Vedaant Kumar, Kathleen L. May, Alan J. Lough, Robert A. Gossage
Abstract The title compound 1-ferrocenyl-3,3- bis (methylthio)prop-2-en-1-one ( 1 ), a key intermediate in the synthesis of ferrocene-containing heterocycles, has been characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space group P 2 1 / c with 8 molecules in the unit cell. Unit cell parameters are 12.8159(10), 10.8121(9), and 20.8411(16) Å for a , b and c , respectively with β = 98.985(4)°. There are two distinct molecules in the asymmetric unit ( A and B ). Both molecules display a nearly eclipsed conformation with respect to the individual intramolecular cyclopentadienyl units in addition to close intramolecular contacts between the carbonyl O atom and one S atom of the bis -methylthiol functionality. Close intermolecular contacts involving A and B are noted with respect to S⋯H interactions between a thiol-S and the substituted Cp group in addition to C=O∙∙∙HC= interactions with the ene -moiety and a H atom located on one of the thiomethyl groups.
{"title":"The crystal and molecular structure of 1-ferrocenyl-3,3-<i>bis</i>(methylthio)prop-2-en-1-one","authors":"Vedaant Kumar, Kathleen L. May, Alan J. Lough, Robert A. Gossage","doi":"10.1515/znb-2023-0079","DOIUrl":"https://doi.org/10.1515/znb-2023-0079","url":null,"abstract":"Abstract The title compound 1-ferrocenyl-3,3- bis (methylthio)prop-2-en-1-one ( 1 ), a key intermediate in the synthesis of ferrocene-containing heterocycles, has been characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space group P 2 1 / c with 8 molecules in the unit cell. Unit cell parameters are 12.8159(10), 10.8121(9), and 20.8411(16) Å for a , b and c , respectively with β = 98.985(4)°. There are two distinct molecules in the asymmetric unit ( A and B ). Both molecules display a nearly eclipsed conformation with respect to the individual intramolecular cyclopentadienyl units in addition to close intramolecular contacts between the carbonyl O atom and one S atom of the bis -methylthiol functionality. Close intermolecular contacts involving A and B are noted with respect to S⋯H interactions between a thiol-S and the substituted Cp group in addition to C=O∙∙∙HC= interactions with the ene -moiety and a H atom located on one of the thiomethyl groups.","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136227593","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract Two cationic heteroleptic four-coordinate Cu(I) complexes were successfully synthesized and characterized by 1 H NMR, 13 C NMR, 31 P NMR spectroscopy and mass spectrometry. The crystal structures of the complexes have been determined by single-crystal X-ray diffraction. UV/Visible absorption spectra of these complexes show ligand-centered π - π * and charge transfer transitions. In the solid state the complexes show intense emissions with microsecond-scale lifetime and relatively high efficiency at room temperature. The photophysical behavior at T = 298 and 77 K indicates that the emissions of these complexes are thermally activated delayed fluorescence mixed with phosphorescence.
{"title":"Synthesis, structures and photophysical properties of two new Cu(I) complexes","authors":"Xiaojuan Sun, Zhiqiang Wang","doi":"10.1515/znb-2023-0046","DOIUrl":"https://doi.org/10.1515/znb-2023-0046","url":null,"abstract":"Abstract Two cationic heteroleptic four-coordinate Cu(I) complexes were successfully synthesized and characterized by 1 H NMR, 13 C NMR, 31 P NMR spectroscopy and mass spectrometry. The crystal structures of the complexes have been determined by single-crystal X-ray diffraction. UV/Visible absorption spectra of these complexes show ligand-centered π - π * and charge transfer transitions. In the solid state the complexes show intense emissions with microsecond-scale lifetime and relatively high efficiency at room temperature. The photophysical behavior at T = 298 and 77 K indicates that the emissions of these complexes are thermally activated delayed fluorescence mixed with phosphorescence.","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135340328","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Konrad Burkmann, Bastian Hansel, Franziska Habermann, Bianca Störr, Martin Bertau, Florian Mertens
Abstract The heat capacities of NaPF 6 and KPF 6 were measured in a broad temperature range using differential scanning calorimetry. The suitability of applying a modified Neumann Kopp rule to calculate the heat capacity of “PF 6 ” was evaluated in order to obtain a general method to predict the heat capacities of other hexafluorophosphates.
