitro; Wherein 3 R 10can identical also can not be identical, and R 10the same, 3 R 11, R 12, R 13can identical also can not be identical; A is-CR 0or N, R 0select H, the straight chained alkyl of C1-C12 or branched-chain alkyl, preferably, R 0be selected from hydrogen, methyl, ethyl, n-propyl and sec.-propyl; Three R 0can be the same or different.
In a preferred embodiment of the present invention, R 10, R 11, R 12in at least one be selected from C 6-C 18straight chained alkyl; Preferred further, the R on each thiophene 10, R 11, R 12in at least one be selected from C 4-C 18straight chained alkyl; Described C 4-C 18straight chained alkyl be preferably C 4-C 8straight chained alkyl.
In another preferred embodiment of the present invention, 3 R wherein 10all be selected from C 4-C 8straight chained alkyl, 3 R 10can be the same or different.
In another preferred embodiment of the present invention, described R 11, R 12, R 13independently be selected from hydrogen and C 1-C 6straight chain and/or branched-chain alkyl; Preferably, described C 1-C 6straight chain and/or branched-chain alkyl be selected from methyl, ethyl, n-propyl and sec.-propyl.
In a preferred embodiment of the present invention, described compound is TAZ-BTTC6:
TAZ-BTTC6 formula
Wherein 3 R 10all be selected from C 4-C 8straight chained alkyl, 3 R 10can be the same or different; Preferably, 3 R 10be selected from normal hexane base simultaneously.
The present invention also relates to the preparation method of above-claimed cpd on the other hand, and it is undertaken by following reaction:
Wherein, Ar, R 10, R 11, R 12and R 13definition such as formula 1 define such; In addition, X represents chlorine, bromine and/or iodine; R 41, R 42, R 43and R 44independently be selected from hydrogen, methyl, ethyl, propyl group and sec.-propyl; The reactant 3 of 3 molecules can be the same or different.
In building-up reactions of the present invention, described reaction is at Pb (Pph 3) 4and carry out under the catalysis of alkali; Preferably, described reaction solvent is selected from toluene, reacts and carries out at 75-100 DEG C.
The present invention also relates to the nano particle formed by above-claimed cpd on the other hand, and described nano particle median size is between 110-190 nanometer.
In another preferred embodiment of the present invention, described nano particle at room temperature stablizes preservation more than 30 days.
In another preferred embodiment of the present invention, described nano particle is prepared from by coprecipitation method.
The present invention also relates to above-mentioned nano particle on the other hand at detection Fe 3+application in content.
In application of the present invention, some preferred embodiment in, for detecting LiFePO 4fe in positive electrode material 3+concentration.
In a preferred embodiment of the present invention, described detection is by detecting Fe 3+ion carries out for the contrast of fluorescence intensity before the cancellation of nano-particle fluorescence and after cancellation.
The concrete grammar of synthesis type 1 compound comprises the steps:
In round-bottomed flask, add the tetrakis triphenylphosphine palladium of compound 3, the 0.15-0.5 equivalent of compound 2, the 4-7 equivalent of 1 equivalent, the tetra-n-butyl ammonium bromide of 0.15-0.5 equivalent, protection of inert gas, add degassed toluene and degassed Na 2cO 3solution, through vacuumizing/applying argon gas is repeatedly after three times, is raised to 70-100 DEG C of reaction more than 40 hours, cooling, add water with chloroform extraction three times, dry organic layer, except desolventizing, the solid column chromatography obtained is purified and is obtained compound 1.
The method that coprecipitation method is prepared into nanoparticle comprises the steps:
Tetrahydrofuran solution containing compound 1 is injected the deionized water be under ultrasonic state, continue the nanoparticle that ultrasound filtration obtains compound 1.
Further, nano particle is used for LiFePO 4the application that ferric ion detects comprises the steps:
1) LiFePO is taken 4/ C composite, adds concentrated hydrochloric acid and deionized water, covers watch-glass, under argon shield, at 70-100 DEG C, heats more than 10min, cooling, crosses and filters carbon black, weighs the weight of filtering gained carbon black, determines LiFePO in this solution 4content;
2), under argon shield, LiFePO is got 4solution, in cuvette, adds nanoparticle, adds deionized water, surveys fluorescence intensity, contrasts namely obtain iron concentration with typical curve.
At least have in some or all of embodiment of the present invention one in following advantage, two kinds, three kinds or all:
1) nanoparticle of compound 1 is good to the selectivity of ferric ion, LiFePO 4material acid dissolve after constant volume, other ion pair nanoparticle fluorescence intensity almost do not affect in addition to iron ions, see Fig. 1.
2) compound 1 nanoparticle fluorescence does not change with pH and changes, and the solution thus after constant volume can directly be used for detecting iron ion content without adjust ph, simplifies operation steps.
3) the highly sensitive detectability to ferric ion of the method can reach 10 -7m, does not introduce heavy metal particles in implementation process, more environmental protection.
4) nano-particle solution of formula 1 has good stability, can keep the several months and not produce gathering, more simplifying operation.
Accompanying drawing explanation
Fig. 1: LiFePO 4material dissolves liquid is on the impact of TAZ-BTTC6 nanoparticle fluorescence intensity in embodiment 2;
Fig. 2: TAZ-BTTC6 nano particle diameter distribution in embodiment 2;
Fig. 3: TAZ-BTTC6 nanoparticle stereoscan photograph a) × 10000 in embodiment 2; B) × 30000;
Fig. 4: the normalization method uv-visible absorption spectra of TAZ-BTTC6 in tetrahydrofuran (THF) and normalization method fluorescence emission spectrum in embodiment 3;
Fig. 5: the normalization method uv-visible absorption spectra in embodiment 3 in the TAZ-BTTC6 nanoparticle aqueous solution and normalization method fluorescence emission spectrum;
