A5064009313- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Organoboron and organosilicon chemistry
- Inorganic Fluorides and Related Compounds
- Crystallography and molecular interactions
- Advanced NMR Techniques and Applications
- Solid-state spectroscopy and crystallography
- Carbon dioxide utilization in catalysis
- Supramolecular Chemistry and Complexes
- Chemical Synthesis and Reactions
- Machine Learning in Materials Science
- Advanced Chemical Physics Studies
- Luminescence and Fluorescent Materials
- Ionic liquids properties and applications
- Thallium and Germanium Studies
- Silicone and Siloxane Chemistry
- Chemical Thermodynamics and Molecular Structure
- Analytical Chemistry and Sensors
- Metal-Organic Frameworks: Synthesis and Applications
- Fluorine in Organic Chemistry
- Molecular spectroscopy and chirality
- Synthesis and characterization of novel inorganic/organometallic compounds
Heidelberg University
2020-2024
Robert Bosch (Germany)
2024
Abstract The computed fluoride ion affinity (FIA) is a valuable descriptor to assess the Lewis acidity of compound. Despite its widespread use, varying accuracy applied computational models hampers broad comparability literature data. Herein, we evaluate performance selected methods (like DLPNO‐CCSD(T)) in FIA computations against CCSD(T)/CBS data and guide for choice suitable density functionals that allow treatment larger acids. Based on benchmarked methods, an extensive set gas‐phase...
IUPAC defines Lewis acidity as the thermodynamic tendency for pair formation. This strength property was recently specified global (gLA), and is gauged example by fluoride ion affinity. Experimentally, usually evaluated effect on a bound molecule, such induced
The computed fluoride ion affinity (FIA) is a widely applied descriptor to gauge Lewis acidity. Like every other single-parameter acidity scale, the FIA metric suffers from one-dimensionality, that prohibits addressing by multidimensionality it inherently requires (i. e., reference base dependency). However, systematic screening of affinities than much less developed. Herein, we extended our CCSD(T)/CBS benchmark different density functionals and DLPNO-CCSD(T) method for chloride (CIA),...
The quantification of Lewis acidity is fundamental and applied importance in chemistry. However, if neutral charged acids are compared, a coherent ranking has been elusive, severe uncertainties were accepted. With this study, we present systematic computational analysis base affinities 784 mono-, di- tricationic their comparison with 149 representative acids. Evaluating vacuum fluoride ion (FIA) reveals charge-caused clustering that prohibits any meaningful ranking. Instead, solvation-corrected FIA
Abstract “How strong is this Lewis acid?” a question researchers often approach by calculating its fluoride ion affinity (FIA) with quantum chemistry. Here, we present FIA49k, an extensive FIA dataset 48,986 data points calculated at the RI‐DSD‐BLYP‐D3(BJ)/def2‐QZVPP//PBEh‐3c level of theory, including 13 different p ‐block atoms as accepting site. The FIA49k was used to train FIA‐GNN, two message‐passing graph neural networks, which predict gas and solution phase values molecules excluded...
Anionic hypercoordinated silicates with weak donors were proposed as key intermediates in numerous silicon-based reactions. However, their short-lived nature rendered even spectroscopic observations highly challenging. Here, we characterize silicon anions, including the first bromido-, iodido-, formato-, acetato-, triflato- and sulfato-silicates. This is enabled by a new, donor-free polymeric form of Lewis superacidic bis(perchlorocatecholato)silane 1. Spectroscopic, structural,...
Abstract The dynamic covalent chemistry (DCvC) of the Si−O bond holds unique opportunities, but has rarely been employed to assemble discrete molecular architectures. This may be due harsh conditions required initiate exchange reactions at silicon in aprotic solvents. Herein, we provide a comprehensive experimental and computational account on reaction trialkoxysilanes with alcohols identify mild for rapid Substituent, solvent salt effects are uncovered, understood exploited construction...
Abstract IUPAC defines Lewis acidity as the thermodynamic tendency for pair formation. This strength property was recently specified global (gLA), and is gauged example by fluoride ion affinity. Experimentally, usually evaluated effect on a bound molecule, such induced 31 P NMR shift of triethylphosphine oxide in Gutmann–Beckett (GB) method. type scaling called effective (eLA). Unfortunately, gLA eLA often correlate poorly, but reason this unknown. Hence, acid are two distinct properties,...
Abstract Anionic hypercoordinated silicates with weak donors were proposed as key intermediates in numerous silicon‐based reactions. However, their short‐lived nature rendered even spectroscopic observations highly challenging. Here, we characterize silicon anions, including the first bromido‐, iodido‐, formato‐, acetato‐, triflato‐ and sulfato‐silicates. This is enabled by a new, donor‐free polymeric form of Lewis superacidic bis(perchlorocatecholato)silane 1 . Spectroscopic, structural,...
Abstract The quantification of Lewis acidity is fundamental and applied importance in chemistry. However, if neutral charged acids are compared, a coherent ranking has been elusive, severe uncertainties were accepted. With this study, we present systematic computational analysis base affinities 784 mono‐, di‐ tricationic their comparison with 149 representative acids. Evaluating vacuum fluoride ion (FIA) reveals charge‐caused clustering that prohibits any meaningful ranking. Instead,...
… carbon nanorings featuring hoop-shaped segments of gyroid-, diamond-, and primitive-type schwarzites are reported by Qing-Hui Guo et al. in their Research Article (e202402255).The cover picture describes the facile efficient synthesis three employing a naturally bent dibenzo[a,e]-cyclooctatetraene scaffold.These believed to represent first step toward precise syntheses schwarzites. Organic SynthesisIn Communication (e202402886), Weiwei Tang report novel crystallization-induced...
The quantification of Lewis acidity is fundamental and applied importance in chemistry. While the computed fluoride ion affinity (FIA) most widely accepted thermodynamic metric, only sparse experimental values exist. Accordingly, a benchmark methods for computing pair formation enthalpies, also with broader set bases against data, missing. Herein, we evaluate different density functionals 112 experimentally determined acid/base binding enthalpies gauge influences such as solvation correction...
Quantifying Lewis acidity is essential for understanding and optimizing the performance of acids in diverse applications. Next to widely accepted Gutmann‐Beckett (GB) method, using triethyl phosphine oxide (TEPO) as a probe, Childs method—employing trans‐crotonaldehyde (TCA)—gained attention an NMR‐based technique measuring effective (eLA). Despite its steady use, robustness method correlation with other measures remain underexplored. Previous comparisons between GB scales revealed...
Abstract “How strong is this Lewis acid?” a question researchers often approach by calculating its fluoride ion affinity (FIA) with quantum chemistry. Here, we present FIA49k, an extensive FIA dataset 48,986 data points calculated at the RI‐DSD‐BLYP‐D3(BJ)/def2‐QZVPP//PBEh‐3c level of theory, including 13 different p ‐block atoms as accepting site. The FIA49k was used to train FIA‐GNN, two message‐passing graph neural networks, which predict gas and solution phase values molecules excluded...
Abstract The dynamic covalent chemistry (DCvC) of the Si−O bond holds unique opportunities, but has rarely been employed to assemble discrete molecular architectures. This may be due harsh conditions required initiate exchange reactions at silicon in aprotic solvents. Herein, we provide a comprehensive experimental and computational account on reaction trialkoxysilanes with alcohols identify mild for rapid Substituent, solvent salt effects are uncovered, understood exploited construction...