{"title":"Helical Ni‐Cluster Organic Framework Constructed from Enantiopure Lactate Derivative: Synthesis, Structure and Properties","authors":"Zhong‐Xuan Xu, Xiu‐Ju Ying, Fei Fei","doi":"10.1002/zaac.202400047","DOIUrl":"https://doi.org/10.1002/zaac.202400047","url":null,"abstract":"Abstract Under hydrothermal condition, lactate derivative ( R )‐4‐(1‐ carboxyethoxy)‐2‐methylbenzoic acid (( R )‐H 2 cma) as chiral synthon assembled with 4,4′‐di(1H‐imidazol‐1‐yl)‐1,1′‐biphenyl (4,4’‐dib) and Ni(II) ions to obtain complex {[Ni 2 (( R )‐cma) 2 (4,4’‐dib) 2 (H 2 O)] ⋅ 2H 2 O} n ( HU20‐ R ). In complex HU20‐ R , carboxyl group from lactate unit of ( R )‐cma 2− anion and coordinating H 2 O molecule adopt a μ 2 ‐coordination mode to obtain dinuclear [Ni 2 (CO 2 ) 2 (H 2 O)] 2+ cluster. ( R )‐cma 2− anions and Ni(II) ions build single left‐handed ( R )‐cma‐Ni‐chain, while 4,4’‐dib ligands are bridged by different Ni(II) centers to form double left‐handed 4,4’‐dib‐Ni‐chain. These helical secondary structures are further connected together to result in an 8‐connected 3D framework. PXRD tests indicated that complex HU20‐ R has well hydro‐stability. UV‐vis absorption experiment confirmed that HU20‐ R is a semi‐conducting material with strong absorption capacity for ultraviolet‐visible (UV‐vis) light. Additionally, electrochemical experiment revealed that HU20‐ R has low impedance and high charge transport capacity. Further test results confirm that HU20‐ R has noticeable photo‐catalytic effect in photodegradation of Rhodamine B (RhB) and antiferromagnetic property.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"650 16","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/zaac.202400047","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147914254","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alexander Missyul, Martin Kreuzer, Oleg Usoltsev, Maxim Arsentev, Mikhail Chislov
{"title":"Lithium tris(oxalato)aluminate and its hydrates: structure, mutual transformations and thermal decomposition","authors":"Alexander Missyul, Martin Kreuzer, Oleg Usoltsev, Maxim Arsentev, Mikhail Chislov","doi":"10.1002/zaac.202400032","DOIUrl":"https://doi.org/10.1002/zaac.202400032","url":null,"abstract":"The double oxalates MI3[MIII(C2O4)3] possess rich crystallochemistry and can be used as precursors for various ceramic materials. The article discusses a case of Li3[Al(C2O4)3]. A series of previously unknown hydrates (Li3[Al(C2O4)3]·5.5H2O, Li3[Al(C2O4)3]·4H2O, Li3[Al(C2O4)3]·H2O) was found for this composition, their crystal structure and temperatures of mutual transformations determined. Transformation from Li3[Al(C2O4)3]·4H2O to Li3[Al(C2O4)3]·H2O was found to be accompanied by a change in the topology of the bonding network. Uniaxial negative thermal expansion was found for anhydrous Li3[Al(C2O4)3]. Thermal decomposition of Li3[Al(C2O4)3] was demonstrated to be a promising way to obtain precursors for aluminate ceramics.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"90 14","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141352618","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}
Heiko Ruppert, Till Schreyer, M. C. Dietl, Matthias Rudolph, Stephen K. Hashmi, L. Greb
{"title":"Dynamic Coordination Behavior of a Structurally Constrained, Nucleophilic Sn(II) Towards Gold(I)","authors":"Heiko Ruppert, Till Schreyer, M. C. Dietl, Matthias Rudolph, Stephen K. Hashmi, L. Greb","doi":"10.1002/zaac.202400081","DOIUrl":"https://doi.org/10.1002/zaac.202400081","url":null,"abstract":"Tetradentate meso‐octaalkylcalix[4]pyrroles are well‐established ligands in d‐ and f‐block chemistry. In contrast to the related porphyrins, the sp3‐hybridized meso‐carbon atoms linking the four pyrrole units result in highly divers coordination modes. We previously reported on the combination of this ligand system with Sn(II) centers yielding tetracoordinated stannate(II) anions which could be employed as electron‐rich, strong σ‐donor ligands in transition metal chemistry. With this work we are extending the coordination chemistry of meso‐octaethylcalix[4]pyrrolato stannate(II) [1]2− onto gold(I). Synthesis of mono‐ and dinuclear gold complexes reveal a new dynamic binding mode involving μ2‐bridging coordination of a pyrrole nitrogen atom to both Sn and Au. Single‐crystal X‐ray diffraction and variable temperature NMR spectroscopy combined with quantum mechanical computations and bond analysis tools shed light on the involved intermediates.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"92 11","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141352595","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}
Tsuyoshi Kato, Shintaro Takahashi, A. Baceiredo, N. Saffon‐Merceron
