Study of the Fluorescence System of Europium–Enoxacin and its Applications

 This paper is the study of the fluorescence enhancement of Eu³⁺-1-ethyl-6-fluoro-4-oxo-7-(1-piperazinyl)-1,8-naphthyridin-3-carbonic acid (enoxacin, EFLX) system by surfactants. It was found that sodium dodecylbenzenesulfonate (SDBS) exhibits great enhancement on the fluorescence of the Eu-EFLX system. The molar ratio is 1:2:1 for Eu:EFLX: SDBS. Under the optimum conditions, the fluorescence intensity is a linear function of europium in the range of 1.0 × 10⁻⁸ ∼ 5.0 × 10⁻⁶ mol/L, the detection limit is 1.0 × 10⁻⁹ mol/L. The application of the Eu-EFLX-SDBS system for the determination of trace europium in rare earth samples gave satisfactory results. Received October 19, 2000. Revision August 10, 2001.     

Cadmium(II)–Triazole Framework as a Luminescent Probe for Ca2+ and Cyano Complexes

A bidentate ligand, 1‐{4‐[4‐(1H‐1,2,4‐triazol‐1‐yl)phenoxy]phenyl}‐1H‐1,2,4‐triazole (TPPT), has been designed and synthesized. By using TPPT as a building block for self‐assembly with Cd(NO₃)₂ ? 4 H₂O and CdCl₂ ? 10.5 H₂O, novel 1D double‐chain {[Cd(TPPT)(NO₃)₂] ? 3 H₂O}_n ( 1 ) and 2D (4,4) layer [Cd(TPPT)Cl₂(H₂O)]_n ( 2 ) have been constructed. When 1 was employed as a precursor and exposed to DMF or N,N′‐dimethylacetamide (DMAC), the crystals of 1 dissolved and reassembled into two types of brown block‐shaped crystals of 1D double chains: {[Cd(TPPT)₂(NO₃)₂] ? DMF}_n ( 1 a ) and {[Cd(TPPT)₂(NO₃)₂] ? DMAC}_n ( 1 b ). The anion‐exchange reactions of complex 2 have also been investigated. After gently stirring crystals of 2 in CHCl₃/C₂H₅OH/H₂O containing NaBr, NaI ? 2 H₂O, or NaOAc ? 3 H₂O, the crystals retained their crystalline appearances. A remarkable single crystal to single crystal transformation was observed and 1D double chains of {[Cd(TPPT)Br₂] ? C₂H₅OH}_n ( 2 a ) and {[Cd(TPPT)₂I₂] ? CHCl₃}_n ( 2 b ), and 1D single chains of [Cd(TPPT)(H₂O)₂(CH₃COO)₂]_n ( 2 c ), can be obtained. Luminescent properties indicate that 1 shows excellent selectivity for Ca²⁺ and cyano complexes. To the best of our knowledge, this is the first example of a luminescent probe for Ca²⁺ based on triazole derivatives.     

Non‐coordinating‐Anion‐Directed Reversal of Activation Site: Selective C−H Bond Activation of N‐Aryl Rings

An Rh‐catalyzed selective C?H bond activation of diaryl‐substituted anilides is described. In an attempt to achieve C?H activation of C‐aryl rings, we unexpectedly obtained an N‐aryl ring product under non‐coordinating anion conditions, whereas the C‐aryl ring product was obtained in the absence of a non‐coordinating anion. This methodology has proved to be an excellent means of tuning and adjusting selective C?H bond activation of C‐aryl and N‐aryl rings. The approach has been rationalized by mechanistic studies and theoretical calculations. In addition, it has been found and verified that the catalytic activity of the rhodium catalyst is obviously improved by non‐coordinating anions, which provides an efficient strategy for obtaining a highly chemoselective catalyst. Mechanistic experiments also unequivocally ruled out the possibility of a so‐called “silver effect” in this transformation involving silver.     

Incorporation of a Phenanthrene Subunit into a Sapphyrin Framework: Synthesis of Expanded Aceneporphyrinoids

32‐Hetero‐5,6‐dimethoxyphenanthrisapphyrins—macrocycles that link structural features of polycylic aromatic hydrocarbons and expanded porphyrins—were obtained in a straightforward [3+1] condensation reaction of dimethoxyphenanthritripyrrane and 2,5‐bis(arylhydroxymethyl)heterocyclopentadienes. The highly folded conformation of formally 4 n π‐electron macrocycles causes them to manifest only limited macrocyclic π conjugation as explored by means of NMR spectroscopic and X‐ray structural analyses, and supported by DFT calculations. Although protonation does not change their π‐conjugation characteristics, the cleavage of ether groups at the phenanthrenylene moiety yields nonaromatic 32‐hetero‐5,6‐dioxophenanthrisapphyrins.     