{"title":"Heat capacity of sodium and potassium hexafluorophosphate","authors":"Konrad Burkmann, Bastian Hansel, Franziska Habermann, Bianca Störr, Martin Bertau, Florian Mertens","doi":"10.1515/znb-2023-0084","DOIUrl":"https://doi.org/10.1515/znb-2023-0084","url":null,"abstract":"Abstract The heat capacities of NaPF 6 and KPF 6 were measured in a broad temperature range using differential scanning calorimetry. The suitability of applying a modified Neumann Kopp rule to calculate the heat capacity of “PF 6 ” was evaluated in order to obtain a general method to predict the heat capacities of other hexafluorophosphates.","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136019549","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ralf J. C. Locke, Florian Ledderboge, Thomas Schleid
Abstract The title compounds have been prepared from the elemental lanthanoids and arsenic sesquioxide in 1:1 and 2:3 molar ratios in the presence of a cesium-halide flux at temperatures near 1000 °C generating elemental arsenic as the by-product. With the preparation of B -type La[AsO 3 ] crystallizing in the monoclinic space group P 2 1 / c with the lattice parameters a = 904.03(8), b = 789.96(7), c = 837.49(7) pm and β = 103.354(3)°, both A - and B -type Ln [AsO 3 ] representatives are now available for lanthanum and cerium. The crystal structure consists of two crystallographically distinct Ln 3+ cations with eight- or ninefold coordination by O 2− anions. The Ln 3+ cations are arranged in layers of ( Ln 1) 3+ and corrugated bilayers of ( Ln 2) 3+ cations in the (100) plane. The two different As 3+ cations appear in [AsO 3 ] 3− units, which differ mainly in their environment of Ln 3+ cations. The successful synthesis of the compounds Ln 2 As 4 O 9 ( Ln = Pr, Nd, Eu and Gd) reported here on the one hand closes the structural gap between cerium and neodymium, and on the other hand also extends the spectrum of ternary oxoarsenates(III) of lanthanoids to gadolinium, with the neodymium compound for the first time at standard temperature. The crystals of the Ln 2 As 4 O 9 compounds are triclinic (space group: P1‾ $Pbar{1}$ ) with lattice parameters nicely reflecting the lanthanoid contraction from a = 690.61(5), b = 768.95(6), c = 959.72(8) pm, α = 96.927(3), β = 103.812(3), γ = 104.441(3)° for Pr 2 As 4 O 9 to a = 676.12(5), b = 751.58(6), c = 951.57(8) pm, α = 96.462(3), β = 103.678(3), γ = 104.409(3)° for Gd 2 As 4 O 9 with two crystallographically independent lanthanoid(III) positions. The oxidic environments on these sites show the shape of square antiprisms with significant distortions, but ( Ln 2) 3+ has a ninth oxygen contact in a capped antiprism. The linkage of the polyhedra creates layers in the ab plane, which are separated by the complex anions of arsenic. The oxoarsenate(III) units [AsO 3 ] 3− are linked by sharing oxygen corners to form both dinuclear [As 2 O 5 ] 4− and cyclic tetranuclear [As 4 O 8 ] 4− complex anions, which is why the compounds can also be represented with their structured molecular formula Ln 4 [As 2 O 5 ] 2 [As 4 O 8 ]. The free electron pairs of the arsenic(III) cations point into channels, which are built up in the crystal structure along [010].
