Article
Chemistry, Organic
Peter R. Schreiner, Lars Rummel, Kai Hanke, Jonathan Becker
Summary: In this study, the thermodynamic stability of cis- and trans-alkenes substituted with dispersion energy donor (DED) groups was investigated through a combination of experimental and computational methods. The equilibrium between the two isomers was found to shift towards the more crowded cis-alkene as the substituent size increased. Noncovalent interactions, particularly long-range dispersion (LD) and Pauli exchange repulsion, were identified as the dominant factors influencing the equilibrium between cis- and trans-alkenes.
Article
Chemistry, Multidisciplinary
Artur Mardyukov, Raffael C. Wende, Peter R. Schreiner
Summary: 1,2-Ethenediols are key intermediates in prebiotic and interstellar syntheses of carbohydrates. In this study, we synthesized these enediols in the gas phase and trapped them in cryogenic argon matrices. Importantly, when subjected to photolysis at a wavelength of 180-254 nm, the enols rearrange into the simplest sugar, glycolaldehyde.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Alexander Seitz, Raffael C. C. Wende, Peter R. R. Schreiner
Summary: We describe the site-selective acetylation of partially protected monosaccharides using immobilized oligopeptide catalysts, synthesized via solid-phase peptide synthesis. The catalysts exhibit a reversed selectivity compared to N-methylimidazole and show high selectivity for various pyranosides. The catalysts demonstrate stability for multiple reaction cycles and can be easily reused after separation from the reaction solution. They can also be used in flow without any loss of reactivity and selectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Sebastian Schwan, Andreas J. Achazi, Ferdinand Ziese, Peter R. Schreiner, Kerstin Volz, Stefanie Dehnen, Simone Sanna, Doreen Mollenhauer
Summary: A systematic study of cluster dimers in adamantane-like molecular materials reveals that the binding energy between the dimers increases with the size of the core and the substituents. The cluster interactions can be classified as substituent-substituent-dominated or core-core-dominated. Understanding the interaction of the cluster dimers allows for an initial assessment of the interactions in the materials.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Organic
Finn M. Wilming, Benito Marazzi, Paul P. Debes, Jonathan Becker, Peter R. Schreiner
Summary: We synthesized 14 2,2'-disubstituted 9,9'-bifluorenylenes to quantify London dispersion interactions between dispersion energy donors. Delta G(Z/E) was measured at 333 K using 1H NMR in seven solvents. Alkyl and aryl substituents showed a preference for the folded Z-isomer due to attractive London dispersion interactions, except for tert-butyl, which unexpectedly favored the unfolded E-isomer due to increased Pauli repulsion caused by close proximity of functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jan M. Schuemann, Lukas Ochmann, Jonathan Becker, Ahmet Altun, Ingolf Harden, Giovanni Bistoni, Peter R. Schreiner
Summary: We conducted an experimental study on a cyclooctatetraene-based molecular balance with disubstituted tert-butyl (tBu), adamantyl (Ad), and diamantyl (Dia) substituents in the 1,4-/1,6-positions. Our measurements, supported by solvation computations, showed that the more sterically crowded 1,6-isomer is always favored and that the free energy is insensitive to substituent size, regardless of the solvent.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
David King, Tatjana Sumanovac, Steven Murkli, Peter R. Schreiner, Marina Sekutor, Lyle Isaacs
Summary: We synthesized quaternary (di)cationic triamantane derivatives G1 and G3 by permethylating the corresponding primary ammonium ions G2 and G4. The complexation behaviors of G1-G4 with CB[7] and CB[8] were examined using H-1 NMR spectroscopy. CB[8] fully encapsulated G1-G4 while CB[7] formed inclusion complexes with G1, G2, and G4 but could not fully encapsulate the central hydrophobic core of G3. The geometries of the CB[n]-guest complexes were determined by analyzing complexation-induced changes in chemical shifts and confirmed using molecular modeling.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Weiyu Qian, Raffael C. Wende, Peter R. Schreiner, Artur Mardyukov
