Jesvita Cardozo, Ouchan He, Wanli Ma, Kallol Ray, Thomas Braun
A [(POCN)Ir(H)(OAc)] complex bearing an iminophosphinite pincer ligand was synthesized. The complex showed catalytic transfer dehydrogenation of various linear and cyclic alkanes with reasonable conversions and a maximum TON of 400 for n‐octane. A catalytic isomerization of 1‐octene to yield internal octenes was also possible. It is notable that the catalyst could perform catalytic transfer dehydrogenation even at a temperature of 100 °C with a TON of 100.
合成了一种带有亚氨基膦钳配体的[(POCN)Ir(H)(OAc)]配合物。该配合物对各种线性和环状烷烃具有催化转移脱氢作用，转化率合理，对正辛烷的最大转化率为 400。还可以催化 1-辛烯的异构化反应，生成内辛烯。值得注意的是，即使在 100 °C 的温度下，该催化剂也能进行催化转移脱氢反应，吨当量为 100。
{"title":"An Iminophosphinite Pincer Iridium Complex: Synthesis and Catalytic Tool for Alkane Transfer Dehydrogenations","authors":"Jesvita Cardozo, Ouchan He, Wanli Ma, Kallol Ray, Thomas Braun","doi":"10.1002/zaac.202400028","DOIUrl":"https://doi.org/10.1002/zaac.202400028","url":null,"abstract":"A [(POCN)Ir(H)(OAc)] complex bearing an iminophosphinite pincer ligand was synthesized. The complex showed catalytic transfer dehydrogenation of various linear and cyclic alkanes with reasonable conversions and a maximum TON of 400 for n‐octane. A catalytic isomerization of 1‐octene to yield internal octenes was also possible. It is notable that the catalyst could perform catalytic transfer dehydrogenation even at a temperature of 100 °C with a TON of 100.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"192 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141194658","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}
Molecular structures and properties of molecular silicon clusters and oligo/polysilanes depend on the substituents on the silicon skeletons. Herein, we report the synthesis of new bicyclo[1.1.1]pentasilanes (BPS) having various alkyl substituents (ethyl, iBu, or 2‐ethylbutyl) at the bridge silicon atoms. All new BPS are characterized by NMR spectroscopy, MS spectrometry, and single crystal X‐ray diffraction (sc‐XRD) analysis. Introduction of longer alkyl groups and unsymmetrical substitution of alkyl groups at the bridge positions on the BPS skeleton substantially improve the solubility toward organic solvents, while the electronic properties are similar to each other.
分子硅簇和低聚/多聚硅烷的分子结构和性质取决于硅骨架上的取代基。在此，我们报告了在桥硅原子上具有各种烷基取代基（乙基、iBu 或 2-乙基丁基）的新型双环[1.1.1]五硅烷（BPS）的合成。所有新型 BPS 均通过核磁共振光谱、质谱分析和单晶 X 射线衍射（sc-XRD）分析进行表征。在 BPS 骨架的桥上位置引入较长的烷基和烷基的非对称取代大大提高了对有机溶剂的溶解性，而电子特性则彼此相似。
{"title":"Selective Synthesis of New Hexaalkylbicyclo[1.1.1]pentasilanes with Improved Solubility","authors":"Yukihiro Morino, S. Ishida, T. Iwamoto","doi":"10.1002/zaac.202400056","DOIUrl":"https://doi.org/10.1002/zaac.202400056","url":null,"abstract":"Molecular structures and properties of molecular silicon clusters and oligo/polysilanes depend on the substituents on the silicon skeletons. Herein, we report the synthesis of new bicyclo[1.1.1]pentasilanes (BPS) having various alkyl substituents (ethyl, iBu, or 2‐ethylbutyl) at the bridge silicon atoms. All new BPS are characterized by NMR spectroscopy, MS spectrometry, and single crystal X‐ray diffraction (sc‐XRD) analysis. Introduction of longer alkyl groups and unsymmetrical substitution of alkyl groups at the bridge positions on the BPS skeleton substantially improve the solubility toward organic solvents, while the electronic properties are similar to each other.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"14 11","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141112525","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}
David van Gerven, Alisha Mertens, Katrin Eppers, Jasper Nickelsen, Mathias Wickleder