Fig. 6: TAZ-BTTC6 nanoparticle aqueous solution fluorescence emission spectrum at various ph values in embodiment 3;
Fig. 7: Fe in embodiment 4 3+the typical curve of concentration and fluorescence intensity.
Embodiment
Below in conjunction with embodiment, the present invention is described further, embodiment only illustratively property, and unrestricted the present invention.
Embodiment 1:
The synthesis of formula 1 derivative TAZ-BTTC6:
The structural formula of TAZ-BTTC6, synthetic method and characterization result are as follows:
3 are added in 25ml round-bottomed flask, 4, 5-tri-(4-bromobenzene)-4H-1, 2, 4-triazole (280mg, 0.52mmol), 4-(5-normal hexane base thiophene)-7-(4, 4, 5, 5-tetramethyl--1, 3, 2-bis-mixes oxygen pentaborane) benzo [c] [1, 2, 5-thiadiazoles] (1.22g, 2.85mmol) (the synthesized reference ACS Appl.Mater.Inter.2010 of reactant, 2, 2679.), tetrakis triphenylphosphine palladium (164mg, 0.13mmol), tetra-n-butyl ammonium bromide (40mg, 0.13mmol), argon shield 10 minutes, add the degassed Na of degassed toluene 12ml and 2mol/L 2cO 3solution 5ml, through vacuumizing/applying argon gas is repeatedly after three times, is raised to 85 DEG C of reactions 42 hours, cooling, adds water with chloroform extraction three times, organic over anhydrous Na 2sO 4after drying, except desolventizing, the solid column chromatography obtained is purified and is obtained compound TAZ-BTTC6 red brown solid 400mg, is 64% relative to the productive rate of 3,4,5-tri-(4-bromobenzene)-4H-1,2,4-triazole. 1h NMR (CDCl 3, 400MHz, ppm): δ 8.18-8.16 (t, 3H), 7.97-7.91 (m, 6H), 7.84-7.82 (d, 1H), 7.79-7.77 (d, 2H), 7.69-7.64 (m, 6H), 7.49 (m, 1H), 7.41-7.39 (d, 2H), 6.87-6.84 (m, 3H), 1.73-1.72 (m, 6H), 1.43-1.22 (m, 18H), 0.96-0.88 (m, 9H). 13c NMR (CDCl 3, 400MHz, ppm): δ 154.66, 153.72, 153.59, 152.78, 152.73, 148.63, 148.57, 148.28, 148.22, 138.76, 138.51, 136.55, 136.38, 130.77, 130.65, 129.64, 128.87, 128.75, 128.66, 128.39, 128.19, 128.11, 127.89, 127.33, 126.60, 125.37, 125.26, 124.89, 124.74, 33.70, 31.57, 30.31, 29.98, 28.82, 24.87, 22.57, 22.23, 14.05, 13.80.MS (matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF)), m/z:M +c 68h 63n 9s 6theoretical value: 1198.68, measured value: 1198.6, ultimate analysis: C 68h 63n 9s 6theoretical value C 68.14, H 5.30, N 10.52, measured value C 67.44, H5.58, N 10.23.
Embodiment 2:
Prepared by TAZ-BTTC6 nanoparticle
By compound TAZ-BTTC6, be dissolved in tetrahydrofuran solution with the concentration of 2mg/ml, get this solution of 0.25ml, be injected into 10ml be in ultrasonic state under deionized water in, continue ultrasonic 10min, filter the TAZ-BTTC6 nanoparticle obtaining compound with the tetrafluoroethylene filter of 0.22 μm, the median size of this particle is 175 nanometers, zate current potential is-26.1mV, because particle repels mutually with identical charges, makes nanoparticle can stable existence in the solution.The size distribution of nanoparticle is shown in Fig. 2, is added drop-wise to stereoscan photograph (spray platinum) measured by the dry solvent of silicon chip Back stroke sees Fig. 3 by nano-particle solution.
Embodiment 3:
Record the normalization method uv-visible absorption spectra in the TAZ-BTTC6 nanoparticle aqueous solution and normalization method fluorescence spectrum, and record this nanoparticle aqueous solution fluorescence emission spectrum at various ph values, result as Figure 4-Figure 6.
Embodiment 4:
LiFePO 4sample preparation and ferric ion are to the cancellation curve plotting of fluorescence
Take LiFePO 4/ C composite 0.1000g, adds concentrated hydrochloric acid 1ml, and deionized water 10ml, covers watch-glass, under argon shield, at 85 DEG C, heats 20min, cooling, crosses and filters carbon black, weighs the weight of carbon black, learns LiFePO 4/ C effective content is about 0.0800g.Under argon shield, add 2.5 × 10 -4mol tin protochloride, keeps 20min in a heated condition, guarantees that by ferric iron complete oxidation be ferrous ion, adds 5 × 10 -4stannous ion is all oxidized by mol bivalent cupric ion, and cooling, transfer to constant volume in 1000ml volumetric flask under argon shield, the pH value recording this solution is 2.55.
Under argon shield; get the solution of above-mentioned 1.96ml respectively in cuvette; add the nanoparticle of 20 μ l compound TAZ-BTTC6; add the ferric ion of 20 μ l different concns; record fluorescence intensity under different ferric ion concentration, different ferric ion concentration is as shown in table 1 to TAZ-BTTC6 nanoparticle fluorescence cancellation result.
Table 1: TAZ-BTTC6 fluorescence intensity under different ferric ion concentration
[Fe 3+](molL -1) I
0 3655
1E-7 3489
5E-7 3299
1E-6 3221
2E-6 3061
4E-6 2734
6E-6 2578
8E-6 2354
1E-5 1823
2E-5 1598
4E-5 1247
6E-5 1187
8E-5 1015
1E-4 774
2E-4 571
4E-4 304
Described I is fluorescence intensity, and the typical curve of drafting as shown in Figure 7.
Embodiment 5:
Choose a LiFePO 4/ C sample, implements to carry out Fe according to method of the present invention 3+detection:
Take LiFePO 4/ C composite 0.1000g, adds concentrated hydrochloric acid 1ml, and deionized water 10ml, covers watch-glass, under argon shield, at 85 DEG C, heats 20min, cooling, crosses and filters carbon black.Under argon shield, the solution getting above-mentioned 1.96ml respectively, in cuvette, adds the nanoparticle of 20 μ l compound TAZ-BTTC6, surveys fluorescence intensity.
It is 3390 that experiment records fluorescence intensity, and contrast standard curve obtains Fe 3+concentration be 3.6 × 10 -7m, calculates Fe in this sample 3+content be 0.202%.
Above content is further illustrating of doing the present invention of several preferred implementation method specifically; but the present invention is not limited to this explanation; do not departing under concept thereof of the present invention; any process provides for simple replacement of quasi-drugs; or change drug dosage and replace experiment condition; or carry out simple reasoning replacement, all should be considered as belonging to protection scope of the present invention.

