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.
通过用相应的碱金属氢氧化物处理羧酸官能化络合物，可以很容易地获得镍、钯、铂和铜的二价氨基酸衍生双（二硫代氨基甲酸酯）络合物的锂、钠和钾衍生物。我们分离出了 A4[M(L1)2]、A2[M(HL1)2]、A[M(HL1)(H2L1)]（N-二硫代亚氨基二乙酸酯，L1）和 A2[M(L2,3)2]（N-二硫代-l-脯氨酸，L2 和-N-苄基甘氨酸，L3；A = Li、Na、K；M = Ni、Pd、Pt、Cu）等类型的代表性衍生物，并通过光谱和热学方法对其进行了表征。其中六种化合物可以进行单晶 X 射线结构测定，揭示出固态中存在不同的配位聚合物结构和氢键集合体，其中包括溶剂分离的阳离子。过渡金属始终保持全硫配位，并具有确定的几何形状，而碱金属的结构则更为灵活。后者通常由羧酸盐和水配位，但在某些情况下也会与硫供体发生额外的相互作用。
{"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}
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.
{"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}
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.
由于通常用作燃料电池催化剂支撑材料的碳黑（CB）在热力学上不稳定，因此需要找到具有高化学稳定性和导电性的替代支撑材料。早先发表的一篇文章对掺杂 Nb 和 Ta 的 SnO2 进行了研究，揭示了其有趣的导电性能，之后我们将稳定氧化物中的元素相互掺杂到其他氧化物中，并在此报告将 Sn、Hf 和 W 作为客体掺杂到基本氧化物 Nb2O5 和 Ta2O5 中的情况。在 x = 0 - 10 摩尔%的掺杂范围内，研究了作为掺杂成功指标的单胞参数的变化。从 Hf 和 W 掺杂时客体离子在基底氧化物中的完全溶解性到 Sn 掺杂时的有限溶解性，得到了一系列不同的结果。通过漫反射的紫外/可见光谱研究以及电导率测量，我们获得了更多的启示。
{"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}
Daichi Uchida, Mariko Yukimoto, N. Tokitoh, Hiroko Yamada, Y. Mizuhata
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.
{"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}
{"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}
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.
{"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}
Ernesto Ballestero-Martínez, Gerardo Antonio Rodríguez Díaz, Roberto Andrés González León, Terrance J. Hadlington, Jürgen H. Antony, Cristopher Camacho
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.
{"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}
V. V. Lennikov, A. Gómez-Herrero, L. A. Angurel, German Francisco de la Fuente, L. C. Otero-Díaz
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.
{"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}
SAUGATA KONAR, Shibashis Halder, Yeasin Sikdar, Mohd Afzal, Mridula Guin
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.
{"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}
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.
{"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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：