In this Article, we report the self-assembly of lanthanide complexes formed with two new tripodal ligands, L2 and L3, where binding strands are connected to a rigid triptycene anchor. The pyridine moieties are functionalized with methoxy and PEG groups to enhance ligand solubility and to evaluate the effect of these substituents on lanthanide coordination. These ligands were successfully synthesized and characterized, and their coordination properties were examined along the lanthanide series through speciation studies with NMR and ESI-MS. Well-defined tetranuclear complexes are formed with both ligands, but their stabilities with heavier lanthanides are considerably reduced, especially for complexes with L3. This is attributed to a destabilizing effect of pending PEG arms in combination with increased steric hindrance between binding strands upon complexation with smaller cations. The sensitization of lanthanide luminescence in tetranuclear complexes occurs despite one water molecule being coordinated to a metal ion.
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http://dx.doi.org/10.1021/acs.inorgchem.6b02900 | DOI Listing |
Biochemistry
January 2025
Department of Chemistry, Washington University in St. Louis, One Brookings Drive, St. Louis, Missouri 63130, United States.
Branch-point syntheses in nonribosomal peptide assembly are rare but useful strategies to generate tripodal peptides with advantageous hexadentate iron-chelating capabilities, as seen in siderophores. However, the chemical logic underlying the peptide branching by nonribosomal peptide synthetase (NRPS) often remains complex and elusive. Here, we review the common strategies for the biosynthesis of branched nonribosomal peptides (NRPs) and present our biochemical investigation on the NRPS-catalyzed assembly of fimsbactin A, a branched mixed-ligand siderophore produced by the human pathogenic strain .
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, California 92697, United States.
The development of molecular species with switchable magnetic properties has been a long-standing challenge in chemistry. One approach involves binding an analyte, such as protons, to a compound to trigger a change in magnetism. Transition metal complexes have been targeted for this type of magnetic modulation because they can undergo changes in their spin states.
View Article and Find Full Text PDFInorg Chem
January 2025
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong 999077, China.
The protonolysis and redox reactivity of a Ce(IV) carbonate complex supported by the Kläui tripodal ligand [(η-CH)Co{P(O)(OEt)}] (L) have been studied. Whereas treatment of [Ce(L)(CO)] () with RCOH afforded [Ce(L)(RCO)] ( = Me (), Ph (), 2-NOCH ()), the reaction of with PhCHCOH resulted in formation of a mixture of Ce(IV) () and Ce(III) () carboxylate species. In benzene in the dark, was slowly converted into via Ce(IV)-O(carboxylate) homolysis.
View Article and Find Full Text PDFChem Asian J
December 2024
Tokyo College, U-Tokyo Institutes for Advanced Study (UTIAS), The University of Tokyo, Mitsui Link Lab Kashiwanoha 1, FS CREATION, 6-6-2 Kashiwanoha, Kashiwa-shi, Chiba, 277-0882, Japan.
The control of the sequential self-assembly processes of highly entangled (AgL) (n=2,4,6,8) and AgL coordination polyhedra using side-chain effects was studied via the introduction of linear or branched side chains into the tripodal ligands. In addition to changes in the intermediate polyhedral species affording the multi- pathway process, disruption of the kinetic control of the sequential self-assembly was observed, thus demonstrating the utility of steric control for the construction of 3D-entangled molecular materials on the 5 nm scale with high molecular complexity.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, People's Republic of China.
The integration of spin crossover (SCO) magnetic switching and electric polarization properties can engender intriguing correlated magnetic and electric phenomena. However, achieving substantial SCO-induced polarization change through rational molecular design remains a formidable challenge. Herein, we present a polar Fe(II) compound that exhibits substantial polarization change in response to a thermally regulated low-spin ↔ high-spin transition.
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