硝基取代苯腙类荧光受体的阴离子识别与传感性能

合成了含萘荧光基团的硝基取代苯腙类受体,利用紫外-可见分光光度法、荧光发射光谱法和核磁等方法研究了受体的阴离子识别与光化学传感性能. 结果表明,在DMSO有机溶剂体系中,单硝基取代受体选择性比色和荧光识别氟离子,而双硝基取代受体可以比色和荧光识别氟离子和醋酸根离子. 归因于腙=N-NH基团质子酸性的进一步增强,双硝基取代受体能够在DMSO-H2O体系中实现对氟离子的比色和荧光识别. 此类受体是有效的“off-on”型阴离子荧光传感分子.     

Synthesis,structures and photophysical properties of phosphorus-containing silver 3,5-bis(trifluoromethyl)pyrazolates

Reaction of a trinuclear silver pyrazolate {[3,5-(CF₃)₂Pz]Ag}₃ complex with tricyclohexylphosphine at different reagent ratios leads to the formation of heteroleptic dinuclear or tetranuclear complexes. According to the single crystal X-ray analysis of the dinuclear complex, hexane molecules are incorporated into the cavities formed as the result of supramolecular packing. Coordination of a phosphine ligand makes dinuclear silver pyrazolate to exhibit blue emission at room temperature.     

Synthesis of a new colorimetric receptor based on calix[4]pyrrole binding oxime for selective recognition of fluoride ions

A colorimetric anion sensor α-meso-heptaethylcalix[4]pyrrole-meso-3-aminophenyl-p-nitrobenzaldoxime was synthesised and characterised by various spectroscopic techniques. Anion-binding studies were carried out using UV–vis, and ¹H NMR titrations, revealing that the receptor exhibits selective recognition towards F^?  over other anions. The selectivity for F^?  among the halides is attributed mainly to the hydrogen bond interaction of the receptor with F^? . Receptor showed colour change from colourless to yellow in the presence of tetrabutylammonium fluoride with 1:2 stoichiometry. Cyclic voltammetry studies, carried out in CH₃CN, provided evidence of an anion-dependent electrochemical response with F^?  ion. This response was particularly dramatic in the case of receptor after the addition of ～1 equiv. of F^?  ion.     

Synthesis and Crystal Structure of 1-(N,N-Di-(p-toluenesulfonyl))-amino-2-(N'-p-toluenesulfonyl)-amino-3,5-dinitrobenzene

The title compound,1-(N,N-di-(p-toluenesulfonyl))-amino-2-(N'-p-toluenesulfonyl)-amino-3,5-dinitrobenzene,was synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in orthorhombic,space group Pna21 with a=13.723(2),b=25.354(4),c=8.6565(12) ,V=3011.9(8) 3,Z=4,Mr=660.68,F(000)=1368,Dc=1.457 g/cm3,μ=0.309,the final R=0.0609 and wR=0.1042. The H atom of N2-H group,which is the unique recognition site to anion,is enveloped by two oxygen atoms and one benzene from two and one p-toluenesulfonyl moieties,respectively.     

N-(9-蒽甲基)-L-酪氨酸盐酸盐的合成及其对阴离子的分子识别

利用荧光基团9-蒽醛与L-酪氨酸反应,合成了荧光主体N-(9-蒽甲基)-L-酪氨酸盐酸盐;采用荧光光谱方法检测了荧光主体与不同阴离子之间的识别作用;通过加入不同摩尔比的配体确定了主体与配体之间识别的最佳摩尔配比.结果表明,配置浓度为5×10-5mol·L-1的Cr2O2-7溶液后,用微量进样器加入100μL浓度为1×1...     