Methanesulfonic acid, CH3SO3H, has been crystallized using an in situ technique on a single crystal diffractometer. The crystal structure is monoclinic (P21/c, Z = 4, a = 842.07(4) pm, b = 582.20(3) pm, c = 820.38(4) pm, β = 106.459(2)°) and stamped by the presence of strong hydrogen bonds. Single crystals of the anhydride of methanesulfonic acid, (CH3)2S2O5, formed as a side product in the reaction of bis‐trimethylsilyl‐sulfate, [(CH3)3SiO]2SO2 with SO3 in a sealed glass ampoule. The monoclinic crystal structure (P21/n, Z = 12, a = 1794.5(2) pm, b = 831.75(7) pm, 1383.4(1) pm, β = 110.630(4)°) shows three crystallographically different (CH3)2S2O5 molecules in the unit cell. According to the orientation of the CH3 groups with respect to each other the (CH3)2S2O5 molecule appears as the so‐called trans‐conformer. The structure of both molecules is corroborated by quantum mechanical DFT calculations.
{"title":"In situ crystallization of methanesulfonic acid, CH3SO3H, and serendipitous single crystal formation of its anhydride, (CH3)2S2O5","authors":"David van Gerven, Alisha Mertens, Katrin Eppers, Jasper Nickelsen, Mathias Wickleder","doi":"10.1002/zaac.202400019","DOIUrl":"https://doi.org/10.1002/zaac.202400019","url":null,"abstract":"Methanesulfonic acid, CH3SO3H, has been crystallized using an in situ technique on a single crystal diffractometer. The crystal structure is monoclinic (P21/c, Z = 4, a = 842.07(4) pm, b = 582.20(3) pm, c = 820.38(4) pm, β = 106.459(2)°) and stamped by the presence of strong hydrogen bonds. Single crystals of the anhydride of methanesulfonic acid, (CH3)2S2O5, formed as a side product in the reaction of bis‐trimethylsilyl‐sulfate, [(CH3)3SiO]2SO2 with SO3 in a sealed glass ampoule. The monoclinic crystal structure (P21/n, Z = 12, a = 1794.5(2) pm, b = 831.75(7) pm, 1383.4(1) pm, β = 110.630(4)°) shows three crystallographically different (CH3)2S2O5 molecules in the unit cell. According to the orientation of the CH3 groups with respect to each other the (CH3)2S2O5 molecule appears as the so‐called trans‐conformer. The structure of both molecules is corroborated by quantum mechanical DFT calculations.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"7 12","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141113436","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}
Hydrogel flexible sensors are widely used in wearable devices, health care, intelligent robots and other fields due to their excellent flexibility, biocompatibility and high sensitivity. With the development of single sensor to multi‐channel and multi‐mode sensor network, the sensor data also presents the characteristics of multi‐dimension, complex and massive. Traditional data analysis methods can no longer meet the data analysis requirements of hydrogel flexible sensor networks. The introduction of machine learning (ML) technology optimizes the process of data analysis. With the continuous development of multi‐layer neural network technology and the improvement of computer performance, deep learning (DL) algorithm is increasingly used to achieve higher efficiency and accuracy, provides a powerful tool for data analysis of hydrogel flexible sensor, and accelerates the intelligent process of hydrogel flexible sensor equipment. This paper introduces the classification of hydrogel flexible sensors and the working mechanism and common algorithms of ML, and summarizes the application of ML technology to assist hydrogel flexible sensors in data analysis in the fields of health care and information recognition. This review will provide inspiration and reference for integrating ML technology into the field of hydrogel flexible sensors.