Claims (7)

1. triazole derivative shown in a formula 1:
Wherein R is-C 6h 13.
2. the preparation method of compound described in claim 1, it is undertaken by following reaction:
Wherein R is-C 6h 13.
3. the preparation method of compound according to claim 2, described reaction is at Pd (pph 3) 4katalysis under, reaction solvent is selected from degassed toluene and degassed Na 2cO 3solution, reacts and carries out at 85 DEG C.
4. the nano particle made of compound according to claim 1, described nano particle median size is between 110-190 nanometer, and this nano particle at room temperature stablizes preservation more than 30 days.
5. the application of nano particle according to claim 4, is characterized in that, described nano particle can be used for detecting Fe 3+content.
6. the application of nano particle according to claim 5, is characterized in that, described nano particle is for detecting LiFePO 4fe in positive electrode material 3+concentration.
7. the application of the nano particle according to claim 5 or 6, is characterized in that, it is by detecting Fe that described nano particle detects 3+ion carries out for the contrast of fluorescence intensity before the cancellation of nano-particle fluorescence and after cancellation.
CN201210560226.8A 2012-12-20 2012-12-20 Triazole derivative, preparation method thereof, nano particles thereof and application of nano particles Expired - Fee Related CN102993196B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210560226.8A CN102993196B (en) 2012-12-20 2012-12-20 Triazole derivative, preparation method thereof, nano particles thereof and application of nano particles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210560226.8A CN102993196B (en) 2012-12-20 2012-12-20 Triazole derivative, preparation method thereof, nano particles thereof and application of nano particles

