铕（Ⅲ）与HTTA及Phen类衍生物的三元固体配合物的红外及荧光光谱研究

合成了铕（Ⅲ）与２－噻吩甲酰三氟丙酮（ＨＴＴＡ）和１，１０－邻菲罗啉（Ｐｈｅｎ）及其衍生物的三元固体配合物，研究了它们的红外光谱和荧光光谱。     

Die Bestimmung der spezifischen Aktivität trägerarmer Radiojodidlösungen durch papierchromatographische Ermittlung der prozentualen Radioaktivitätsverteilung auf die Jodsubstitutionsproduke von Bromsulfan

Es wird eine neue Methode zur Bestimmung der spezifischen Aktivität trägerarmer Radiojodidlösungen zwischen 5 und 17 Ci/mg (185 bis 630 G Bq/mg) beschrieben, die wesentlich einfacher ist als die bekannten, zum Teil sehr komplizierten Mikroanalysenmethoden und im Prinzip auf eine einfache Trennung eines Radiojodierungsgemisches hinausläuft. Hierzu werden 1 bzw. 2 nmol Bromsulfan (BSP) mit einer exakt zu messenden Menge Na¹²⁵ J bzw. Na¹³¹ J unter Verwendung von Chloramin T radiojodiert. Da die Reaktionsgeschwindigkeitskonstanten der Mono- und Dijodierung des Bromsulfans nicht differierèn, ist es möglich, aus der papierchromatographisch ermittelten prozentualen Radioaktivitätsverteilung das molare Verhältnis der an ein BSP-Molekül gebundenen Jodalome zu berechnen. Bei bekannter BSP-Menge läßt sich daraus die an der Radiojodierung beteiligte Jodmasse ableiten.

Bei der Radiojodierung mit Chloramin T wird jedoch kein 100%iger Jodeinbau erreicht. Die gemessene Aktivitätsmenge muß deshalb durch einen Faktor korrigiert werden, der aus dem Ergebnis der papierchromalographischen Trennung des Reaktionsgemisches abgeleitet wird und der lediglich die auf Mono- und Dijod-BSP entfallenden Radioaktivitätsanteile, nicht dagegen das anorganische Radiojodid berücksichtigt. Die spezifische Aktivität der verwendeten Radiojodidlösung ergibt sich dann als Quotient der korrigierten Radioaktivitätsmenge und der berechneten Radiojodmasse.

Wir haben die erhaltenen Ergebnisse mit den nach einer Referenzmethode gefundenen Werten verglichen. Hierbei wurden die spezifischen Aktivitäten von Na¹²⁵ J aus T3-RIA-Standurdkurven mit ¹²⁵J-T3-Tracern bestimmt, die unter Verwen-dung dieses Na¹²⁵ J präpariert wurden. Es wurde eine Präzision mit einem mittleren Variationskoeffizienlen von ±4% festgestellt.     

Mixed-Valence BN-Doped Corannulene Trimer Radical Cations

Mixed-valence (MV) dimers have been extensively investigated, however, the structure and properties of purely organic MV trimers based on open-shell polycyclic aromatic hydrocarbons remain elusive. Herein, unprecedented MV BN-doped corannulene radical cations [ BN-Cor1 ]₃⋅⋅²⁺ ⋅ 2[BAryl^F₄]⁻ and [ BN-Cor2 ]₃⋅⋅²⁺ ⋅ 2[BAryl^F₄]⁻ were synthesized via chemical oxidation, and their structures were unambiguously confirmed by single-crystal X-ray diffraction. These uncommon radical cations consist of three corannulene cores and two [BAryl^F₄]⁻ anions, and three corannulene motifs [ BN-Cor1 ]₃⋅⋅²⁺ and [ BN-Cor2 ]₃⋅⋅²⁺ in the unit cell exhibit a trimer structure with a slipped π-stacking configuration. Detailed structural analyses further revealed that the corannulene cores exhibit an infinite layered self-assembly configuration, allowing their potential applications as building blocks for molecular conductors. The detection of a forbidden transition (Δm_s=±2) by electron paramagnetic resonance (EPR) spectroscopy further confirmed the existence of two unpaired electrons in the π-trimers and the MV characteristic of these two species. Variable-temperature EPR and conductivity measurements suggested that the BN-doped π-trimers exhibited antiferromagnetic coupling and conductivity properties.     