水凝胶柔性传感器因其优异的柔韧性、生物相容性和高灵敏度，被广泛应用于可穿戴设备、医疗保健、智能机器人等领域。随着单传感器向多通道、多模式传感器网络的发展，传感器数据也呈现出多维度、复杂、海量的特点。传统的数据分析方法已无法满足水凝胶柔性传感器网络的数据分析要求。机器学习（ML）技术的引入优化了数据分析过程。随着多层神经网络技术的不断发展和计算机性能的提升，深度学习（DL）算法得到越来越多的应用，实现了更高的效率和精度，为水凝胶柔性传感器的数据分析提供了有力工具，加速了水凝胶柔性传感器装备的智能化进程。本文介绍了水凝胶柔性传感器的分类以及 ML 的工作机理和常用算法，总结了 ML 技术在医疗保健和信息识别领域辅助水凝胶柔性传感器进行数据分析的应用。本综述将为把 ML 技术融入水凝胶柔性传感器领域提供启发和参考。
{"title":"Recent Advances in Machine Learning Assisted Hydrogel Flexible Sensing","authors":"Song Zhou, Dengke Song, Lisha Pu, Wenlong Xu","doi":"10.1002/zaac.202400051","DOIUrl":"https://doi.org/10.1002/zaac.202400051","url":null,"abstract":"Hydrogel flexible sensors are widely used in wearable devices, health care, intelligent robots and other fields due to their excellent flexibility, biocompatibility and high sensitivity. With the development of single sensor to multi‐channel and multi‐mode sensor network, the sensor data also presents the characteristics of multi‐dimension, complex and massive. Traditional data analysis methods can no longer meet the data analysis requirements of hydrogel flexible sensor networks. The introduction of machine learning (ML) technology optimizes the process of data analysis. With the continuous development of multi‐layer neural network technology and the improvement of computer performance, deep learning (DL) algorithm is increasingly used to achieve higher efficiency and accuracy, provides a powerful tool for data analysis of hydrogel flexible sensor, and accelerates the intelligent process of hydrogel flexible sensor equipment. This paper introduces the classification of hydrogel flexible sensors and the working mechanism and common algorithms of ML, and summarizes the application of ML technology to assist hydrogel flexible sensors in data analysis in the fields of health care and information recognition. This review will provide inspiration and reference for integrating ML technology into the field of hydrogel flexible sensors.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"54 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140927970","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}
Two stereoisomers of bicyclic ladder oligosilanes bearing phenyl and tert‐butyldimethylsilyl groups were synthesized, and their structures and electronic properties are compared with previously reported perisopropyl‐substituted analog. These novel ladder oligosilanes have highly twisted structures with the twist angles between the two terminal Si–Si bonds of av. 37.7 and 39.8°. The UV spectra of these compounds show bathochromically shifted absorption maxima with the longest wavelength compared with that of the perisopropyl‐substituted bicyclic ladder oligosilane. The electronic properties of the ladder oligosilanes were analyzed by theoretical calculations.
{"title":"Highly Twisted Ladder Oligosilanes Bearing Phenyl and tert‐Butyldimethylsilyl Groups","authors":"Soichiro Kyushin, Koichi Arai, Ken-ichiro Kanno","doi":"10.1002/zaac.202400034","DOIUrl":"https://doi.org/10.1002/zaac.202400034","url":null,"abstract":"Two stereoisomers of bicyclic ladder oligosilanes bearing phenyl and tert‐butyldimethylsilyl groups were synthesized, and their structures and electronic properties are compared with previously reported perisopropyl‐substituted analog. These novel ladder oligosilanes have highly twisted structures with the twist angles between the two terminal Si–Si bonds of av. 37.7 and 39.8°. The UV spectra of these compounds show bathochromically shifted absorption maxima with the longest wavelength compared with that of the perisopropyl‐substituted bicyclic ladder oligosilane. The electronic properties of the ladder oligosilanes were analyzed by theoretical calculations.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"21 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140927880","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}
We present complexes of alkali metal ions and the ammonium ion with the large cyclodimethylsiloxanes D7 and D8 (D = Me2SiO). The formation of such complexes is accompanied by rearrangements of the ligands to form complexes with a suitable ring size for the metal used. These rearrangements could be suppressed by suitable reaction conditions and rapid work‐up of the reaction mixtures. This enabled the isolation of [Li(D7)][GaI4] (1), [Li(D8)][GaI4] (2), [Na(D8)][GaI4] (3), [K(D8)][GaI4] (4) and [NH4(D8)][GaI4] (5). All of the prepared compounds were analysed using single‐crystal X‐ray diffraction as well as multinuclear NMR spectroscopy. This reveals very different coordination modes in the compounds obtained.