Synthesis, spectral, electrochemical, and anion binding properties of 3,5-bis(dipyrromethanyl) boron-dipyrromethenes

Four new boron-dipyrromethenes (BODIPYs) containing dipyrromethanyl substituents at 3,5-positions, bis(3,5-dipyrromethanyl) BODIPYs 5-8, were synthesized by treating their corresponding 3,5-diformyl BODIPYs 1-4 with excess pyrrole under mild acid catalyzed reaction conditions. The compounds 5-8 are stable and freely soluble in common organic solvents. One-dimensional, two-dimensional NMR, high resolution mass spectrometry (HRMS), absorption, fluorescence, and electrochemical techniques were used to characterize the compounds. The spectral and electrochemical studies indicated that dipyrromethanyl groups at 3,5-positions of BODIPY are less electron deficient compared to formyl groups at the same positions. The anion binding studies indicated that bis(3,5-dipyrromethanyl) BODIPY compounds containing four pyrrole NH groups showed preferential binding with F(-) ion over other anions, as confirmed by using NMR, fluorescence, and electrochemical studies.     

meso‐3,5‐Bis(trifluoromethyl)phenyl‐Substituted Expanded Porphyrins: Synthesis,Characterization, and Optical,Electrochemical, and Photophysical Properties

Trifluoroacetic acid‐catalyzed condensation of pyrrole with electron‐deficient and sterically hindered 3,5‐bis(trifluoromethyl)benzaldehyde results in the unexpected production of a series of meso‐3,5‐bis(trifluoromethyl)phenyl‐substituted expanded porphyrins including [22]sapphyrin 2 , N‐fused [22]pentaphyrin 3 , [26]hexaphyrin 4 , and intact [32]heptaphyrin 5 together with the conventional 5,10,15,20‐tetrakis(3,5‐bis(trifluoromethyl)phenyl)porphyrin 1 . These expanded porphyrins are characterized by mass spectrometry, ¹H NMR spectroscopy, UV/Vis/NIR absorption spectroscopy, and fluorescence spectroscopy. The optical and electrochemical measurements reveal a decrease in the HOMO–LUMO gap with increasing size of the conjugated macrocycles, and in accordance with the trend, the deactivation of the excited singlet state to the ground state is enhanced.     

Synthesis and evaluation of fluorimetric and colorimetric chemosensors for anions based on (oligo)thienyl-thiosemicarbazones

A family of heterocyclic thiosemicarbazone dyes (3a–d) containing thienyl groups has been synthesized, characterized, and their chromo-fluorogenic response in acetonitrile in the presence of selected anions was studied. Acetonitrile solutions of 3a–d show absorption bands in the 338–425 nm range, which are modulated by the groups attached to the thiosemicarbazone moiety. The fluoride, chloride, bromide, iodide, dihydrogen phosphate, hydrogen sulfate, nitrate, acetate, and cyanide anions were used in the recognition studies. Only sensing features were observed for fluoride, cyanide, acetate, and dihydrogen phosphate anions. Two different chromogenic responses were found, (i) a small shift of the absorption band due to coordination of the anions with the thiourea protons and (ii) the appearance of a new red-shifted band due to deprotonation of the receptor. For the latter process changes in the color solutions from pale-yellow to orange-red were observed. Fluorescence studies showed a different emission behavior according to the number of thienyl rings in the π-conjugated bridges. Stability constants for the two processes (complex formation+deprotonation) for receptors 3a–d in the presence of fluoride and acetate anions were determined from spectrophotometric titrations using the HypSpec program. The interaction of 3d with fluoride was studied through ¹H NMR titrations. Semiempirical calculations to evaluate the hydrogen-donating ability of the receptors were also performed.     

Synthesis of 1,1-bis(trifluoromethyl)alkyl isocyanates, carbamates, and ureas

A convenient preparative method for the synthesis of 1,1-bis(trifluoromethyl)alkyl isocyanates was proposed. The reactions of the isocyanates with alcohols, phenols, and alkyl-, aryl-, and hetarylamines were studied. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1205–1209, July, 2000.     

