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The photophysical characterization of four supramolecular complexes based on covalent cages , , , and , consisting in either two free-base porphyrins or one Zn(II) porphyrin and one free-base porphyrin connected by four flexible linkers of different lengths incorporating triazole binding sites, and their Ag(I) complexation are reported. The complexation processes have been followed by means of absorption and emission spectroscopies, and a comprehensive computational study explains the behavior of the free-base porphyrin-containing cages. Absorption and emission features have been interpreted on the bases of conformational changes, metalation processes, and modification of energy transfer efficiencies occurring in the different cases. In all cages, except , the coordination of four Ag(I) ions to the lateral triazole groups of the linkers leads to the enlargement of their cavity. Only for is a different behavior observed, where the process of silver metalation of the porphyrins' core prevails.
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http://dx.doi.org/10.1021/acs.jpcb.2c01111 | DOI Listing |
Anticancer Res
September 2025
Department of Math and Sciences, Walsh University, North Canton, OH, U.S.A.
Background/aim: Platinum-based chemotherapeutics remain the standard of care for many solid tumors; however, they have dose-limiting toxicities. Silver(I) -heterocyclic carbene complexes represent a novel class of metallodrugs with potential anticancer activity and improved tolerability. This study evaluated SCC5, a silver(I) acetate complex derived from 1,3-dimethyl-4,5-dichloroimidazole-2-ylidene, across a panel of human cancer cell lines and toxicity models.
View Article and Find Full Text PDFJ Fluoresc
August 2025
Department of Chemistry, Guru Ghasidas Vishwavidyalaya, Bilaspur, (C.G), India.
Herein we describe a quinoxaline mono Schiff base, synthesised from benzil and o-phenylene diamine that may be used as a fluorescent-colourimetric chemosensor to detect Ag ions in organic media with high selectivity and sensitivity over other competitive ions. The sensing processes were operated by visual change, absorption, and emission measurements, and the binding sites were confirmed by FTIR and single-crystal structure of the Ag(I)- complex. From Job-plot analysis, ESI-mass spectra and XRD studies 1:2 binding stoichiometry between host-guest was observed.
View Article and Find Full Text PDFDalton Trans
September 2025
Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Engesserstr. 15, 76131 Karlsruhe, Germany.
The syntheses of luminescent heterobimetallic ionic complexes based on the bis(phosphine)-functionalized β-diketiminate ligand [HC{(CH)C}{(-[P(CH)]CH)N}] (PNac) are reported. This orthogonal ligand is characterized by its PNNP pocket, which contains both hard and soft donor sites and therefore enables the selective coordination of two different metal ions in spatial proximity, significantly changing the photoluminescent properties. Salt elimination reaction of [PNacK] with zinc chloride yields the monometallic complex [PNacZnCl], in which the zinc ion is square-pyramidally coordinated within the PNNP pocket.
View Article and Find Full Text PDFDalton Trans
August 2025
Department of Chemistry and Pharmacy, Opole University, 48 Oleska Street, Opole 45-052, Poland.
N-Heterocyclic carbenes (NHCs) are among the most versatile ligands in transition metal catalysis with their steric and electronic properties playing a critical role in governing reactivity and selectivity. In this area, the wingtip unsymmetrical IPaul ligand introduced by Nelson and co-workers offers a unique balance of steric bulk and flexibility characterized by spatially-defined steric features. Herein, we report a new class of IPaul-based ligands bearing benzoxazole and benzothiazole donor wingtips.
View Article and Find Full Text PDFNat Commun
August 2025
Department of Chemistry, University of Jyvaskyla, Jyväskylä, Finland.
Metal-metal bonds between metal cations are ubiquitous in coordination complexes, whereas similar bonding characteristics between non-metal and metal cations are not. Here, we report an X-ray crystal structure of a centrosymmetric complex [Ag(m-OSCF){(4MePyNO)I}] (1-AgI), where the iodine(I) cation forms an unusual 3-centre 4-electron [O-I-O] halogen bond with two oxygen atoms from two 4-methylpyridine N-oxide (4MePyNO). The iodine(I) atoms from two [4MePyNO-I-ONPyMe4] cations, which, together with the two silver(I) atoms from the paddlewheel [Ag(m-OSCF)] structure, establish two unique I-Ag bonds at 2.
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