{"title":"Complexes of Alkali Metal and the Ammonium Ion with the Cyclodimethylsiloxane ligands D7 and D8 (D = Me2SiO)","authors":"Carsten von Hänisch, Roman-Malte Richter","doi":"10.1002/zaac.202400036","DOIUrl":"https://doi.org/10.1002/zaac.202400036","url":null,"abstract":"We present complexes of alkali metal ions and the ammonium ion with the large cyclodimethylsiloxanes D7 and D8 (D = Me2SiO). The formation of such complexes is accompanied by rearrangements of the ligands to form complexes with a suitable ring size for the metal used. These rearrangements could be suppressed by suitable reaction conditions and rapid work‐up of the reaction mixtures. This enabled the isolation of [Li(D7)][GaI4] (1), [Li(D8)][GaI4] (2), [Na(D8)][GaI4] (3), [K(D8)][GaI4] (4) and [NH4(D8)][GaI4] (5). All of the prepared compounds were analysed using single‐crystal X‐ray diffraction as well as multinuclear NMR spectroscopy. This reveals very different coordination modes in the compounds obtained.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"90 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140928103","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}
Curing agents for epoxy resin (EP) are one of the most important branches in the polymer materials field due to their enormous potential in many fields, but constructing them in a well‐controlled curing temperature remains challenging. Herein, a novel curing agent is constructed by the zirconium metal‐organic framework (UiO‐66) and [P4442]2[IDA] through an impregnation method. [P4442]2[IDA]@UiO‐66 is utilized as a functional nanofiller and curing agent to construct the [P4442]2[IDA]@UiO‐66/EP nanocomposites. The chemical structures of [P4442]2[IDA]@UiO‐66 were investigated by XRD, SEM, DSC, and TG characterizations. The various [P4442]2[IDA]@UiO‐66 with different loading amounts of [P4442]2[IDA] were used to investigate the curing behaviors of the EP‐51. The DSC results confirm that the curing temperature of the [P4442]2[IDA]@UiO‐66/EP is higher than that of [P4442]2[IDA]/EP. In addition, the kinetic parameters and the activation energy of the curing reaction were acquired according to the fitting of Kissinger equation and Ozawa equation. The drying time of [P4442]2[IDA]@UiO‐66/EP system at 40 °C was enhanced 17 times compare to that of [P4442]2[IDA]/EP system. This study opens new avenues for the rational design of EP nanocomposites by employing ionic liquids@MOFs composite materials as curing agent for wide engineering applications.