新有机锡化合物的合成及分子内O→Sn配位键的离解与—1NMR相关性的研究

用具有抗癌活性的(Z)-1-[2-(二卤化苯基锡基乙烯基)]-环辛醇与含氮的双齿配体作用,合成了一系列新的有机锡络合物,通过IR,1HNMR,元素分析和摩尔电导值的测定对其结构、性质进行了表征,特别对有机锡化合物分子内O→Sn配位键的离解与配体中烯基质子化学位移(1HNMR)的相关性进行了讨论.     

吸附/一级热解吸/气相色谱联用测定室内空气中的挥发性有机物

本文以高聚物TenaxTA动态吸附,一级热解吸/毛细管气相色谱法联用测定室内空气中的挥发性有机物。优化了热解吸温度和热解吸时间,建立了苯、甲苯、乙酸正丁酯、乙苯、对二甲苯、苯乙烯、邻二甲苯、正十一烷等8种典型有机污染物的外标定量曲线,各化合物线性范围为103,相关系数R为0.9983～0.9999,最低检出浓度可达2×10-4mg/m3;考察了方法的重复性、热解吸率和残留率,并分析了实际空气样品。     

The Ternary Stannides MgRuSn4 and MgxRh3Sn7—x (x = 0.98—1.55)

The magnesium transition metal stannides MgRuSn₄ and Mg_xRh₃Sn_7—x (x = 0.98—1.55) were synthesized from the elements in glassy carbon crucibles in a water‐cooled sample chamber of a high‐frequency furnace. They were characterized by X‐ray diffraction on powders and single crystals. MgRuSn₄ adopts an ordered PdGa₅ type structure: I4/mcm, a = 674.7(1), c = 1118.1(2) pm, wR2 = 0.0506, 515 F² values and 12 variable parameters. The ruthenium atoms have a square‐antiprismatic tin coordination with Ru—Sn distances of 284 pm. These [RuSn_8/2] antiprisms are condensed via common faces forming two‐dimensional networks. The magnesium atoms fill square‐prismatic cavities between adjacent [RuSn₄] layers with Mg—Sn distances of 299 pm. The rhodium based stannides Mg_xRh₃Sn_7—x crystallize with the cubic Ir₃Ge₇ type structure, space groupe Im3m. The structures of four single crystals with x = 0.98, 1.17, 1.36, and 1.55 have been refined from X‐ray diffractometer data. With increasing tin substitution the a lattice parameter decreases from 932.3(1) pm for x = 0.98 to 929.49(6) pm for x = 1.55. The rhodium atoms have a square antiprismatic tin/magnesium coordination. Mixed Sn/Mg occupancies have been observed for both tin sites but to a larger extend for the 12d Sn2 site. Chemical bonding in MgRuSn₄ and Mg_xRh₃Sn_7—x is briefly discussed.     

一些含半夹心结构ⅥB族金属的1,1’-二硫(硒)二茂铁化合物的合成

CpCr(NO)(CO)_2与Fe(C_5H_4S)_2S反应,形成氧化-还原产物CpCr(NO)(SC_5H_4)_2Fe(1)。双杂核二茂铁化合物CpM(NO)(EC_5H_4)_2Fe[M=Mo,E=S(2a),Se(2b);M=W,E=S(4a),Se(4b)]、CpMo(NO)(SC_5H_4)_2Fe(3)、Cp_2Mo(SeC_5H_4)_2Fe(6)和Cp_2W(SC_5H_4)_2Fe(7)可通过Fe(C_5H_4ELi)_2·2THF(E=S,Se)与CpM(NO)I_2(M=Mo,W)、[CpMo(NO)I_2]_2或Cp_2MCl_2(M=Mo,W)反应制得。三核杂原子二茂铁化合物[CpCr(NO)_2]_2(EC_5H_4)_2Fe[E=S(8a),Se(8b)],由Fe(C_5H_4ELi)_2·2THF(E=S,Se)与二倍摩尔量的CpCr(NO)_2I反应制备。通过AgBF_4氧化2a得到二茂铁离子型化合物[CpMo(NO)(SC_5H_4)_2Fe]~ BF_4~-(5)。采用元素分析、红外光谱、~1H和~(13)C NMR谱以及EI-MS表征了所合成的新型化合物。     

