Journal of the American Chemical Society

This record consists of the results from the work 'Informative Training Data for Efficient Property Prediction in Metal-Organic Frameworks by Active Learning', DOI:10.1021/jacs.3c13687 (arxiv DOI: 10.26434/chemrxiv-2023-sw9kv). Training sets selected by Regression-Tree based Active Learning (RT-AL), as well as MAE values on test sets are provided as a benchmark for MOF datasets. Descriptors computed for each dataset are also provided. The codes and a comprehensive example of the usage of RT-AL is provided at https://github.com/AshnaJose/Regression-Tree-based-Active-Learning-for-MOFs.

Data for paper published Feb 05 2024 in the Journal of the American Chemical Society (JACS)IR spectroscopy data.Crystallography data in CIF format.NMR spectroscopy data.EPR spectroscopy data.UV/vis/NIR spectroscopy data.Conductivity data.Thin film characterization data.DFT optimized geometries for 1-Th and 1-U.AbstractAromatic 𝝅-stacking is a weakly attractive, non-covalent interaction often found in biological macromolecules and syn-thetic supramolecular chemistry. The weak non-directional nature of 𝝅-stacking can present challenges in the design of materials owing to their weak, non-directional nature. However, when aromatic 𝝅-systems contain an unpaired electron, stronger attraction involving face-to-face 𝝅-orbital overlap is possible, resulting in covalent so-called ‘pancake’ bonds. Two-electron, multicentre single pancake bonds are well-known whereas four-electron double pancake bonds are rare. Higher-order pancake bonds have been predicted, but experimental systems are unknown. Here, we show that six-electron triple pancake bonds can be synthesized by threefold reduction of hexaazatrinaphthylene (HAN) and subse-quent stacking of the [HAN]³– tri-radicals. Our analysis reveals a multicentre covalent triple pancake bond consisting of a 𝝅-orbital and two equivalent 𝝅-orbitals. An electrostatic stabilizing role is established for tetravalent thorium and urani-um ions in these systems. We also show that the electronic absorption spectrum of the triple pancake bonds closely matches computational predictions, providing experimental verification of these unique interactions. The discovery of conductivity in thin films of the triply bonded 𝝅-dimers presents new opportunities for the discovery of single-component molecular conductors and other spin-based molecular materials

Data for paper published Feb 2024 in the Journal of the American Chemical Society (JACS) (PUBLICATION DATE TBC) IR spectroscopy data. Crystallography data in CIF format. NMR spectroscopy data. EPR spectroscopy data. UV/vis/NIR spectroscopy data. Conductivity data. Thin film characterization data. DFT optimized geometries for 1-Th and 1-U. Abstract Aromatic 𝝅-stacking is a weakly attractive, non-covalent interaction often found in biological macromolecules and syn-thetic supramolecular chemistry. The weak non-directional nature of 𝝅-stacking can present challenges in the design of materials owing to their weak, non-directional nature. However, when aromatic 𝝅-systems contain an unpaired electron, stronger attraction involving face-to-face 𝝅-orbital overlap is possible, resulting in covalent so-called ‘pancake’ bonds. Two-electron, multicentre single pancake bonds are well-known whereas four-electron double pancake bonds are rare. Higher-order pancake bonds have been predicted, but experimental systems are unknown. Here, we show that six-electron triple pancake bonds can be synthesized by threefold reduction of hexaazatrinaphthylene (HAN) and subse-quent stacking of the [HAN]³– tri-radicals. Our analysis reveals a multicentre covalent triple pancake bond consisting of a 𝝅-orbital and two equivalent 𝝅-orbitals. An electrostatic stabilizing role is established for tetravalent thorium and urani-um ions in these systems. We also show that the electronic absorption spectrum of the triple pancake bonds closely matches computational predictions, providing experimental verification of these unique interactions. The discovery of conductivity in thin films of the triply bonded 𝝅-dimers presents new opportunities for the discovery of single-component molecular conductors and other spin-based molecular materials

Complete set of data underlying the experiments conducted in "Redox-Controlled Shunts in a Synthetic Chemical Reaction Cycle". The aim of this publication is to demonstrate a new use of beta'-substituted Michael acceptors (MAs). A new Chemical Reaction Network (CRN) is based based on addition-elimination- as well as oxidation-chemistry. An amine-functionalised MA can be turned into a thiol-functionalised MA with a thiol. This deactivated MA can be reactivated with different oxidants, making it prone to amine-readdition, recovering the starting material. We show that different oxidants lead to different pathways of this CRN with different side products and kinetics. Further, we show a flow-controlled switching between different species of this CRN, offering the ability to recover the starting material and recycle the waste species (disulfide).Please refer to the readme file, explaining the experiment identifiers and conditions of each experiment.