{"title":"Construction of [P4442]2[IDA]/Zirconium Metal‐Organic Framework (UiO‐66) for Curing with Epoxy Resin","authors":"Zhiwei Fan, Yilin Ma, Encheng Liu, Junjie Cheng, Fengfeng Chen, Bin Ling, Ningyu Di, Junkuo Gao","doi":"10.1002/zaac.202400031","DOIUrl":"https://doi.org/10.1002/zaac.202400031","url":null,"abstract":"Curing agents for epoxy resin (EP) are one of the most important branches in the polymer materials field due to their enormous potential in many fields, but constructing them in a well‐controlled curing temperature remains challenging. Herein, a novel curing agent is constructed by the zirconium metal‐organic framework (UiO‐66) and [P4442]2[IDA] through an impregnation method. [P4442]2[IDA]@UiO‐66 is utilized as a functional nanofiller and curing agent to construct the [P4442]2[IDA]@UiO‐66/EP nanocomposites. The chemical structures of [P4442]2[IDA]@UiO‐66 were investigated by XRD, SEM, DSC, and TG characterizations. The various [P4442]2[IDA]@UiO‐66 with different loading amounts of [P4442]2[IDA] were used to investigate the curing behaviors of the EP‐51. The DSC results confirm that the curing temperature of the [P4442]2[IDA]@UiO‐66/EP is higher than that of [P4442]2[IDA]/EP. In addition, the kinetic parameters and the activation energy of the curing reaction were acquired according to the fitting of Kissinger equation and Ozawa equation. The drying time of [P4442]2[IDA]@UiO‐66/EP system at 40 °C was enhanced 17 times compare to that of [P4442]2[IDA]/EP system. This study opens new avenues for the rational design of EP nanocomposites by employing ionic liquids@MOFs composite materials as curing agent for wide engineering applications.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"89 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140927965","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}
Hugh Sanderson, Sumanta Banerjee, Mandeep Kaur, Alan Kennedy, Gabriele Kociok-Köhn, Ulrich Hintermair, Stuart Robertson
The solid‐state structures of the first rubidium and caesium pentalenides, [Rb(THF)]2[Ph4Pn] and [Cs(THF)]2[Ph4Pn] have been determined by single crystal X‐ray diffraction. Both were found to be polymeric in the solid state through interactions of the cations with the phenyl substituents, in contrast to their lighter group 1 congeners which are monomeric for lithium and sodium and THF‐bridged for potassium. Both [Rb(THF)]2[Ph4Pn] and [Cs(THF)]2[Ph4Pn] displayed increased η8 coordination, demonstrating a shift towards higher hapticities down the group as previously predicted computationally for the parent M2[Pn] complexes (M = group 1 metal). The solid‐state structures of the polydentate donor adducts [M(DME)x]2[Ph4Pn] (M = Li, x = 1; M = Na, x = 2) and [M(Me6TREN)]2[Ph4Pn] (M = K, Rb, Cs) were all monomeric and displayed increased metal‐carbon distances and decreased ring slippage values relative to the THF adducts.
{"title":"Synthesis and Structure of Heavy Alkali Metal Pentalenides","authors":"Hugh Sanderson, Sumanta Banerjee, Mandeep Kaur, Alan Kennedy, Gabriele Kociok-Köhn, Ulrich Hintermair, Stuart Robertson","doi":"10.1002/zaac.202400039","DOIUrl":"https://doi.org/10.1002/zaac.202400039","url":null,"abstract":"The solid‐state structures of the first rubidium and caesium pentalenides, [Rb(THF)]2[Ph4Pn] and [Cs(THF)]2[Ph4Pn] have been determined by single crystal X‐ray diffraction. Both were found to be polymeric in the solid state through interactions of the cations with the phenyl substituents, in contrast to their lighter group 1 congeners which are monomeric for lithium and sodium and THF‐bridged for potassium. Both [Rb(THF)]2[Ph4Pn] and [Cs(THF)]2[Ph4Pn] displayed increased η8 coordination, demonstrating a shift towards higher hapticities down the group as previously predicted computationally for the parent M2[Pn] complexes (M = group 1 metal). The solid‐state structures of the polydentate donor adducts [M(DME)x]2[Ph4Pn] (M = Li, x = 1; M = Na, x = 2) and [M(Me6TREN)]2[Ph4Pn] (M = K, Rb, Cs) were all monomeric and displayed increased metal‐carbon distances and decreased ring slippage values relative to the THF adducts.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"91 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140884500","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}
Heidi Annemarie Schwartz, Markus Rödl, Kira Küssner
Understanding the interactions between hosts and guests in two‐component systems remains a formidable challenge due to the diverse array of adjusting factors at play. Particularly intriguing within the realm of two‐component systems are those incorporating a photoswitchable molecule within a porous metal‐organic framework (MOF) host. In such configurations, the non‐covalently attached guest molecule undergoes distinct physicochemical changes influenced by factors like guest structure, guest density, and the shape of the MOF pores. In this study, fluorinated azobenzenes (Fx‐AZB) were introduced into the rigid UiO‐66 host, and the resulting optical properties were examined with a focus on the degree of fluorination. The photoisomers of all examined compounds exhibited remarkable stability under repetitive light exposure, showing no signs of fatigue. Moreover, both photoisomers remained stable at room temperature, defying the typical T‐type photochromism associated with azobenzenes. Most notably, all fluorinated azobenzene derivatives displayed nearly complete photoswitching upon exposure to visible light within the UiO‐66 MOF host. This positions these composite materials as leaders in the realm of azobenzene‐based switch@MOF systems.
