Association constants of the chiral dirhodium(II) carboxamidate Rh(2)(5S-MEPY)(4) with Lewis bases including acetonitrile and amides have been determined by UV-vis titration experiments. With chiral lactams and acyclic acetamides in their R- and S-configurations equilibrium constants with chiral dirhodium carboxamidates are measures of chiral differentiation, and equilibrium constant ratios as high as three have been determined. From equilibrium associations with acetamide, N-methylacetamide, and N,N-dimethylacetamide, as well as equilibrium constants for lactams and acyclic amides, higher values occur when both the amide carbonyl oxygen and N-H are bound to Rh(2)(5S-MEPY)(4). This cooperative bonding mode is confirmed by NMR measurements that show a distinctive shift of a N-H absorption, as well as perturbation of the ligands on dirhodium compound, and they suggest N-H association with a ligated oxygen of Rh(2)(5S-MEPY)(4). Measurements were made on the dirhodium(II) compound from which protective axial ligands have been removed to enhance their reliability.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/ic200609u | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
In this paper, the focusing and tight-focusing properties of radially polarized (RP) Bessel-Gaussian (BG) rotationally-symmetric power-exponent-phase vortex beam (RPVBs) were investigated theoretically and experimentally. Based on the theory of vector beam, the propagation and tight-focusing models were derived to reveal the focusing and tight-focusing properties of the RP-BG-RPVBs by numerical simulation. Then, the experimental setup was established to validate that the RP-BG-RPVBs presented the fan-shaped and polycyclic intensity distribution, which possessed the features of RP beams, BG beams, and RPVBs, similarly.
View Article and Find Full Text PDFHelical Quintulene: Synthesis, Chirality, and Supramolecular Assembly.
Angew Chem Int Ed Engl
January 2025
Xiamen University, Department of Chemistry, Siminnan Road 422, 361005, Xiamen, CHINA.
Quintulene is a quintuply symmetrical cycloarene with a positively curved molecular geometry. First described by Staab and Sauer in 1984, its successful synthesis was not achieved until 2020. Due to the challenges posed by its positive curvature, structural extensions of quintulene have been studied rarely.
View Article and Find Full Text PDFHomochiral BINOL-Based Metal-Organic Frameworks for Luminescence Sensing of Hydrobenzoin Enantiomers.
Inorg Chem
January 2025
Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States.
Luminescent chiral metal-organic frameworks (CMOFs) are promising candidates for the enantioselective sensing of important chiral molecules. Herein, we report the synthesis and characterization of Zn and Cd CMOFs based on 1,1'-bi-2-naphthol (BINOL)-derived 3,3',6,6'-tetra(benzoic acids), H-OEt and H-OH. Four CMOFs, -OEt, -OH, -OEt, and -OH, based on these ligands were crystallographically characterized.
View Article and Find Full Text PDFMagnetophononics and the chiral phonon misnomer.
PNAS Nexus
January 2025
The Harrison M. Randall Laboratory of Physics, University of Michigan, Ann Arbor, MI 48109-1040, USA.
The direct, ultrafast excitation of polar phonons with electromagnetic radiation is a potent strategy for controlling the properties of a wide range of materials, particularly in the context of influencing their magnetic behavior. Here, we show that, contrary to common perception, the origin of phonon-induced magnetic activity does not stem from the Maxwellian fields resulting from the motion of the ions themselves or the effect their motion exerts on the electron subsystem. Through the mechanism of electron-phonon coupling, a coherent state of circularly polarized phonons generates substantial non-Maxwellian fields that disrupt time-reversal symmetry, effectively emulating the behavior of authentic magnetic fields.
View Article and Find Full Text PDFThe critical role of the variable domain in driving proteotoxicity and aggregation in full-length light chains.
J Mol Biol
January 2025
Department of Biosciences, University of Milan, Italy; Institute of Molecular and Translational Cardiology, IRCCS, Policlinico San Donato, Milan, Italy. Electronic address:
Light chain (AL) amyloidosis is the most common systemic amyloid disease characterized by abnormal accumulation of amyloid fibrils derived from immunoglobulin light chains (LCs). Both full-length (FL) LCs and their isolated variable (VL) and constant (CL) domains contribute to amyloid deposits in multiple organs, with the VL domain predominantly forming the fibril core. However, the role and interplay of these domains in amyloid aggregation and toxicity are poorly understood.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!