在卤化铯熔剂的存在下，在1000℃左右的温度下，以1∶1和2∶3的摩尔比制备了元素类镧和倍半氧化砷，生成了副产物砷。随着B型La[AsO 3]在单斜空间群p21 / c中结晶，晶格参数a = 904.03(8)， B = 789.96(7)， c = 837.49(7) pm， β = 103.354(3)°的制备，a型和B型Ln [AsO 3]代表镧和铈。晶体结构由两种晶体学上不同的ln3 +阳离子组成，由o2 -阴离子配位8或9倍。Ln 3+阳离子在(100)平面上排列成(Ln 1) 3+层和(Ln 2) 3+波纹状双层。在[AsO 3] 3−单元中出现了两种不同的as3 +阳离子，其主要区别在于它们的ln3 +阳离子环境。本文报道的化合物Ln 2 As 4 O 9 (Ln = Pr, Nd, Eu和Gd)的成功合成一方面缩小了铈和钕之间的结构差距，另一方面也将类镧系三元氧砷酸盐(III)的光谱扩展到钆，首次在标准温度下与钕化合物结合。Ln晶体的2 4 O 9化合物三斜(酒吧空间群:P 1‾$ P {1} $)晶格参数很好地反映出lanthanoid = 690.61(5)收缩,b = 768.95 (6), c = 959.72(8)点,α= 96.927(3),β= 103.812(3),γ= 104.441(3)为公关2°4 O 9 = 676.12 (5), b = 751.58 (6), c = 951.57(8)点,α= 96.462(3),β= 103.678(3),γ= 104.409(3)°Gd 2与4 O 9两个结晶学独立lanthanoid (III)的位置。这些位置上的氧化环境显示出方形反棱镜的形状，有明显的畸变，但(ln2) 3+在帽形反棱镜中有第9个氧接触。多面体的连接在ab平面上形成了层，这些层被砷的复杂阴离子分开。氧化砷酸盐(III)单元[aso3] 3−通过共享氧角连接，形成双核[as2o5] 4−和环四核[as2o8] 4−络合物阴离子，这就是为什么这些化合物也可以用它们的结构分子式Ln 4 [as2o5] 2 [as2o8]表示。砷(III)阳离子的自由电子对指向沿[010]在晶体结构中建立的通道。
{"title":"Zur Kenntnis ternärer Oxoarsenate(III) dreiwertiger Lanthanoide: Synthese und Charakterisierung von <i>Ln</i>AsO<sub>3</sub>- und <i>Ln</i> <sub>2</sub>As<sub>4</sub>O<sub>9</sub>-Vertretern mit <i>Ln</i> = La und Ce sowie <i>Ln</i> = Pr, Nd, Sm–Gd","authors":"Ralf J. C. Locke, Florian Ledderboge, Thomas Schleid","doi":"10.1515/znb-2023-0069","DOIUrl":"https://doi.org/10.1515/znb-2023-0069","url":null,"abstract":"Abstract The title compounds have been prepared from the elemental lanthanoids and arsenic sesquioxide in 1:1 and 2:3 molar ratios in the presence of a cesium-halide flux at temperatures near 1000 °C generating elemental arsenic as the by-product. With the preparation of B -type La[AsO 3 ] crystallizing in the monoclinic space group P 2 1 / c with the lattice parameters a = 904.03(8), b = 789.96(7), c = 837.49(7) pm and β = 103.354(3)°, both A - and B -type Ln [AsO 3 ] representatives are now available for lanthanum and cerium. The crystal structure consists of two crystallographically distinct Ln 3+ cations with eight- or ninefold coordination by O 2− anions. The Ln 3+ cations are arranged in layers of ( Ln 1) 3+ and corrugated bilayers of ( Ln 2) 3+ cations in the (100) plane. The two different As 3+ cations appear in [AsO 3 ] 3− units, which differ mainly in their environment of Ln 3+ cations. The successful synthesis of the compounds Ln 2 As 4 O 9 ( Ln = Pr, Nd, Eu and Gd) reported here on the one hand closes the structural gap between cerium and neodymium, and on the other hand also extends the spectrum of ternary oxoarsenates(III) of lanthanoids to gadolinium, with the neodymium compound for the first time at standard temperature. The crystals of the Ln 2 As 4 O 9 compounds are triclinic (space group: <m:math xmlns:m=\"http://www.w3.org/1998/Math/MathML\"> <m:mrow> <m:mi>P</m:mi> <m:mover accent=\"true\"> <m:mn>1</m:mn> <m:mo>‾</m:mo> </m:mover> </m:mrow> </m:math> $Pbar{1}$ ) with lattice parameters nicely reflecting the lanthanoid contraction from a = 690.61(5), b = 768.95(6), c = 959.72(8) pm, α = 96.927(3), β = 103.812(3), γ = 104.441(3)° for Pr 2 As 4 O 9 to a = 676.12(5), b = 751.58(6), c = 951.57(8) pm, α = 96.462(3), β = 103.678(3), γ = 104.409(3)° for Gd 2 As 4 O 9 with two crystallographically independent lanthanoid(III) positions. The oxidic environments on these sites show the shape of square antiprisms with significant distortions, but ( Ln 2) 3+ has a ninth oxygen contact in a capped antiprism. The linkage of the polyhedra creates