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Structural Study on Alkali‐Carboxylate Functionalized Late‐Transition Metal Bis(dithiocarbamate) Complexes 碱羧酸官能化晚期过渡金属双（二硫代氨基甲酸酯）配合物的结构研究
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-08-09 DOI: 10.1002/zaac.202400064
Phil Liebing, Vreni Behling, Juliane Witzorke
{"title":"Structural Study on Alkali‐Carboxylate Functionalized Late‐Transition Metal Bis(dithiocarbamate) Complexes","authors":"Phil Liebing, Vreni Behling, Juliane Witzorke","doi":"10.1002/zaac.202400064","DOIUrl":"https://doi.org/10.1002/zaac.202400064","url":null,"abstract":"Lithium, sodium, and potassium derivatives of amino‐acid derived bis(dithiocarbamate) complexes of bivalent nickel, palladium, platinum, and copper are readily available by treatment of the carboxylic‐acid functionalized complexes with the respective alkali metal hydroxide. Representative derivatives of the types A4[M(L1)2], A2[M(HL1)2], A[M(HL1)(H2L1)] (N‐dithioato‐iminodiacetate, L1), and A2[M(L2,3)2] (N‐dithioato‐l‐prolinate, L2, and ‐N‐benzylglycinate, L3; A = Li, Na, K; M = Ni, Pd, Pt, Cu) were isolated and characterized by spectroscopic and thermal methods. Six entries were accessible to single‐crystal X‐ray structure determination, revealing the presence of different coordination‐polymeric structures and hydrogen‐bonded assemblies comprising solvent‐separated cations in the solid state. While the transition metal always retains its all‐sulfur coordination with defined geometry, the alkali metals are structurally more flexible. The latter are usually coordinated by carboxylate and water, but additional interactions with sulfur donors are also relevant in some cases.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"40 11","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141922785","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}
引用次数: 0
Synthesis, Crystal Structure, and Optical Properties of a New Quaternary Tin Polychalcogenide K2BaSnSe5 新型四价锡多粲化物 K2BaSnSe5 的合成、晶体结构和光学特性
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-08-08 DOI: 10.1002/zaac.202400050
Jinlong shi, mengran sun, Chunxiao Li, Jiyong Yao
{"title":"Synthesis, Crystal Structure, and Optical Properties of a New Quaternary Tin Polychalcogenide K2BaSnSe5","authors":"Jinlong shi, mengran sun, Chunxiao Li, Jiyong Yao","doi":"10.1002/zaac.202400050","DOIUrl":"https://doi.org/10.1002/zaac.202400050","url":null,"abstract":"One new quaternary tin polychalcogenide K2BaSnSe5 has been synthesized by high temperature solid‐state reaction. It crystallizes in the centrosymmetric space group P21/c of the monoclinic system with cell constants a = 11.948(2) Å, b = 10.367(2) Å, c = 9.2902(19) Å, β = 91.33(3)°, and V = 1150.4(4) Å3. The compound features an interesting zero‐dimensional structure consisting of SnSe5 units, made up of SnSe4 tetrahedra and [Se2] unit, with K+, Ba2+ cations locating in the interstitial sites for charge‐balance. Diffuse reflectance spectrum indicates semiconducting property with an optical band gap of 1.45 eV. Theoretical calculations demonstrate that the band gap of the title compound is determined by [SnSe5] units, and the title compound has a large birefringence of 0.28 at wavelength 1.06 . which implies that K2BaSnSe5 may be an intriguing photoelectronic material.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"119 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141933258","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}
引用次数: 0
Aliovalent doping of niobium and tantalum pentoxide as potential alternative support material for fuel cell catalysts 以五氧化二铌和五氧化二钽的异价掺杂作为燃料电池催化剂的潜在替代支撑材料
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-08-08 DOI: 10.1002/zaac.202400121
Klaus Stöwe, Andreas Giehr
{"title":"Aliovalent doping of niobium and tantalum pentoxide as potential alternative support material for fuel cell catalysts","authors":"Klaus Stöwe, Andreas Giehr","doi":"10.1002/zaac.202400121","DOIUrl":"https://doi.org/10.1002/zaac.202400121","url":null,"abstract":"As the usually used Carbon Blacks (CB) as support materials in fuel cell catalysts are thermodynamically unstable, alternative supports with high chemical stability and electrical conductivity are to be found. After the investigation of Nb and Ta‐doped SnO2 in an earlier publication, which revealed interesting conductivity properties, we expanded our portfolio of mutual doping of elements of stable oxides into the oxides of the others by reporting here on the Sn, Hf and W‐doping as guests into the base oxides Nb2O5 and Ta2O5. The changes in unit cell parameters as indicators for the doping success were investigated in the doping range of x = 0 – 10 mol% guest fraction. From a complete solubility of the guest ions in case of Hf and W‐doping in the base oxides to a limited solubility in case of Sn‐doping, a whole spectrum of different results was obtained. Additional insight came from UV/vis spectroscopic investigations in diffuse reflectance as well as electrical conductivity measurements.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"29 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141968937","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}
引用次数: 0