新型呋咱阴离子探针的合成、晶体结构及性质研究

设计合成了一种AcO-和F-的阴离子比色/荧光探针4-氯-7-硝基-2,1,3-苯并呋咱(NBD-Cl)衍生物。探针结构经X-ray单晶衍射测定属于三斜晶系、空间群为P1。用紫外-可见吸收及荧光光谱研究了其识别性能。探针的乙腈溶液加入AcO-,F-后,在较短时间内裸眼能观察到颜色由橘黄色变为红色,同时有显著的荧光增强。核磁滴定及质子溶剂实验证明识别过程为探针与阴离子之间形成的氢键作用力,伴随着质子化过程发生。     

Synthesis and luminescent properties of Zn complex based on 8-hydroxyquinoline group containing 3,5-bis(trifluoromethyl) benzene unit with unique crystal structure

The use of a novel 2-substituted-8-hydroxyquinoline ligand (E)-2-{2-[3,5-bis (trifluoromethyl)phenyl]ethenyl}-8-hydroxyquinoline(4, BFHQ) characterized by EIMS, ¹H NMR spectroscopy, elemental analysis, and FTIR spectroscopy enabled the isolation of a trimeric Zn(II) complex with the formula Zn₃(BFHQ)₆ (5, Scheme 1). X-ray structural analysis shows that 5 exhibits a trinuclear core, which is bridged by four 8-hydroxyquinoline rings. The trinuclear core is surrounded by three pairs of BFHQ ligands with offset π-π stacking, showing propeller-like molecular structure. The aggregation behavior of Zn(AcO)₂ and the ligand 4 in solution was investigated by UV-vis. The luminescence properties of compound 5 were investigated by UV-vis and fluorescence spectra at room temperature. The experimental results show that the complex 5 emits yellow luminescence at 553 nm (λ_{em, max}) in DMSO solution and at 610 nm (λ_em, max) in solid state. The thermogravimetric analysis was carried out to examine the thermal stability.     

Synthesis and anion recognition of neutral receptors based on multiamide calix[4]arene

Two multiamide calix[4]arenes (5, 6) were synthesized and characterized by NMR, MS and elemental analysis. The binding properties of receptors with some anions (π-O₂NPhOPO₃²⁻, π-O₂NPhO⁻, H₂PO₄⁻, Ac⁻, Cl⁻, Br⁻ and I⁻) were studied by UV-Vis spectra. The results indicate that the tetraamide calix[4]arenes (5, 6) have a good selectivity to the anions containing aromatic ring (π-O₂NPhOPO₃ ²⁻, π-O₂NPhO⁻). The 1 : 1 complexes between host and guest were formed through multiple hydrogen bonding and π-π interactions. The hosts 5 and 6 also show a definite binding ability for the anions (H₂PO₄⁻, Ac⁻, Cl⁻) that have no ultraviolet absorption, which provides a simple method of spectrum detection for these anions.     

A chiral polymer‐based turn‐on fluorescent sensor for specific recognition of hydrogen sulfate

A new kind of polymeric chemosensor containing chiral naphthaldimine moiety in the side chain was synthesized by the reversible addition‐fragmentation chain transfer polymerization of N‐{[2‐(4‐vinylbenzyloxy)‐1‐naphthyl]‐methylene}‐(S)‐2‐phenylglycinol (VNP). The resulting polymers (PVNP) showed high selectivity for hydrogen sulfate relative to other anions including F^?, Cl^?, Br^?, H₂PO, CH₃CO, and NO in tetrahydrofuran (THF) solution as judged from UV?vis, fluorescence, and circular dichroism spectrophotometric titrations. Compared with its monomer, the polymer has proven to be more attractive for detection of HSO in terms of sensitivity and reproducibility. Upon addition of the anion it gives remarkable spectral responses concomitant with detectable color change from colorless to pale yellow. Furthermore, the HSO‐induced CD or fluorescence signal can be totally reversed with addition of base and eventually recovered the initial state, leading to a reproducible molecular switch with two distinguished “on” and “off” states. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Complexations of tweezer molecule (2s, 8s)-bis(2-naphthoyl aminomethyl)-1,5,9-triazabicyclo[4,4,0]dec- 5-ene with organic anions

1H NMR studies have been made on the effects of complexation of tweezer molecule (2s, 8s)-bis(2-naphthoyl aminomethyl)-1,5,9-triazabicyclo[4,4,0] dec-5-ene chloride with the salts of p-nitrobenzoate, p-methoxybenzoate and (L)-N-acetyltryptophan. The stability constants of these complexes nave been determined in CDCl3. The results show that the tweezer molecule and aromatic carboxylates are self-associated by hydrogen bonding, electrostatic interaction and aromatic π-π stacking interaction, forming sandwich supramolecular complexes.     