Publications (2)

Publication Number Publication Date
CN102993196A CN102993196A (en) 2013-03-27
CN102993196B true CN102993196B (en) 2015-01-28

Family

ID=47922366

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210560226.8A Expired - Fee Related CN102993196B (en) 2012-12-20 2012-12-20 Triazole derivative, preparation method thereof, nano particles thereof and application of nano particles

Country Status (1)

Country Link
CN (1) CN102993196B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105842266A (en) * 2016-03-23 2016-08-10 合肥国轩高科动力能源有限公司 Fluorescence analysis method for measuring element content of lithium iron phosphate
CN106674212B (en) * 2017-01-04 2019-08-09 云南大学 Thiophene triazole wave draws (Bola) compound
CN107056717B (en) * 2017-03-14 2019-07-30 吉林大学 D-A type organic fluorescence small molecule material and its application in ferric ion detection

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1391952A2 (en) * 1996-12-30 2004-02-25 Hydro-Quebec Salts of pentacyclic or tetrapentaline derived anions, and their uses as ionic conductive materials
CN101470078A (en) * 2007-12-25 2009-07-01 深圳市比克电池有限公司 Method for measuring content of iron element in different valence states in lithium iron phosphate anode material
CN102295641A (en) * 2010-06-28 2011-12-28 中国科学院化学研究所 Star-type three-dimensional conjugate molecule based on triphenylamine-benzothiadiazole, and preparation method and application thereof
CN102323228A (en) * 2011-06-22 2012-01-18 恒正科技（苏州）有限公司 The assay method of ferrous iron and ferric iron content in the lithium iron phosphate cathode material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1391952A2 (en) * 1996-12-30 2004-02-25 Hydro-Quebec Salts of pentacyclic or tetrapentaline derived anions, and their uses as ionic conductive materials
CN101470078A (en) * 2007-12-25 2009-07-01 深圳市比克电池有限公司 Method for measuring content of iron element in different valence states in lithium iron phosphate anode material
CN102295641A (en) * 2010-06-28 2011-12-28 中国科学院化学研究所 Star-type three-dimensional conjugate molecule based on triphenylamine-benzothiadiazole, and preparation method and application thereof
CN102323228A (en) * 2011-06-22 2012-01-18 恒正科技（苏州）有限公司 The assay method of ferrous iron and ferric iron content in the lithium iron phosphate cathode material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Mononuclear, oligonuclear and polynuclear metal coordination compounds with 1,2,4-triazole derivatives as ligands";Jaap G. Haasnoot;《Coordination Chemistry Reviews》;20001231;第200-202卷;第131-185页 *
Ke Liu,等."The coordination chemistry of Zn(II), Cd(II) and Hg(II) complexes with 1,2,4-triazole derivatives".《Dalton Trans.》.2011,第40卷第8475-8490页. *
Youtian Tao,等."Highly Efficient Phosphorescent Organic Light-Emitting Diodes Hosted by 1,2,4-Triazole-Cored Triphenylamine Derivatives: Relationship between Structure and Optoelectronic Properties".《J. Phys. Chem. C》.2009,第114卷(第1期),第601–609页. *