layers in the ab plane, which are separated by the complex anions of arsenic. The oxoarsenate(III) units [AsO 3 ] 3− are linked by sharing oxygen corners to form both dinuclear [As 2 O 5 ] 4− and cyclic tetranuclear [As 4 O 8 ] 4− complex anions, which is why the compounds can also be represented with their structured molecular formula Ln 4 [As 2 O 5 ] 2 [As 4 O 8 ]. The free electron pairs of the arsenic(III) cations point into channels, which are built up in the crystal structure along [010].","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135094395","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Maximilian Kai Reimann, Wilma Pröbsting, Aylin Koldemir, Jana Palms, Rainer Pöttgen
Abstract CeAuGe and CeAuSn (both NdPtSb type, space group P 6 3 mc ) form a complete solid solution CeAuGe 1− x Sn x with Vegard-type behavior of the cell volume. Samples with steps of x = 0.1 were synthesized from the pure elements by arc-melting. The structure of CeAuGe 0.13(2) Sn 0.87(2) was refined from single-crystal X-ray diffractometer data: a = 469.10(6), c = 773.90(10) pm, wR 2 = 0.0359, 251 F 2 values and 12 variables. The induced structural disorder caused by the Ge/Sn mixing affects the magnetic ground state of the cerium ions. From the germanium-rich side, the Curie temperature of CeAuGe (10.0 K) decreases towards CeAuGe 0.6 Sn 0.4 , while the Néel temperature of CeAuSn (4.4 K) decreases at the tin-rich side toward CeAuGe 0.4 Sn 0.6 . The switch of the magnetic ground state occurs approximately around the Ge/Sn ratio of 1:1. 119 Sn Mössbauer spectra of CeAuGe 0.1 Sn 0.9 and CeAuGe 0.7 Sn 0.3 confirm the presence of single crystallographic tin sites in both cases, and the isomer shifts are comparable to that of pure CeAuSn, indicating similar electron density distribution at the tin nuclei.
CeAuGe和CeAuSn(均为NdPtSb型，空间群P 6 3 mc)形成完整的固溶体CeAuGe 1−x Sn x，胞体体积呈维加德型行为。采用电弧熔炼法制备了步长为x = 0.1的纯元素样品。根据单晶x射线衍射数据，对CeAuGe 0.13(2) Sn 0.87(2)的结构进行了细化:a = 469.10(6)， c = 773.90(10) pm, wr2 = 0.0359, f2值251，变量12。Ge/Sn混合引起的结构紊乱影响了铈离子的磁性基态。富锗侧CeAuGe (10.0 K)的居里温度向CeAuGe 0.6 Sn 0.4方向降低，富锡侧CeAuGe (4.4 K)的n温度向CeAuGe 0.4 Sn 0.6方向降低。磁性基态的切换大约发生在Ge/Sn比为1:1左右。CeAuGe 0.1 Sn 0.9和CeAuGe 0.7 Sn 0.3的Sn Mössbauer谱图证实了在这两种情况下单晶锡位的存在，并且同分异构体位移与纯CeAuSn相当，表明锡核处的电子密度分布相似。
{"title":"A switch from ferro- to antiferromagnetic ordering in the solid solutions CeAuGe<sub>1−<i>x</i> </sub>Sn<sub> <i>x</i> </sub>","authors":"Maximilian Kai Reimann, Wilma Pröbsting, Aylin Koldemir, Jana Palms, Rainer Pöttgen","doi":"10.1515/znb-2023-0073","DOIUrl":"https://doi.org/10.1515/znb-2023-0073","url":null,"abstract":"Abstract CeAuGe and CeAuSn (both NdPtSb type, space group P 6 3 mc ) form a complete solid solution CeAuGe 1− x Sn x with Vegard-type behavior of the cell volume. Samples with steps of x = 0.1 were synthesized from the pure elements by arc-melting. The structure of CeAuGe 0.13(2) Sn 0.87(2) was refined from single-crystal X-ray diffractometer data: a = 469.10(6), c = 773.90(10) pm, wR 2 = 0.0359, 251 F 2 values and 12 variables. The induced structural disorder caused by the Ge/Sn mixing affects the magnetic ground state of the cerium ions. From the germanium-rich side, the Curie temperature of CeAuGe (10.0 K) decreases towards CeAuGe 0.6 Sn 0.4 , while the Néel temperature of CeAuSn (4.4 K) decreases at the tin-rich side toward CeAuGe 0.4 Sn 0.6 . The switch of the magnetic ground state occurs approximately around the Ge/Sn ratio of 1:1. 119 Sn Mössbauer spectra of CeAuGe 0.1 Sn 0.9 and CeAuGe 0.7 Sn 0.3 confirm the presence of single crystallographic tin sites in both cases, and the isomer shifts are comparable to that of pure CeAuSn, indicating similar electron density distribution at the tin nuclei.","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135548133","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Martin Klotz, Markus Seibald, Dominik Baumann, Klaus Wurst, Gunter Heymann, Hubert Huppertz