Summary: The interstellar candidate phosphorus mononitride PN, a metastable species, was generated through high-vacuum flash pyrolysis of (o-phenyldioxyl)phosphinoazide in cryogenic matrices. Although the PN stretching band was not directly detected because of its low infrared intensity and possible overlaps with other strong bands, o-benzoquinone, carbon monoxide, and cyclopentadienone as additional fragmentation products were clearly identified. Moreover, an elusive o-benzoquinone-PN complex formed when (o-phenyldioxyl)phosphinoazide was exposed to UV irradiation at lambda=254 nm. Its recombination to (o-phenyldioxyl)-lambda(5)-phosphinonitrile was observed upon irradiation with the light at lambda=523 nm, which demonstrates for the first time the reactivity of PN towards an organic molecule. Energy profile computations at the B3LYP/def2-TZVP density functional theory level reveal a concerted mechanism. To provide further evidence, UV/Vis spectra of the precursor and the irradiation products were recorded and agree well with time-dependent DFT computations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Jack McAlpine, Alex Bloemendal, Jeremy E. Dahl, Robert M. K. Carlson, Ilia A. Guzei, Catherine F. M. Clewett, Boryslav O. Tkachenko, Peter R. Schreiner, Matthew A. Gebbie
Summary: As the deployment of large-scale lithium-ion batteries accelerates, the use of flammable organic electrolytes exacerbates the problem of battery fires during operation and disposal. Ionic liquid-derived electrolytes promise to be safe and nonflammable alternatives, but their use is hindered by poor lithium transport. However, a new study reports the design and characterization of novel ionic liquid-inspired organic electrolytes that leverage the unique self-assembly properties of diamondoids to enhance lithium-ion mobility.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Qigang Zhong, Artur Mardyukov, Ephrath Solel, Daniel Ebeling, Andre Schirmeisen, Peter R. Schreiner
Summary: On-surface synthesis is being recognized as the preferred method for generating and visualizing unconventional molecules. In this study, the structurally elusive cyclotriphosphazene (P3N3) was successfully synthesized on Cu(111) and Au(111) surfaces using molecular manipulation with unprecedented precision. The achieved atomic-level imaging revealed the planar D-3h-symmetric ring structure of cyclotriphosphazene.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Editorial Material
Chemistry, Multidisciplinary
Karsten Danielmeier, Peter R. Schreiner
Summary: The German Chemical Society (GDCh) has chosen "Rethinking Chemistry" as the guiding principle to address challenges related to climate change, loss of natural resources, and geopolitical conflicts. By encouraging scientists to approach chemistry from different perspectives, the GDCh aims to foster innovative and sustainable advancements in the field. This motto is also reflected in the upcoming GDCh Science Forum Chemistry (WiFo) 2023 and a dedicated Special Collection in Angewandte Chemie, showcasing the various aspects of Rethinking Chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Guanqi Qiu, Peter R. Schreiner
Summary: This study introduces the concepts of intrinsic and thermodynamic contributions to the barrier width in chemical reactions. Experimental and theoretical studies are used to demonstrate their distinct roles. The findings shed light on conflicting trends in chemical reactivities and contribute to a more comprehensive understanding of chemical reactions.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Akkad Danho, Artur Mardyukov, Peter R. Schreiner
Summary: This study demonstrates the successful gas-phase synthesis of the previously unreported higher energy tautomer of propionic acid, prop-1-ene-1,1-diol. The enol was characterized using IR and UV/Vis spectroscopy along with density functional theory computations. Upon photolysis, the enol rearranges to propionic acid and methylketene.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Laura M. Grimm, Jeffry Setiadi, Boryslav Tkachenko, Peter R. Schreiner, Michael K. Gilson, Frank Biedermann
Summary: The thermodynamic parameters of host-guest binding can be used to describe, understand, and predict molecular recognition events in aqueous systems. This study focuses on the contributions of water to binding by studying binding thermodynamics for a series of host-guest systems. It is found that the enthalpic driving forces for binding increase at higher temperatures, and heat capacity changes appear to be a general feature of host-guest complex formation in water.
Article
Chemistry, Multidisciplinary
Akkad Danho, Artur Mardyukov, Peter R. Schreiner
Summary: The gas-phase synthesis of a higher energy tautomer, prop-1-ene-1,1-diol, of propionic acid is demonstrated in this study. The enol species is trapped in an argon matrix and characterized using IR and UV/Vis spectroscopy along with density functional theory calculations. Upon photolysis, the enol undergoes rearrangement to form propionic acid and methylketene.
CHEMICAL COMMUNICATIONS
(2023)