Drei Alkalimetall‐Erbium‐Thiophosphate: Von der Schichtstruktur bei KEr[P2S7] zur dreidimensionalen Vernetzung in NaEr[P2S6] und Cs3Er5[PS4]6

Three Alkali‐Metal Erbium Thiophosphates: From the Layered Structure of KEr[P₂S₇] to the Three‐Dimensional Cross‐Linkage in NaEr[P₂S₆] and Cs₃Er₅[PS₄]₆ The three alkali‐metal erbium thiophosphates NaEr[P₂S₆], KEr[P₂S₇], and Cs₃Er₅[PS₄] show a small selection of the broad variety of thiophosphate units: from ortho‐thiophosphate [PS₄]^3? and pyro‐thiophosphate [S₃P–S–PS₃]^4? with phosphorus in the oxidation state +V to the [S₃P–PS₃]^3? anion with a phosphorus‐phosphorus bond (d(P–P) = 221 pm) and tetravalent phosphorus. In spite of all differences, a whole string of structural communities can be shown, in particular for coordination and three‐dimensional linkage as well as for the phosphorus‐sulfur distances (d(P–S) = 200 – 213 pm). So all three compounds exhibit eightfold coordinated Er³⁺ cations and comparably high‐coordinated alkali‐metal cations (CN(Na⁺) = 8, CN(K⁺) = 9+1, and CN(Cs⁺) ≈ 10). NaEr[P₂S₆] crystallizes triclinically ( ; a = 685.72(5), b = 707.86(5), c = 910.98(7) pm, α = 87.423(4), β = 87.635(4), γ = 88.157(4)°; Z = 2) in the shape of rods, as well as monoclinic KEr[P₂S₇] (P2₁/c; a = 950.48(7), b = 1223.06(9), c = 894.21(6) pm, β = 90.132(4)°; Z = 4). The crystal structure of Cs₃Er₅[PS₄] can also be described monoclinically (C2/c; a = 1597.74(11), b = 1295.03(9), c = 2065.26(15) pm, β = 103.278(4)°; Z = 4), but it emerges as irregular bricks. All crystals show the common pale pink colour typical for transparent erbium(III) compounds.     

Zincophilic Interfacial Manipulation against Dendrite Growth and Side Reactions for Stable Zn Metal Anodes

Constructing multifunctional interphases to suppress the rampant Zn dendrite growth and detrimental side reactions is crucial for Zn anodes. Herein, a phytic acid (PA)-ZnAl coordination compound is demonstrated as a versatile interphase layer to stabilize Zn anodes. The zincophilic PA-ZnAl layer can manipulate Zn²⁺ flux and promote rapid desolvation kinetics, ensuring the uniform Zn deposition with dendrite-free morphology. Moreover, the robust PA-ZnAl protective layer can effectively inhibit the hydrogen evolution reaction and formation of byproducts, further contributing to the reversible Zn plating/stripping with high Coulombic efficiency. As a result, the Zn@PA-ZnAl electrode shows a lower Zn nucleation overpotential and higher Zn²⁺ transference number compared with bare Zn. The Zn@PA-ZnAl symmetric cell exhibits a prolonged lifespan of 650 h tested at 5 mA cm⁻² and 5 mAh cm⁻². Furthermore, the assembled Zn battery full cell based on this Zn@PA-ZnAl anode also delivers decent cycling stability even under harsh conditions.     

Rarefaction on natural compound extracts diversity among genus

The aim of our study was to investigate the intrinsic diversity of genus based on chemical composition of natural extracts of Cacalia, Dracocephalum, Jatropha, Saussurea and Senecio. Four rarefaction approaches (richness, Shannon's entropy, Simpson's diversity, and max-entropy) were implemented as an algorithm and run 10,000 times. Our results showed similar patterns of richness in natural compounds according to genus and of Simpson's diversity index while max-entropy has a similar pattern as Shannon's entropy. The analysis of both richness in active compounds and weight of most frequent extracted compound revealed that Dracocephalum genus is most suitable for propagation.