Abstract The compounds Li 6 MoN 4 and Li 6 WN 4 were prepared from the reactants M ( M = Mo, W) and Li 3 N in a radiofrequency furnace at 1000 °C. The lithonitridometallates crystallize in the tetragonal system with the lattice parameters: a = 6.6844(1), c = 4.9294(1) Å for Li 6 WN 4 based on single-crystal X-ray diffraction data and a = 6.6611(3), c = 4.9338(3) Å for Li 6 MoN 4 taken from powder X-ray diffraction data. Colorless to slightly reddish single-crystals of the tungsten compound were isolated and the crystal structure was refined in the space group P 4 2 / nmc (no. 137) with Z = 2 and the powder X-ray data of the molybdenum compound were analyzed by a Rietveld refinement. Both structures belong to the Li 6 [ZnO 4 ] type published by Hoppe et al. in 1987 (Untenecker H., Hoppe R. Z. Anorg. Allg. Chem. 1987, 551 , 147–150) and could be doped with Ce 3+ for the first time. The investigated compounds show a reddish color impression upon UV to blue irradiation and exhibit a broad emission band with a maximum at λ max = 693 nm (fwhm 97 nm) for Li 6 MoN 4 and at λ max = 653 nm (fwhm 133 nm) for Li 6 WN 4 .
摘要:以反应物M (M = Mo, W)和Li 3n为原料，在1000℃的射频炉中制备了化合物Li 6mon4和Li 6w4。单晶x射线衍射数据表明，锂氮金属在四角形体系中结晶，晶格参数为a = 6.6844(1)， c = 4.9294(1) Å;粉末x射线衍射数据表明，锂氮金属在四角形体系中结晶，晶格参数为a = 6.6611(3)， c = 4.9338(3) Å。分离出无色至微红色的钨化合物单晶，并在p42 / nmc (no. 6)空间群中细化了晶体结构。采用Rietveld细化法对钼化合物的粉末x射线数据进行了分析。这两种结构都属于Hoppe等人在1987年发表的Li 6 [ZnO 4]型(Untenecker H.， Hoppe R. Z. Anorg.)。Allg。化学，1987,551,147-150)，并且首次可以掺杂ce3 +。所研究的化合物在紫外至蓝光照射下呈现红色，并且具有较宽的发射带，Li 6 mon4的最大波长为λ max = 693 nm (fwhm为97 nm)， Li 6 w4的最大波长为λ max = 653 nm (fwhm为133 nm)。
{"title":"Crystal structures and luminescence properties of Li<sub>6</sub> <i>M</i>N<sub>4</sub>:Ce<sup>3+</sup> (<i>M</i> = Mo, W)","authors":"Martin Klotz, Markus Seibald, Dominik Baumann, Klaus Wurst, Gunter Heymann, Hubert Huppertz","doi":"10.1515/znb-2023-0057","DOIUrl":"https://doi.org/10.1515/znb-2023-0057","url":null,"abstract":"Abstract The compounds Li 6 MoN 4 and Li 6 WN 4 were prepared from the reactants M ( M = Mo, W) and Li 3 N in a radiofrequency furnace at 1000 °C. The lithonitridometallates crystallize in the tetragonal system with the lattice parameters: a = 6.6844(1), c = 4.9294(1) Å for Li 6 WN 4 based on single-crystal X-ray diffraction data and a = 6.6611(3), c = 4.9338(3) Å for Li 6 MoN 4 taken from powder X-ray diffraction data. Colorless to slightly reddish single-crystals of the tungsten compound were isolated and the crystal structure was refined in the space group P 4 2 / nmc (no. 137) with Z = 2 and the powder X-ray data of the molybdenum compound were analyzed by a Rietveld refinement. Both structures belong to the Li 6 [ZnO 4 ] type published by Hoppe et al. in 1987 (Untenecker H., Hoppe R. Z. Anorg. Allg. Chem. 1987, 551 , 147–150) and could be doped with Ce 3+ for the first time. The investigated compounds show a reddish color impression upon UV to blue irradiation and exhibit a broad emission band with a maximum at λ max = 693 nm (fwhm 97 nm) for Li 6 MoN 4 and at λ max = 653 nm (fwhm 133 nm) for Li 6 WN 4 .","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136237716","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yu-Shu Zhu, Cui-Er Deng, Xue-Chun Zhang, Kun-Lin Huang, Xi Liu