{"title":"Hydrosilylation Reactions with a Dihydrosilylium Ion Stabilized by Coordination of a σ‐Donating Ni(0) Ligand","authors":"Tsuyoshi Kato, Shintaro Takahashi, A. Baceiredo, N. Saffon‐Merceron","doi":"10.1002/zaac.202400062","DOIUrl":"https://doi.org/10.1002/zaac.202400062","url":null,"abstract":"The hydrosilylation reactions of dihydrosilylium ion, stabilized by coordination of a σ‐donating Ni(0) fragment, has been investigated. This complex with two reactive sites, dihydrosilylium and Ni(0) centers, readily reacts with diphenylacetylene via a selective mono‐hydrosilylation reaction to afford the corresponding Ni(0)‐stabilized (hydro)(vinyl)silylium ion. In the case of ethylene, three equivalents of olefin are consumed to give a cationic Ni(II)‐complex featuring a Bu‐Si+‐NiII‐Et moiety with a NHC‐supported Si atom. DFT calculations indicate that the hydrosilylation proceeds by a classical (Chalk‐Harrod type) mechanism with the assistance of NHC ligand moving between Si and Ni centers according to their stabilization requirements.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"72 18","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141357917","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}
Marc Hunsicker, Johannes Krebs, Michael Zimmer, Bernd Morgenstern, Volker Huch, D. Scheschkewitz
{"title":"Synthesis and ligand properties of silsesquioxane‐caged phosphite T7Ph7P","authors":"Marc Hunsicker, Johannes Krebs, Michael Zimmer, Bernd Morgenstern, Volker Huch, D. Scheschkewitz","doi":"10.1002/zaac.202400068","DOIUrl":"https://doi.org/10.1002/zaac.202400068","url":null,"abstract":"The synthesis of the phosphorus‐capped heptaphenylsilsesquioxane T7Ph7P is reported. We show that, unlike previous examples, it readily forms Lewis acid‐base adducts with boranes of different steric demand and the FeCO4 fragment. All complexes were characterized by multinuclear NMR and IR spectroscopy in solution and the solid state. The molecular structures of the adducts with BPh3 and B(C6F5)3 were determined from XRD suitable single crystals. The relative conformation of the Ph and C6F5 rings in T7Ph7P‐B(C6F5)3 suggests favorable π‐interactions, stabilizing the adducts to such a degree that attempts to activate H2 or CO2 were unsuccessful.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"112 38","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141362365","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}
Hans Jürgen Meyer, Markus Stöbele, Albert T Schwarz
{"title":"The Mixed‐Anion compound La2S2(CN2)","authors":"Hans Jürgen Meyer, Markus Stöbele, Albert T Schwarz","doi":"10.1002/zaac.202400038","DOIUrl":"https://doi.org/10.1002/zaac.202400038","url":null,"abstract":"The new binary metal carbodiimide La2S2(CN2) was synthesized via solid‐state metathesis reaction. The crystal structure was solved and refined on basis of single‐crystal X‐ray diffraction data with space group C2/m. The structure is represented by a layered structure, based on alternating layers of lanthanum, sulfide, and carbodiimide units. A close resemblance of the structure with that of La2O2C2 is discussed, as well as the less‐common coordination number seven of the lanthanum atom.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"121 20","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141360528","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}
Jiarong Mai, Shuang Xia, Nan Wang, L. Fu, Lili Liu, Nengfei Yu, Yuping Wu, Rudolf Holze
{"title":"Adding CNTs into Anthracite towards High Performance Anode Materials for Lithium Ion Batteries","authors":"Jiarong Mai, Shuang Xia, Nan Wang, L. Fu, Lili Liu, Nengfei Yu, Yuping Wu, Rudolf Holze","doi":"10.1002/zaac.202400041","DOIUrl":"https://doi.org/10.1002/zaac.202400041","url":null,"abstract":"Commercial graphite anodes face the problems of high preparation temperature and limited specific capacity in lithium‐ion batteries (LIBs). Amorphous carbon anode materials are prepared at low temperatures and have abundant sources of preparation. As a low‐cost carbon source material, anthracite has a practical application value in storing lithium as anode electrodes of LIBs. However, the capacity is not enough to meet the present increasing demand. We added CNTs to enhance the performance of anthracite‐based carbon anodes. The addition of CNTs significantly improves the electrical properties of amorphous carbon anode materials due to the good electronic conductivity. This anthracite‐based carbon with CNTs (A‐C) anode displays a specific cycling capacity of 360 mAh·g‐1 at the current density of 200 mA·g‐1 after 200 cycles in LIBs. We believe that the work has far‐reaching significance for improving the practicability of amorphous carbon anode materials.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"104 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141361310","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}
