A Bifunctional Luminescent Metal–Organic Framework for the Sensing of Paraquat and Fe3+ Ions in Water

The hydrothermal reaction of Zn²⁺ ions with a mixture of two ligands, Hcptpy and H₃btc (Hcptpy=4‐(4‐carboxyphenyl)‐2,2′:4′,4′′‐terpyridine; H₃btc=1,3,5‐benzenetricarboxylic acid), led to the formation of a 3D metal–organic framework (MOF) with 1D channels, [Zn₂(cptpy)(btc)(H₂O)]_n ( 1 ), which was structurally characterized by using single‐crystal X‐ray diffraction (SXRD). In MOF 1 , two independent Zn²⁺ ions were interconnected by btc^3? ligands to form a 1D chain, whilst adjacent Zn²⁺ ions were alternately bridged by cptpy^? ligands to generate a 2D sheet, which was further linked by 1D chains to form a 3D framework with a new (3,3,4,4)‐connected topology. Furthermore, compound 1 also exhibited excellent stability towards air and water and, more importantly, luminescence experiments indicated that it could serve as a probe for the sensitive detection of paraquat (PAQ) and Fe³⁺ ions in aqueous solution.     

Diastereoselective synthesis of 3-tert-butyl-3,4-dihydropyrazolo[5,1-c][1,2,4]triazine-3,4-diyl dicarboxylates

The reactions of 3-tert-butyl-7-R¹-8-R²-pyrazolo[5,1-c][1,2,4]triazines (R¹ = H, Br; R² = Me, n-Bu) with N-bromosuccinimide in the presence of R³CO₂H (R³ = Me, t-Bu, Ph) afforded novel diastereomerically pure 3-tert-butyl-7-R¹-8-R²-3,4-dihydropyrazolo[5,1-c][1,2,4]triazine-3,4-diyl dicarboxylates. The structures of the isolated products were established on the basis of IR, ¹H, ¹³C, 2D NOESY NMR, high resolution mass spectrometry and X-ray single-crystal analysis. The steric and mechanistic origins of the observed regio- and stereoselectivity were also discussed.     

Synthesis of novel racemic 3,4-dihydroferroceno[c]pyridines via the Ritter reaction

A new approach for the synthesis of functionalized racemic 3,4-dihydroferroceno[c]pyridines via the Ritter reaction of 2-methyl-1-ferrocenylpropan-1-ol with nitriles in the presence of methansulfonic acid was developed. The scope and limitations of the reaction were evaluated. Selected racemic 3,4-dihydroferroceno[c]pyridines were successfully separated by preparative HPLC on a Chiralcel OD-H column. The absolute configuration of the enantiomers was determined by X-ray crystal structure analysis.     

Real‐time Probing the Formation of [M(2,2‐bipyridine)2(NO3)3] (M = Ce,La, Tb) Complexes and Influence of Synthesis Parameters

Despite the strong technological importance of lanthanide complexes, their formation processes are rarely investigated. This work is dedicated to determining the influence of synthesis parameters on the formation of [Ce(bipy)₂(NO₃)₃] as well as Ce³⁺‐ and Tb³⁺‐substituted [La(bipy)₂(NO₃)₃] (bipy = 2,2′‐bipyridine) complexes. To this end, we performed in situ luminescence measurements, synchrotron‐based X‐ray diffraction (XRD) analysis, infrared spectroscopy (IR), and measured pH value and/or ion conductivity during their synthesis process under real reaction conditions. For the [Ce(bipy)₂(NO₃)₃] complex, the in situ luminescence measurements initially presented a broad emission band at 490 nm, assigned to the 5d→4f Ce³⁺ ions within the ethanolic solvation shell. Upon the addition of bipy, a red shift to 700 nm was observed. This shift was attributed to the changes in the environment of the Ce³⁺ ions, indicating their desolvation and incorporation into the [Ce(bipy)₂(NO₃)₃] complex. The induction time was reduced from 8 to 3.5 min, by increasing the reactant concentration by threefold. In contrast, [La(bipy)₂(NO₃)₃] crystallized within days instead of minutes, unless influenced by high Ce³⁺ and Tb³⁺ concentrations. Monitoring and controlling the influence of the reaction parameters on the structure of emissive complexes is important for the development of rational synthesis approaches and optimization of their structure‐related properties like luminescence.     

Melamium Thiocyanate Melam,a Melamium Salt with Disordered Anion Sites

Melamium salts are a group of ionic carbon nitride type compounds that has been investigated only scarcely. We herein present a novel representative of this group. A melamium thiocyanate melam (1:1) adduct was synthesized from dicyandiamide and ammonium thiocyanate in sealed glass ampoules. The structure of the adduct was determined from single‐crystal X‐ray diffraction. Melamium thiocyanate melam crystallizes in monoclinic space group P2₁/c (no. 14) with lattice parameters of a = 3.6041(11), b = 28.532(7), c = 10.937(4) Å, β = 99.051(14)°, and Z = 4. While the melamium ions form 2D extended hydrogen bridged networks, the thiocyanate ions are disordered and no distinct structural sites could be assigned to the respective atoms. Instead, continuous columns of electron density located in channels in the porous structure were identified as potential space for anion locations. The compound was further characterized by elemental analysis, FTIR spectroscopy and solid‐state MAS‐NMR spectroscopy of the nuclei ¹H, ¹³C and ¹⁵N. Rietveld refinement of powder samples was performed for phase analysis. Furthermore, DSC‐TG was used to investigate the thermal behavior of the compound.     