Abstract A novel three-dimensional coordination compound has been solvothermally synthesized based on a tetracarboxylate ligand H 4 L (H 4 L = 1,3,6,8-tetrakis(4-carboxylphenyl)pyrene), Zn 2 L(H 2 O) 2 ·2DEF ( 1 ) (DEF = N , N ′-diethylformamide). Each Zn ion is coordinated by four carboxylate oxygen atoms from four L 4− ligands and one oxygen atom from a water molecule to provide a distorted square-pyramidal geometry. Pairs of adjacent Zn cations are bridged by four carboxylate groups of four different L 4− ligands to generate a paddle-wheel [Zn 2 (COO) 4 (H 2 O) 2 ] secondary building unit (SBU). Each SUB is further linked to four L 4− ligands to give a three-dimensional framework with cds-type (CdSO 4 -type) topology. The crystal structure has been determined via single-crystal X-ray diffraction, and the compound was characterized by elemental and thermal analysis, infrared spectroscopy, powder X-ray diffraction, and solid-state photoluminescence measurements.
{"title":"A zinc coordination compound showing green photoluminescence","authors":"Yu-Shu Zhu, Cui-Er Deng, Xue-Chun Zhang, Kun-Lin Huang, Xi Liu","doi":"10.1515/znb-2023-0063","DOIUrl":"https://doi.org/10.1515/znb-2023-0063","url":null,"abstract":"Abstract A novel three-dimensional coordination compound has been solvothermally synthesized based on a tetracarboxylate ligand H 4 L (H 4 L = 1,3,6,8-tetrakis(4-carboxylphenyl)pyrene), Zn 2 L(H 2 O) 2 ·2DEF ( 1 ) (DEF = N , N ′-diethylformamide). Each Zn ion is coordinated by four carboxylate oxygen atoms from four L 4− ligands and one oxygen atom from a water molecule to provide a distorted square-pyramidal geometry. Pairs of adjacent Zn cations are bridged by four carboxylate groups of four different L 4− ligands to generate a paddle-wheel [Zn 2 (COO) 4 (H 2 O) 2 ] secondary building unit (SBU). Each SUB is further linked to four L 4− ligands to give a three-dimensional framework with cds-type (CdSO 4 -type) topology. The crystal structure has been determined via single-crystal X-ray diffraction, and the compound was characterized by elemental and thermal analysis, infrared spectroscopy, powder X-ray diffraction, and solid-state photoluminescence measurements.","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136263888","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract Crystals of tBuPCl2 were obtained by a short-path sublimation at 80 °C/0.150 mbar. The structure determination of tBuPCl2 was based on X-ray powder data. The measurements were carried out in a temperature range from 173 K to r. t. At 173 K the X-ray powder pattern has been assigned to an orthorhombic phase, and that at 213 K to a plastic-crystalline, cubic phase. We further investigated the reactivity of tBuPCl2 towards Na(thf)2[SitBu3] at ambient temperature. The reaction of tBuPCl2 with two equivalents of Na(thf)2[SitBu3] gave together with tBu3SiCl the yet unknown phosphanediide Na2[PtBu] by a chlorine-sodium exchange. The identity of Na2[PtBu] was confirmed by 31P NMR spectroscopy and its existence was unambiguously demonstrated by its protonation with methanol and the consequent formation of tBuPH2.