A Unique Synthetic Route toward a 1,2‐Dihydrodigermene via Formal α‐Elimination of Bromo and Silyl Groups from a Bromo(phenylsilyl)germane 通过溴（苯基硅基）锗中溴基和硅基的正式 α-升华获得 1,2-二氢二锗烯的独特合成路线
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-08-08 DOI: 10.1002/zaac.202400131
Daichi Uchida, Mariko Yukimoto, N. Tokitoh, Hiroko Yamada, Y. Mizuhata
{"title":"A Unique Synthetic Route toward a 1,2‐Dihydrodigermene via Formal α‐Elimination of Bromo and Silyl Groups from a Bromo(phenylsilyl)germane","authors":"Daichi Uchida, Mariko Yukimoto, N. Tokitoh, Hiroko Yamada, Y. Mizuhata","doi":"10.1002/zaac.202400131","DOIUrl":"https://doi.org/10.1002/zaac.202400131","url":null,"abstract":"A 1,2‐dihydrodigermene bearing Tbb {4‐t‐butyl‐1,3‐bis[bis(trimethylsilyl)methyl]phenyl} groups was successfully synthe­sized and isolated via formal α‐elimination of bromo and silyl groups from the corresponding Tbb‐substituted boromo(phenylsilyl)­germane. This novel synthetic method is conducted under mild conditions, representing a significant advantage in the field concerned. The synthesized 1,2‐dihydrodigermene was characterized by NMR spectroscopy, mass spectrometry, and single‐crystal X‐ray crystallography. In the 1H NMR spectrum, the Ge–H unit was found to be less electronically affected from the substituents compared to that of the previously reported 1,2‐dihydrodigermene. Moreover, the UV/vis spectra at various temperatures indicated the formation of the isomeric (dihydrogermyl)germylene. In fact, the 1,2‐dihydrodiger­mene once isolated reacted with DMAP in solution to afford the corresponding complex of the (dihydrogermyl)germylene.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"118 19","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141926228","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}
引用次数: 0
Front Cover: 15/2024) 封面：15/2024)
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-08-05 DOI: 10.1002/zaac.202471501
{"title":"Front Cover: 15/2024)","authors":"","doi":"10.1002/zaac.202471501","DOIUrl":"https://doi.org/10.1002/zaac.202471501","url":null,"abstract":"","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"22 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141933257","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}
引用次数: 0
Functionalization of Si‐ and Al‐based materials with phosphorus dendrimers and their properties 磷树枝状聚合物对硅基和铝基材料的功能化及其特性
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-08-01 DOI: 10.1002/zaac.202400118
Anne-Marie Caminade
{"title":"Functionalization of Si‐ and Al‐based materials with phosphorus dendrimers and their properties","authors":"Anne-Marie Caminade","doi":"10.1002/zaac.202400118","DOIUrl":"https://doi.org/10.1002/zaac.202400118","url":null,"abstract":"The interactions of dendrimers having a phosphorus atom at each branching point, of type poly(phosphorhydrazone) (PPH), with different types of materials based on silicon and aluminum are reviewed. These dendrimers can be used for the functionalization of solid surfaces at the nanoscale, either by covalent immobilization, or by electrostatic interactions, especially for constructing perfectly controlled multi‐layers by layer‐by‐layer (LbL) deposit. The properties of such hybrid materials as chemical sensors, as very sensitive biological sensors, as well as substrates for the growing of cells are described. The PPH dendrimers can also be embedded inside materials. The resulting hybrid materials have been used for the capture of pollutants, in particular CO2 in air and chromate and methylene blue in waste water.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"31 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141885976","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}
引用次数: 0
A structural, spectroscopic and DFT theoretical comparison of the cis and trans isomers of a cyclohexasilane 环己硅烷顺式和反式异构体的结构、光谱和 DFT 理论比较
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-08-01 DOI: 10.1002/zaac.202400093
Ernesto Ballestero-Martínez, Gerardo Antonio Rodríguez Díaz, Roberto Andrés González León, Terrance J. Hadlington, Jürgen H. Antony, Cristopher Camacho
{"title":"A structural, spectroscopic and DFT theoretical comparison of the cis and trans isomers of a cyclohexasilane","authors":"Ernesto Ballestero-Martínez, Gerardo Antonio Rodríguez Díaz, Roberto Andrés González León, Terrance J. Hadlington, Jürgen H. Antony, Cristopher Camacho","doi":"10.1002/zaac.202400093","DOIUrl":"https://doi.org/10.1002/zaac.202400093","url":null,"abstract":"We report a synthesis of the trans and cis isomers of 1,4‐di‐tert‐butyl‐2,2,3,3,5,5,6,6‐octamethyl‐1,4‐diphenylcyclohexasilane (3), together with the solid‐state structure of cis‐3. Both isomers were characterized using multinuclear NMR and UV spectroscopies and were compared based on these data, together with DFT calculations. Remarkably, we found that both isomers of 3 showcase redshifted UV maxima when compared with other known cyclosilanes. To explain this, the theoretical calculations show that the transitions involved in the excited states of trans‐3 and cis‐3 have, in addition to the expected σ conjugation component of the Si6 ring, significant π contributions of phenyl substituents. The results presented herein show the effect of the substituent’s electronic properties regarding reactivity of intermediates, reaction yield, identity, and electronic properties of novel silicon‐containing molecules.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"25 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141885977","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}