Evidence for the Existence of (SiP6H2)2– and its Homologs as Examples of Binary Nortricyclane‐Type Zintl Anions

The extraction of stoichiometric ternary K/Si/P, K/Ge/P, and K/Si/As solid mixtures with en/crypt‐222 afforded compounds with binary anions of the respective groups 14/15 elemental combination. Although the analysis of the products turned out to be extremely difficult owing to their intrinsically poor crystallinity and low solubility, we have evidence that one of them contains (SiP₆H₂)^2– anions. Preliminary data from the two other compounds indicate the existence of the heavier Ge/P and Si/As variants as well. The combination of all analytical results, including X‐ray crystallography, energy‐dispersive X‐ray (EDX) spectroscopy, electrospray ionization mass spectrometry (ESI‐MS), and nuclear magnetic resonance (NMR) spectroscopy, point towards the named composition of the anions and their doubly protonated nature. By this, they represent the first binary Zintl anions of the Si/P and Si/As elemental combination and complement the recent endeavors to synthesize binary Zintl anions of the light(er) p‐block elements. We discuss our attempts to elucidate the clusters' identity and provide our results as the most probable interpretation of the data, additionally corroborated by quantum chemical analyses.     

Crystal Growth and Structure Determination of Pigment Orange 82

The crystal structure of the important industrial orange pigment PO82, major part of the BASF Colors & Effects^® product Sicopal^® Orange K/L 2430, was solved from combined X‐ray single crystal, X‐ray and neutron powder diffraction, ¹¹⁹Sn Mössbauer spectroscopy, transmission electron microscopy, electron diffraction, and chemical analyses. The structure contains Keggin type clusters composed of four [M₃O₁₃] trimers consisting each of three MO₆ octahedra that share edges and one common oxygen atom connecting the trimers to the central ZnO₄ tetrahedron. The octahedrally coordinated metal atom position is mixed occupied by Ti⁴⁺, Sn⁴⁺, and Zn²⁺. Adjacent Keggin clusters share vertices and are further interconnected to four ZnO₄ tetrahedra. This framework of interconnected MO₆ octahedra and ZnO₄ tetrahedra contains channels along [110], in which the Sn²⁺ cations are located.     

可获得高分辨率谱线信息的新型太阳极紫外成像仪

极紫外光谱观测和诊断是研究太阳大气基本物理过程的最重要手段之一。但因为波长短，很多可见光仪器的设计方案不再适用，且极紫外观测只能在太空中开展。国际上现有卫星上的太阳极紫外成像仪和光谱仪都有各自的不足，比如极紫外成像仪不能获得高光谱分辨率的谱线信息；狭缝式光谱仪通过扫描可得到活动区域的信息，但扫描时间过长，对于研究剧烈变化的太阳活动有很大的局限性。这些不足制约了对日冕物质抛射(CME)和耀斑等太阳活动的高精度观测及对其机理的研究：无法看到CME在内日冕的加速过程，而且无法将可见光看到的CME现象同极紫外看到的日面源区直接联系；缺少观测目标的视向速度信息，难以识别CME的触发过程。采用多级衍射成像方式的一种新型太阳极紫外成像仪，除实现传统极紫外成像仪功能外，还可以在太阳活动变化过程中同步获得全日面各区域的光谱信息。新型成像仪可以得到高光谱分辨率数据，用于反演低日冕的等离子体视向速度，获得全日面的速度分布，与同时得到的高空间分辨率图像相结合，可以识别太阳活动现象对应的物质运动, 为空间科学研究提供数据；因为没有狭缝和运动部件，可以实现对大视场的太阳活动区域的高时间分辨率成像，有利于捕捉日面活动的快速变化。新型成像仪采用无狭缝光谱分光成像的设计理念，即同一时间把一定光谱带宽的信息记录到一个二维的图像上，此过程可以看成是从某一个角度将空间和光谱数据立方体投影到一个面上，然后再利用反演得到空间分辨图像和光谱信息。多级光谱成像的光学设计与传统光谱仪最大的不同是其不存在逐行扫描的狭缝，这使得其能够同时获得大视场内太阳的空间信息和光谱信息。因为极紫外波段的特殊性，以及本仪器面向卫星遥感应用，不可能像可见光波段或者医用CT机一样实现很多衍射级的同时成像。因此，新型极紫外成像仪光学系统由反射镜、色散光栅和五个探测器组成，入射的太阳极紫外辐射经过光栅色散后分别由五个级次的探测器接收，其中四个探测器分部接收±1和±2衍射级图像，另外一个接收0级图像。空间信息可以直接从0级图像得到，而光谱信息则需要根据五个级次成像的反演结果得出。介绍了光学系统的设计以及反演算法，并分析了反演算法的误差。光路基于变间距光栅设计，可实现空间分辨率1.8 arcsec·pixel-1, 光谱分辨率7.8×10-3 nm·pixel-1，同时减小了体积和重量，适合空间应用。     

Sweet like chocolate

A new crystalline form of αβ‐d ‐lactose prepared by oven drying a concentrated aqueous solution of d ‐lactose is a lesson in the power of observation and the rigorous analysis of powder samples.     

Synthesis and Electronic Properties of Novel 5,7-Diazapentacene Derivatives

A route to the synthesis of novel 5,7-diazapentacenes and some preliminary studies on their properties is reported. A single crystal X-ray diffraction study of the dihexyl derivative showed it had formed a dimer during the analysis. The materials possess lower lying frontier orbitals than pentacene and may have potential applications in organic electronic devices. This synthetic method may be applicable to the synthesis of other azaacenes.