{"title":"tert-Butyldichlorophosphane: crystal structure and its reactivity towards supersilyl sodium","authors":"L. Fink, Marcel Bamberg, E. Alig, H. Lerner","doi":"10.1515/znb-2023-0041","DOIUrl":"https://doi.org/10.1515/znb-2023-0041","url":null,"abstract":"Abstract Crystals of tBuPCl2 were obtained by a short-path sublimation at 80 °C/0.150 mbar. The structure determination of tBuPCl2 was based on X-ray powder data. The measurements were carried out in a temperature range from 173 K to r. t. At 173 K the X-ray powder pattern has been assigned to an orthorhombic phase, and that at 213 K to a plastic-crystalline, cubic phase. We further investigated the reactivity of tBuPCl2 towards Na(thf)2[SitBu3] at ambient temperature. The reaction of tBuPCl2 with two equivalents of Na(thf)2[SitBu3] gave together with tBu3SiCl the yet unknown phosphanediide Na2[PtBu] by a chlorine-sodium exchange. The identity of Na2[PtBu] was confirmed by 31P NMR spectroscopy and its existence was unambiguously demonstrated by its protonation with methanol and the consequent formation of tBuPH2.","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77886191","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Valentin Antoine Chamard, Samir F. Matar, Lars Schumacher, Christian Paulsen, Jutta Kösters, Theresa Block, Rainer Pöttgen
Abstract Single crystals of Y 3 Ru were obtained as a side product during phase analytical studies of yttrium-rich compounds in the system Y–Ru–Zn. The structure of Y 3 Ru was refined from single-crystal X-ray diffractometer data: Fe 3 C type, Pnma , a = 732.51(7), b = 925.61(8), c = 633.66(10) pm, w R = 0.0639, 811 F 2 values, 23 variables. The ruthenium atoms have coordination number 9 in form of a strongly distorted tricapped trigonal yttrium prism with Ru–Y distances ranging from 275–391 pm. The second substructure concerns empty Y 6 octahedra ( d (Y–Y) = 344–396 pm). Electronic structure calculations show a net charge transfer from yttrium to ruthenium and underpin the essentially covalent Y–Ru bonding. A phase-pure sample of Y 3 Ru was synthesized from the elements by arc-melting. Temperature-dependent magnetic susceptibility studies of this sample reveal Pauli paramagnetism (3.6(1) × 10 −5 emu mol −1 at T = 300 K).