Also Published As

Publication number Publication date
CN102993196A (en) 2013-03-27

Similar Documents

Publication Publication Date Title
Liu et al. Synthesis, Structures and Electrochemical Properties of Nitro‐and Amino‐Functionalized Diiron Azadithiolates as Active Site Models of Fe‐Only Hydrogenases
Bourgeois et al. Regioselective Synthesis of trans‐1 Fullerene Bis‐Adducts Directed by a Crown Ether Tether: Alkali Metal Cation Modulated Redox Properties of Fullerene–Crown Ether Conjugates
Zapata et al. Imidazole-annelated ferrocene derivatives as highly selective and sensitive multichannel chemical probes for Pb (II) cations
Palanna et al. Nanomolar detection of mercury (II) using electropolymerized phthalocyanine film
Rajeswara Rao et al. Boron complexes of oxasmaragdyrin, a core-modified expanded porphyrin
Kaur et al. Ferrocene-BODIPY Push–Pull dyad: A common platform for the sensing of Hg2+ and Cr3+
Allain et al. Hybrid organic–inorganic porphyrin–polyoxometalate complexes
Zayed et al. Transition metal complexes of novel Schiff base: Synthesis, spectroscopic characterization, and in vitro antimicrobial activity of complexes
Michel et al. Peripheral metal-ion binding to tris (thia− oxo crown) porphyrazines
Shetti et al. Supramolecular tetrads containing Sn (IV) porphyrin, Ru (II) porphyrin, and expanded porphyrins assembled using complementary metal− ligand interactions
Zapata et al. A Selective Redox and Chromogenic Probe for Hg (II) in Aqueous Environment Based on a Ferrocene− Azaquinoxaline Dyad
Tamayo et al. New fluorescence PET systems based on N2S2 pyridine-anthracene-containing macrocyclic ligands. Spectrophotometric, spectrofluorimetric, and metal ion binding studies
CN102993196B (en) Triazole derivative, preparation method thereof, nano particles thereof and application of nano particles
Delecluse et al. Highly selective fluoride recognition by a small tris-urea covalent cage
Jayaseelan et al. Synthesis, spectral characterization, electrochemical and anti-microbial activities of new binuclear Schiff base metal complexes derived from 3, 3’diaminobenzedine
Thakur et al. A triazole based triferrocene derivative as a multiresponsive chemosensor for Hg (II) ion and a redox chemosensor for H2PO4− ion
Li et al. Twisted-Planar-Twisted expanded porphyrinoid dimer as a rudimentary reaction-based methanol indicator
Ou et al. Gold (III) porphyrins containing two, three, or four β, β′-fused quinoxalines. synthesis, electrochemistry, and effect of structure and acidity on electroreduction mechanism
Ganapathi et al. Stable nonaromatic [20] dithiaporphyrin (2.1. 1.1) macrocycles: Synthesis, structure, spectral, electrochemical, and metal ion sensing studies
Chien et al. Novel linear hexanuclear cobalt string complexes (Co 6 12+) and one-electron reduction products (Co 6 11+) supported by four bpyany 2− ligands
He et al. Facile synthesis of an isolable and ambient stable bay-substituted perylene diimide radical anion salt and its optical response to base–acid and metal ions
Kalita et al. Phosphorus Complexes of meso-Triaryl-25-oxasmaragdyrins
Su et al. Selective anion receptor for fluoride detection using ferrocenyl–boronate derivative
Bhyrappa et al. β-Tetrakis (2-thienyl)-meso-tetraphenylporphyrins: Synthesis, structural and electrochemical redox properties
Roy et al. E-Bodipy fluorescent chemosensor for Zn2+ ion

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20150128

Termination date: 20181220