The conceptual understanding of the reactivity of localized main group element radicals in molecules and ions has so far been strongly focused on carbon radicals in organic compounds.In this study,permanent anions wit...The conceptual understanding of the reactivity of localized main group element radicals in molecules and ions has so far been strongly focused on carbon radicals in organic compounds.In this study,permanent anions with a radical site localized on the vacant vertex of icosahedral closo-dodecaborate anions and 1-carba-closo-dodecaborate anions have been characterized by both various(radical)ion-molecule reactions in the gas phase and by computational investigations,including conceptual DFT,potential energy surfaces(PES)and energy decomposition analysis(EDA).The reactivity of these radical ions towards electron-deficient and electron-rich double bonds as well as their halogen and hydrogen atom abstraction reactions have been studied.The radical ions were varied with respect to their charge state,the nature of the spin-carrying atom and their substituents.Additionally,their reactivity was compared with that of prototypical electrophilic and nucleophilic aryl radicals.Interestingly,not all the(di)anionic radicals are nucleophilic;particularly the ion[CB_(11)I_(11)]^(·-)was characterized as highly electrophilic.Furthermore,simple categorization based on“polarity matching”arguments is not sufficient to fully explain the reactivity of these radical ions towards allyl iodide.Element-specific spatial extension of the spin density and non-covalent interactions of the allyl iodide with the closo-borate or closo-carborate anion framework determine the transition state geometries and energies and therefore strongly influence the relative rate of competing reactions.These results showcase both the transferability and the limitations of“classical”concepts(as typically applied successfully in organic chemistry)for the characterization of ionic borane cluster radicals.Our approach represents a broadly applicable,general method for understanding radical reactivity towards a broad range of reaction partners.展开更多
Zero-dimensional(0D)lead-free perovskites have garnered significant attention due to their unique optoelectronic properties and non-toxicity.However,the single response to stimuli in lead-free perovskites limits the v...Zero-dimensional(0D)lead-free perovskites have garnered significant attention due to their unique optoelectronic properties and non-toxicity.However,the single response to stimuli in lead-free perovskites limits the versatility of multifunctional compounds.In this study,we abandoned the toxic bromic acid and utilized water as the reaction medium,to achieve an environmentally friendly green chemical route.We successfully prepared a zero-dimensional lead-free halide Cs_(2)In_(1−x)Sb_(x)Br_(5)(H_(2)O)perovskite with a fractal structure using an in situ solution crystallization method.Herein,we discovered that the recrystallization occurred beneath the smooth-grown rhombic crystal surface,forming fractal branched crystals.Interestingly,reversible luminescence color transitions from orange-red to yellow and return to the initial state were achieved in response to the individual stimuli of temperature and humidity.We found that H_(2)O molecules played a crucial role in the color tuning,enabling reversible“on–off”switching modes with rapid modulation rates.Moreover,the 0D lead-free halide perovskite Cs_(2)InBr_(5)(H_(2)O):Sb^(3+)also exhibited excellent temperature sensitivity,with the relative sensitivity(SR)reaching up to 9.39%K^(−1).This study provides valuable insights for the further development of halide perovskites in design and application fields,laying a foundation for the development of multifunctional smart materials and temperature sensing applications.展开更多
基金Volkswagen foundation for a Freigeist Fellowshipthe Exploration Grants program of the Boehringer Ingelheim Foundation(BIS)+2 种基金Funding by the Deutsche Forschungsgemeinschaft(DFG,German Research Foundation)Project 498397108TRR 325-444632635(for K.Z.)is gratefully acknowledgedgrateful to Purdue University for the Bilsland Dissertation Fellowship.
文摘The conceptual understanding of the reactivity of localized main group element radicals in molecules and ions has so far been strongly focused on carbon radicals in organic compounds.In this study,permanent anions with a radical site localized on the vacant vertex of icosahedral closo-dodecaborate anions and 1-carba-closo-dodecaborate anions have been characterized by both various(radical)ion-molecule reactions in the gas phase and by computational investigations,including conceptual DFT,potential energy surfaces(PES)and energy decomposition analysis(EDA).The reactivity of these radical ions towards electron-deficient and electron-rich double bonds as well as their halogen and hydrogen atom abstraction reactions have been studied.The radical ions were varied with respect to their charge state,the nature of the spin-carrying atom and their substituents.Additionally,their reactivity was compared with that of prototypical electrophilic and nucleophilic aryl radicals.Interestingly,not all the(di)anionic radicals are nucleophilic;particularly the ion[CB_(11)I_(11)]^(·-)was characterized as highly electrophilic.Furthermore,simple categorization based on“polarity matching”arguments is not sufficient to fully explain the reactivity of these radical ions towards allyl iodide.Element-specific spatial extension of the spin density and non-covalent interactions of the allyl iodide with the closo-borate or closo-carborate anion framework determine the transition state geometries and energies and therefore strongly influence the relative rate of competing reactions.These results showcase both the transferability and the limitations of“classical”concepts(as typically applied successfully in organic chemistry)for the characterization of ionic borane cluster radicals.Our approach represents a broadly applicable,general method for understanding radical reactivity towards a broad range of reaction partners.
基金funding from the National Natural Science Foundation of China(52073165).
文摘Zero-dimensional(0D)lead-free perovskites have garnered significant attention due to their unique optoelectronic properties and non-toxicity.However,the single response to stimuli in lead-free perovskites limits the versatility of multifunctional compounds.In this study,we abandoned the toxic bromic acid and utilized water as the reaction medium,to achieve an environmentally friendly green chemical route.We successfully prepared a zero-dimensional lead-free halide Cs_(2)In_(1−x)Sb_(x)Br_(5)(H_(2)O)perovskite with a fractal structure using an in situ solution crystallization method.Herein,we discovered that the recrystallization occurred beneath the smooth-grown rhombic crystal surface,forming fractal branched crystals.Interestingly,reversible luminescence color transitions from orange-red to yellow and return to the initial state were achieved in response to the individual stimuli of temperature and humidity.We found that H_(2)O molecules played a crucial role in the color tuning,enabling reversible“on–off”switching modes with rapid modulation rates.Moreover,the 0D lead-free halide perovskite Cs_(2)InBr_(5)(H_(2)O):Sb^(3+)also exhibited excellent temperature sensitivity,with the relative sensitivity(SR)reaching up to 9.39%K^(−1).This study provides valuable insights for the further development of halide perovskites in design and application fields,laying a foundation for the development of multifunctional smart materials and temperature sensing applications.