引用次数: 0
Direct Laser Synthesis of Fe2O3 modified TiO2 直接激光合成 Fe2O3 改性二氧化钛
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-07-29 DOI: 10.1002/zaac.202400078
V. V. Lennikov, A. Gómez-Herrero, L. A. Angurel, German Francisco de la Fuente, L. C. Otero-Díaz
{"title":"Direct Laser Synthesis of Fe2O3 modified TiO2","authors":"V. V. Lennikov, A. Gómez-Herrero, L. A. Angurel, German Francisco de la Fuente, L. C. Otero-Díaz","doi":"10.1002/zaac.202400078","DOIUrl":"https://doi.org/10.1002/zaac.202400078","url":null,"abstract":"A very fast, selective CO2 laser line scan direct synthesis method is presented and has been applied here to study phase and defect formation within an irradiated mixture of powdered oxides, as a proof‐of‐principle. A nominal composition interval of 0<x<0.03 was conveniently chosen for the TiO2+xFe2O3 system herein reported. X‐ray diffraction analyses were used to determine the main crystalline phase composition. Thus, for 3% mol. Fe2O3, pseudobrookite crystals were found to coexist with rutile‐type MO2‐δ (M=Ti, Fe) with extended defects. These are composed mainly of (121)r and (132)r crystallographic shear planes (CSP`s), where the r sub‐index refers to the rutile subcell. For samples with a lower Fe2O3 content (2, 1, 0.5% mol) only iron‐doped rutile phases were observed, with complex microstructure arising from the presence of multi‐twinned (011)r and (110)r crystals and isolated and/or ordered CSP`s at short length scale. The diverse microstructures observed in the CO2 laser produced samples correlate with the conditions imposed during the laser treatment, which include intrinsically high solidification rates and steep temperature gradients.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"4 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141863285","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}
引用次数: 0
Unraveling strong supramolecular assembly of a novel pyrene based Hg(II)‐complex: Insights from Hirshfeld surface, FMO and molecular electrostatic potential (MEP) analyses 揭示新型芘基 Hg(II)-complex 的强超分子组装：Hirshfeld 表面、FMO 和分子静电位 (MEP) 分析的启示
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-07-29 DOI: 10.1002/zaac.202400074
SAUGATA KONAR, Shibashis Halder, Yeasin Sikdar, Mohd Afzal, Mridula Guin
{"title":"Unraveling strong supramolecular assembly of a novel pyrene based Hg(II)‐complex: Insights from Hirshfeld surface, FMO and molecular electrostatic potential (MEP) analyses","authors":"SAUGATA KONAR, Shibashis Halder, Yeasin Sikdar, Mohd Afzal, Mridula Guin","doi":"10.1002/zaac.202400074","DOIUrl":"https://doi.org/10.1002/zaac.202400074","url":null,"abstract":"A rare pyrene‐based coordination compound of Hg(II) [Hg(L) 2 ] ( 1 ) (where, HL = 2‐((Pyren‐1‐ylmethylene)amino)benzenethiol) was synthesized and characterized by single crystal X‐ Ray diffraction (SC‐XRD) analysis. Crystallographic analysis revealed that complex 1 has seesaw geometry with HL coordinated as a bidentate ligand to a metal ion. The role of weak forces like π∙∙∙π and CH∙∙∙π interactions in influencing the self‐assembly process appears to be of importance. The electronic structure of the complex was predicted using DFT calculations with mixed basis set. DFT calculated structural parameters are in good agreement with the experimentally obtained parameters from XRD. Molecular reactivity and stability of the complex has been assessed through frontier molecular orbital analysis. Evaluation of molecular electrostatic potential (MEP) displaying the electrophilic and nucleophilic reactivity sites. The Hirshfeld surface analysis clearly indicates CH∙∙∙π interaction and π∙∙∙π stacking interactions are responsible to extend the supramolecular network of the complex. Analysis of the finger print plots suggest that H∙∙∙H and H∙∙∙C contacts are major interaction for stabilizing the molecular crystal.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"44 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141863286","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}
引用次数: 0
Structures of Large Tin(IV) Oxo Clusters 大型锡（IV）氧化物团簇的结构
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-07-25 DOI: 10.1002/zaac.202400058
Ulrich Schubert
{"title":"Structures of Large Tin(IV) Oxo Clusters","authors":"Ulrich Schubert","doi":"10.1002/zaac.202400058","DOIUrl":"https://doi.org/10.1002/zaac.202400058","url":null,"abstract":"The article reviews and categorizes the structures of tin oxo clusters with nuclearities ≥6 and compares them with oxo clusters of the other group 4 and 14 metals. Basic construction principles of the cluster core are worked out by comparing the different cluster types and by identifying smaller building blocks. The comparison also shows how the different cluster types are influenced by the interplay between the ligands which stabilize the cluster core and the bridging oxygen atoms.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"60 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141773023","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}
引用次数: 0
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