{"title":"Fluorinated Azobenzenes in UiO‐66: Unveiling Unprecedented Photoswitching Stability and Efficiency in Azobenzene‐Based Switch@MOF Systems","authors":"Heidi Annemarie Schwartz, Markus Rödl, Kira Küssner","doi":"10.1002/zaac.202400018","DOIUrl":"https://doi.org/10.1002/zaac.202400018","url":null,"abstract":"Understanding the interactions between hosts and guests in two‐component systems remains a formidable challenge due to the diverse array of adjusting factors at play. Particularly intriguing within the realm of two‐component systems are those incorporating a photoswitchable molecule within a porous metal‐organic framework (MOF) host. In such configurations, the non‐covalently attached guest molecule undergoes distinct physicochemical changes influenced by factors like guest structure, guest density, and the shape of the MOF pores. In this study, fluorinated azobenzenes (Fx‐AZB) were introduced into the rigid UiO‐66 host, and the resulting optical properties were examined with a focus on the degree of fluorination. The photoisomers of all examined compounds exhibited remarkable stability under repetitive light exposure, showing no signs of fatigue. Moreover, both photoisomers remained stable at room temperature, defying the typical T‐type photochromism associated with azobenzenes. Most notably, all fluorinated azobenzene derivatives displayed nearly complete photoswitching upon exposure to visible light within the UiO‐66 MOF host. This positions these composite materials as leaders in the realm of azobenzene‐based switch@MOF systems.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"85 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140884502","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 bulky aryl thiol, MSFluindSH (1S), and aryl selenol, MSFluindSeH (1Se), possessing a tetramethyl‐s‐hydrindacen‐4’‐yl‐(Rind)‐based substituent containing two fluorenyl groups in 9 and 9’‐positions, were prepared (MSFluind = dispiro[fluorene‐9,3’‐(1’,1’,7’,7’‐tetramethyl‐s‐hydrindacene‐4’‐yl)‐5’,9’’‐fluorene]). The reaction of 1S and 1Se with Et2Zn provided a monomeric zinc aryl thiolate, Zn(SMSFluind)2 (2S), and zinc aryl selenolate, Zn(SeMSFluind)2 (2Se), with essentially two‐coordinate zinc atoms.
{"title":"Hydrindacene‐Based Zinc Aryl Thiolate and Aryl Selenolate Zn(EMSFluind)2 (E = S, Se)","authors":"Jens Beckmann, Pascal Komorr, Pim Puylaert","doi":"10.1002/zaac.202400052","DOIUrl":"https://doi.org/10.1002/zaac.202400052","url":null,"abstract":"The bulky aryl thiol, MSFluindSH (1S), and aryl selenol, MSFluindSeH (1Se), possessing a tetramethyl‐s‐hydrindacen‐4’‐yl‐(Rind)‐based substituent containing two fluorenyl groups in 9 and 9’‐positions, were prepared (MSFluind = dispiro[fluorene‐9,3’‐(1’,1’,7’,7’‐tetramethyl‐s‐hydrindacene‐4’‐yl)‐5’,9’’‐fluorene]). The reaction of 1S and 1Se with Et2Zn provided a monomeric zinc aryl thiolate, Zn(SMSFluind)2 (2S), and zinc aryl selenolate, Zn(SeMSFluind)2 (2Se), with essentially two‐coordinate zinc atoms.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"2012 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140834861","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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