{"title":"LnSb2O4Br (Ln=Nd and Er) and Sb4O5Br2: Lanthanoid‐Bearing and ‐Free Antimony(III) Oxide Bromides","authors":"R. Locke, Maria Weis, Thomas Schleid","doi":"10.1002/zaac.202300243","DOIUrl":"https://doi.org/10.1002/zaac.202300243","url":null,"abstract":"Sb4O5Br2 crystallizes plate‐shaped in the monoclinic space group P21/c with the lattice parameters a=660.82(5) pm, b=513.71(4) pm, c=1346.35(9) pm and β=97.876(3)° for Z=2. Its crystal structure contains \u0000{[Sb4O5]2+} layers with connected [(Sb1)O3+1]5− ψ1‐units and undisturbed pyramidal [(Sb2)O3]3− ψ1‐units, where the free electron pair is counted as a pseudo‐ligand (ψ). The bromide anions required for charge compensation of these cationic \u0000{[Sb4O5]2+} layers form single sheets and are only bonded via van‐der‐Waals interactions in this crystal structure, as the nearest distance to antimony cations is at least 300 pm. NdSb2O4Br crystallizes plate‐shaped in the monoclinic space group P21/c as well, but with the lattice parameters a=896.24(6) pm, b=801.16(5) pm, c=799.27(5) pm and β=92.129(3)° for Z=4. The [NdO8]13− polyhedra are linked to each other via four edges and thus form fluorite‐related layers \u0000{[NdO\u0000]5−}, which run parallel to the (100) plane. The [SbO3]3− anions share vertices to build chains \u0000{[SbO\u0000O\u0000]−} along [001], which align parallel within the (100) plane. The isolated Br− anions arrange in layers and show a minimum distance of 319 pm to the next Sb3+ cation. ErSb2O4Br crystallizes plate‐shaped in the non‐centrosymmetric tetragonal space group P4212 with the lattice parameters a=774.76(4) pm, c=899.53(6) pm and c/a=1.161 for Z=4. The erbium‐oxygen environment appears to be roughly the same as in NdSb2O4Br, so the main difference is the linkage of the ψ1‐[SbO3]3− units. Four of these [SbO3]3− anions assemble in a ring structure \u0000{[Sb4O8]4−} by sharing corners. Layers of rings are located in the (001) plane and almost planar bromide‐anion slabs assemble between the antimony‐oxygen layers. In this article, all three crystal structures are compared with each other and single‐crystal Raman spectra were recorded and analyzed for NdSb2O4Br and ErSb2O4Br.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"51 8","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141268915","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}
Sebastian Egner, Oluseun Akintola, Winfried Plass, Phil Liebing, Nils Schlörer, Gerald Hörner, Birgit Weber
{"title":"Axial Perturbation of Intermediate Spin (S = 3/2) Iron(III) Complexes with Square Pyramidal N4X Coordination: Solid State Structures and Electronic Properties","authors":"Sebastian Egner, Oluseun Akintola, Winfried Plass, Phil Liebing, Nils Schlörer, Gerald Hörner, Birgit Weber","doi":"10.1002/zaac.202400061","DOIUrl":"https://doi.org/10.1002/zaac.202400061","url":null,"abstract":"The combination of planar‐directing, strong‐field [N4] ligands with a weak axial field component is known to stabilize five‐coordinate iron(III) complexes in otherwise uncommon spin states. In this work, a series of axially perturbed iron(III) complexes of an [N4] macrocyclic ligand of the Jäger type, [Fe(L)X] (with X: Cl, Br, I, NCS) gave intermediate‐spin ground states with axially steered admixture of the high‐spin state, S = 3/2; 5/2. The nature of the electronic ground‐state as deduced from SQUID magnetometry, 57Fe Mössbauer spectroscopy in the solid, and 1H NMR and EPR spectroscopies in (frozen) solutions was discussed in the light of the solid‐state structures, which were obtained from single‐crystal X‐ray diffraction. A DFT‐based protocol was established to quantify the axial field effects and, by including relevant [N4] systems, predict the differential equatorial ligand field components.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"7 6","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141271054","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}
{"title":"A Fundamental Perspective on the Selective Zn Substitution in Ternary Ordered Intermetallic Compound Cu 6 Zn 2 Sb 2","authors":"Nilanjan Roy","doi":"10.1002/zaac.202400030","DOIUrl":"https://doi.org/10.1002/zaac.202400030","url":null,"abstract":"The unique site substitution of Zn in the structure of tetragonal and atomically ordered Cu6Zn2Sb2, followed by the formation of Cu5Zn3Sb2, has been addressed from fundamental perspectives. First principles energy calculations, and semi‐empirical electronic structure calculations using the density of states, crystal orbital Hamilton population, crystal orbital bond index and Mulliken population analysis were performed to understand the observed substitution pattern and the narrow homogeneity range of the titled compound. Mulliken and Löwdin’s approach of charge analysis explain the experimentally proved ‘coloring’ based on the ‘site energy’ argument. The concept of ‘topological charge stabilization’ has been introduced in this context. Valence electron concentration and the optimization of the partially covalent Cu‐Sb interactions also play pivotal role in the electronic stability of the titled phase.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141273341","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}