摘要在对Y - Ru - zn体系中富钇化合物进行相分析研究时，得到了y3ru单晶作为副产物。利用单晶x射线衍射仪数据对y3 Ru的结构进行了细化:fe3 C型，Pnma, a = 732.51(7)， b = 925.61(8)， C = 633.66(10) pm, w R = 0.0639, f2值811,23个变量。钌原子的配位数为9，呈强畸变三角钇棱镜状，Ru-Y距离为275 ~ 391 pm。第二个子结构涉及空的y6八面体(d (Y - Y) = 344-396 pm)。电子结构计算显示净电荷从钇转移到钌，并支持本质上共价的Y-Ru键。采用电弧熔炼法制备了相纯y3ru样品。温度相关磁化率研究表明，该样品具有泡利顺磁性(T = 300 K时为3.6(1)× 10−5 emu mol−1)。
{"title":"Cementite-type Y<sub>3</sub>Ru","authors":"Valentin Antoine Chamard, Samir F. Matar, Lars Schumacher, Christian Paulsen, Jutta Kösters, Theresa Block, Rainer Pöttgen","doi":"10.1515/znb-2023-0058","DOIUrl":"https://doi.org/10.1515/znb-2023-0058","url":null,"abstract":"Abstract Single crystals of Y 3 Ru were obtained as a side product during phase analytical studies of yttrium-rich compounds in the system Y–Ru–Zn. The structure of Y 3 Ru was refined from single-crystal X-ray diffractometer data: Fe 3 C type, Pnma , a = 732.51(7), b = 925.61(8), c = 633.66(10) pm, w R = 0.0639, 811 F 2 values, 23 variables. The ruthenium atoms have coordination number 9 in form of a strongly distorted tricapped trigonal yttrium prism with Ru–Y distances ranging from 275–391 pm. The second substructure concerns empty Y 6 octahedra ( d (Y–Y) = 344–396 pm). Electronic structure calculations show a net charge transfer from yttrium to ruthenium and underpin the essentially covalent Y–Ru bonding. A phase-pure sample of Y 3 Ru was synthesized from the elements by arc-melting. Temperature-dependent magnetic susceptibility studies of this sample reveal Pauli paramagnetism (3.6(1) × 10 −5 emu mol −1 at T = 300 K).","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135297908","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract A mononuclear Mn(II) complex [Mn( p -MOPhH 2 IDC) 2 (H 2 O) 2 ]·2(DMF), was synthesized by the reaction of p -MOPhH 3 IDC (2-(4-methoxyphenyl)-1 H -imidazole-4,5-dicarboxylic acid) and Mn(CH 3 COO) 2 ·4H 2 O under solvothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, IR and UV–vis spectroscopy. The structure analysis revealed that the manganese(II) center has a six-coordinated octahedral coordination geometry. The performance of a Mn(II) complex-doped carbon paste electrode (Mn-CPE) in the electrocatalytic hydrogen evolution reaction (HER) was evaluated by linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) methods. The polarization curve shows that the η 10 298K (overpotential, 10 mA cm −2 ) of the Mn-CPE was positively shifted by 341 mV compared with the bare CPE (without complex). The Tafel slope of the Mn-CPE was 161 mV dec −1 . These data indicate that the Mn-CPE was effective in the HER electrocatalytic reaction. For EIS experiments, the arc diameter of the high-frequency region of the Mn-CPE was much smaller than that of the bare CPE, which further indicates the effective catalytic capacity of the Mn(II) complex for hydrogen evolution. The information obtained from this study will help to expand the application of Mn(II) complexes in the field of electrochemistry.
{"title":"Electrocatalytic hydrogen evolution at carbon paste electrodes doped with a manganese(II) imidazoledicarboxylate complex","authors":"Zhengwei Wu, Tiantian Wan, Xiaoxia Kong, Qinqin Shen, Kaiyi Li, Huilu Wu","doi":"10.1515/znb-2023-0027","DOIUrl":"https://doi.org/10.1515/znb-2023-0027","url":null,"abstract":"Abstract A mononuclear Mn(II) complex [Mn( p -MOPhH 2 IDC) 2 (H 2 O) 2 ]·2(DMF), was synthesized by the reaction of p -MOPhH 3 IDC (2-(4-methoxyphenyl)-1 H -imidazole-4,5-dicarboxylic acid) and Mn(CH 3 COO) 2 ·4H 2 O under solvothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, IR and UV–vis spectroscopy. The structure analysis revealed that the manganese(II) center has a six-coordinated octahedral coordination geometry. The performance of a Mn(II) complex-doped carbon paste electrode (Mn-CPE) in the electrocatalytic hydrogen evolution reaction (HER) was evaluated by linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) methods. The polarization curve shows that the η 10 298K (overpotential, 10 mA cm −2 ) of the Mn-CPE was positively shifted by 341 mV compared with the bare CPE (without complex). The Tafel slope of the Mn-CPE was 161 mV dec −1 . These data indicate that the Mn-CPE was effective in the HER electrocatalytic reaction. For EIS experiments, the arc diameter of the high-frequency region of the Mn-CPE was much smaller than that of the bare CPE, which further indicates the effective catalytic capacity of the Mn(II) complex for hydrogen evolution. The information obtained from this study will help to expand the application of Mn(II) complexes in the field of electrochemistry.","PeriodicalId":23831,"journal":{"name":"Zeitschrift für Naturforschung B","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135298776","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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