Switchable [3+2] and [4+2] Heteroannulation of Primary Propargylamines with Isonitriles to Imidazoles and 1,6‐Dihydropyrimidines: Catalyst Loading Enabled Reaction Divergence

Isonitrile 1 due to its carbene‐like reactivity serves generally as a one‐carbon synthon in a diverse set of organic transformations. We report in this article that the isocyano group can also act as a polarized triple bond to undergo, as a two‐atom synthon, heteroannulation with primary propargylamines 15 . In addition, we serendipitously discovered that the reaction pathways can be modulated by simply changing the catalyst loading. In the presence of 0.1 equiv of Yb(OTf)₃ or TfOH, the reaction between 1 and 15 afforded exclusively imidazoles 16 by a formal [3+2] cycloaddition. At a higher catalyst loading (Yb(OTf)₃ (0.4 equiv) or TfOH (0.5 equiv)) under otherwise identical conditions, the same reaction furnished 1,6‐dihydropyrimidines 17 in good to excellent yields by way of a formal [4+2] cycloaddition process. Mechanistic investigations indicated that both annulations went through an amidine intermediate resulting from the insertion of the isocyano group to the NH bond of the primary amine. Subsequent catalyst‐loading‐dependent 5‐exo‐dig or 6‐endo‐dig cyclization provided selectively the two heterocycles, respectively.     

A Selective RhI‐Catalyzed Substrate‐Controlled C−C Bond Activation of Benzyl Sulfonamide/Alcohol‐Tethered Alkylidenecyclopropanes

Benzyl sulfonamide/alcohol‐tethered alkylidenecyclopropanes undergo a rhodium‐catalyzed and substrate‐controlled selective C?C bond activation, producing three types of common organic structural units: benzo[c]azepine/oxepines, dihydronaphthalen‐1‐amines, and conjugated dienes. Epoxidation and aromatization of these products to construct two useful compounds have also been achieved.     

Gold‐Catalyzed Fluorination–Hydration: Synthesis of α‐Fluorobenzofuranones from 2‐Alkynylphenol Derivatives

The Au^I‐catalyzed fluorination–hydration of 2‐alkynylphenol derivatives in the presence of Selectfluor [1‐chloromethyl‐4‐fluoro‐1,4‐diazoniabicyclo‐[2.2.2]octane bis(tetrafluoroborate)] has been developed. This method provides straightforward access to α‐fluorobenzofuranones with the construction of C?O, C=O, and C?F bonds in a single step on the basis of an Au^I/Au^III redox catalytic cycle. Several control experiments, including the asymmetric variant of this reaction, were also conducted to gain insight into the reaction mechanism.     

Photochromic Terbium Phosphonates with Photomodulated Luminescence and Metal Ion Sensitive Detection

Rational selection and modification of rare earth metal centers and photoactive organic linkers enables designable multiphotofunctionality to come to fruition in new hybrid coordination polymer materials. By using a viologen‐functionalized diphosphonate linker, two terbium phosphonate compounds ( Tb‐1 and Tb‐2 ) have been constructed, which display reversible photochromic reactions in response to UV light and soft X‐ray irradiation. In addition, the photo‐induced electron‐transfer reaction can modulate the luminescent emission to thus realize photoluminescence switching behavior. Furthermore, both terbium phosphonates can serve as highly sensitive sensors to probe Cu²⁺ in solution through their luminescence. Thus, they represent the first photochromic examples of lanthanide phosphonate‐based materials with photomodulated luminescence and sensitive detection of metal ions.     

吖啶类衍生物的荧光性质

用比较法测得23种啶类衍生物的荧光量子效率（Φf),以评估这些化合物的荧光性质,结果表明,N－烃基吖啶酮类化合物的荧光量子效率要比9－取代苯基吖啶类和9－取代苯亚甲基－10－甲基－9,10－二氢吖啶类化合物的荧光量子效率大,在非极性溶剂中,9－聚代苯亚甲基－9,10二氢吖啶分子内的强吸电子基NO2增强荧光量子效率,强推电子基OCH3降低荧光量子效率,这些测量结果与取代基的电子作用经验规律不相符,这种现象可以用分子内电荷转移理论进行解释。     

校正峰电位漂移偏最小二乘极谱催化波同时测定轻稀土

应用Ｍ２７３．Ａ电化学系统中的线性扫描技术,确定了８．０×１０－５ｍｏｌ／Ｌ二甲酚橙及ｐＨ４．０ＨＡｃ－ＮａＡｃ缓冲体系为偏最小二乘极谱法同时测定Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ的最佳极谱体系。６种稀土元素的线性范围均在１．０× １０－７～１．２ × １０－５ｍｏｌ／Ｌ。并对极谱峰电位随浓度漂移进行了校正,提高了方法的准确度。