Synthesis, structural characterization, and initial electroluminescent properties of bis-cycloiridiated complexes of 2-(3,5-bis(trifluoromethyl)phenyl)-4-methylpyridine

A series of bis-cyclometalated Ir(III) complexes (8-10, 12, 15, 17, 19, 21, 23, 25, 28, 29 and 33) bearing two chromophoric N^∧C cyclometalated ligands derived from 2-(3,5-bis(trifluoromethyl)phenyl)-4-methylpyridine (1) and a third nonchromophoric ligand has been synthesized. A palladium-catalyzed cross-coupling reaction between 2-chloro-4-methylpyridine (2) and 3,5-bis(trifluoromethyl)phenylboronic acid (3) was used to prepare 2-(3,5-bis(trifluoromethyl)phenyl)-4-methylpyridine (1). Cyclometalation of (1) by IrCl₃ was carried out in (MeO)₃PO, with the formation of chloro-bridged dimer [N^∧C]₂Ir(μ-Cl)₂Ir[C^∧N]₂ (8). Reaction of (8) with lithium 2,4-pentanedionate, lithium 2,2,6,6-tetramethyl-heptane-3,5-dionate (13), dipivaloyltrimethylsilylphosphine (14), 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octadione (16), 1,1,1,3,3,3-hexafluoro-2-pyridin-2-yl-propan-2-ol (18), 1,1,1,3,3,3-hexafluoro-2-pyrazol-1-ylmethyl-propan-2-ol (20), 2-diphenylphosphanylethanol (22), and 1-diphenylphosphanylpropan-2-ol (24), afforded octahedral iridium complexes 9, 12, 15, 17, 19, 21, 23 and 25, respectively. Complex 10, which contains three different ligands (L₁ = N^∧C of 1; L₂ = N^∧C of 4,4′-dimethyl-[2,2′]bipyridinyl 4; L₃ = O^∧O of 2,4-pentanedione), and complex 11, which contains no cyclometalated ligands (L₁ = 4; L₂ = L₃ = Cl; L₄ = O^∧O of 2,4-pentanedione) were also isolated as minor products in a one-pot reaction between a 94:5 mixture of 1 and 4, IrCl₃ and lithium 2,4-pentanedionate. Reaction of 8 with diphenylphosphanylmethanol (27) in 1,2-dichloroethane unexpectedly led to complexes 28 and 29. The reactions of 8 with benzoylformic acid resulted in the formation of hydroxyl-bridged dimer [N^∧C]₂Ir(μ-OH)₂Ir[C^∧N]₂ (33). According to X-ray analyses, Ir-to-Ir distances in the crystal cell increase from 6.86 Å for 10 to 13.31 Å for 33. The angle theta, which represents the twisting of two cyclometalated C-Ir-N planes relative to each other, varies from 97.5° for 21 to 90.76 for complex 28. OLED devices were fabricated from several Ir complexes and preliminary results are discussed.     

Preparation of a new receptor for anions, macrocyclic polythiolactam—structure and high anion-binding ability

Thiocarbonylation of a macrocyclic tetralactam gave a new macrocyclic tetrathiolactam. The chemical transformation enhances hydrogen-bonding ability of the NH protons in the cavity of the macrocycle, and provides strong affinity toward anions. The association properties of the polythiolactam with anions was examined, and molecular structures of the macrocycle and its Cl⁻ complex were determined.     

Synthesis and anion recognition of neutral receptors based on multiamide calyx[4]arene

~~Synthesis and anion recognition of neutral receptors based on multiamide calyx[4]arene~~