Complete set of data underlying the experiments conducted in "Redox-Controlled Shunts in a Synthetic Chemical Reaction Cycle". The aim of this publication is to demonstrate a new use of beta'-substituted Michael acceptors (MAs). A new Chemical Reaction Network (CRN) is based based on addition-elimination- as well as oxidation-chemistry. An amine-functionalised MA can be turned into a thiol-functionalised MA with a thiol. This deactivated MA can be reactivated with different oxidants, making it prone to amine-readdition, recovering the starting material. We show that different oxidants lead to different pathways of this CRN with different side products and kinetics. Further, we show a flow-controlled switching between different species of this CRN, offering the ability to recover the starting material and recycle the waste species (disulfide).Please refer to the readme file, explaining the experiment identifiers and conditions of each experiment.

Additional material for Berta et al. J. Am. Chem. Soc. 2023, 145, 37, 20302–20310 Paths: minimised structures corresponding to the the GTP hydrolysis mechanism. MD setup: equilibriated inputs for classical MD simulations for WT and mutant systems in CHARMM/NAMD format, set up for the charmm36m FF. NBO: outputs for Natrual Bonding Orbitals analysis carried out for TS and RS structures. GAP mutants: optimised TS and RS structures of the most promising designed GAP mutants.

Data to report https://doi.org/10.1021/jacs.3c03367: Chiral polycyclic aromatic hydrocarbons can be tailored for next-generation photonic materials by carefully designing their molecular as well as supramolecular architectures. Hence, excitonic coupling can boost the chiroptical response in extended aggregates but is still challenging to achieve by pure self-assembly. Whereas most reports on these potential materials cover the UV and visible spectral range, systems in the near infrared are underdeveloped. We report a new quaterrylene bisimide derivative with a conformationally stable twisted π-backbone enabled by the sterical congestion of a fourfold bay-arylation. Rendering the π-subplanes accessible by small imide substituents allows for a slip-stacked chiral arrangement by kinetic self-assembly in low polarity solvents. The well dispersed solid-state aggregate reveals a sharp optical signature of strong J-type excitonic coupling in both, absorption (897 nm) as well as emission (912 nm) far in the NIR region and reaches absorption dissymmetry factors up to 1.1×10−2. The structural elucidation was achieved by AFM and single-crystal X-ray analysis which we combined to derive a structural model of a fourfold stranded enantiopure superhelix. We could deduce the role of phenyl substituents not only granting stable axial chirality but also guiding the chromophore into a chiral supramolecular arrangement needed for strong excitonic chirality.

Original data to report (Abstract): Two [n]heliceno-bis(naphthalimides) 1 and 2 (n = 5 and 6, respectively) where two electron-accepting naphthalimide moieties are attached at both ends of helicene core were synthesized by effective two-step strategy, and their enantiomers could be resolved by chiral stationary-phase high-performance liquid chromatography (HPLC). The single-crystal X-ray diffraction analysis of enantiopure fractions of 1 and 2 confirmed their helical structure, and together with experimental and calculated circular dichroism (CD) spectra, the absolute configuration was unambiguously assigned. Both 1 and 2 exhibit high molar extinction coefficients for the S0–S1 transition and high fluorescence quantum yields (73% for 1 and 69% for 2), both being outstanding for helicene derivatives. The red circularly polarized luminescence (CPL) emission up to 615 nm for 2 with CPL brightness (BCPL) up to 66.5 M–1 cm–1 demonstrates its potential for applications in chiral optoelectronics. Time-dependent density functional theory (TD-DFT) calculations unambiguously showed that the large transition magnetic dipole moment |m| of 2 is responsible for its high absorbance dissymmetry (gabs) and luminescence dissymmetry (glum) factor.

ABSTRACT: Molecular chaperones are proteins that assist in the (un)folding and (dis)assembly of other macromolecular structures toward their biologically functional state in a non-covalent manner. Transferring this concept from nature to artificial self-assembly processes, here, we show a new strategy to control supramolecular polymerization via a chaperone-like two-component system. A new kinetic trapping method was developed that enables efficient retardation of the spontaneous self-assembly of a squaraine dye monomer. The suppression of supramolecular polymerization could be regulated with a cofactor, which precisely initiates self-assembly. The presented system was investigated and characterized by ultraviolet–visible, Fourier transform infrared, and nuclear magnetic resonance spectroscopy, atomic force microscopy, isothermal titration calorimetry, and single-crystal X-ray diffraction. With these results, living supramolecular polymerization and block copolymer fabrication could be realized, demonstrating a new possibility for effective control over supramolecular polymerization processes.