Novel monometallic (μ-LL')Ru, Ru(μ-LL'), homobimetallic Ru(μ-LL')Ru, and heterodimetallic Ru(μ-LL')Os and Os(μ-LL')Ru complexes based on two asymmetrical ligands LL' (where LL' = LL, LL) have been synthesized and characterized. Spectroscopic analysis indicates that all complexes exhibit intense spin-allowed ligand-centered (LC) transitions at 288 nm and Ru-based moderate spin-allowed MLCT absorption between 440-450 nm. The Ru(μ-LL')Os and Os(μ-LL')Ru dinuclear complexes show Os-based unit absorption in the range of 565-583 nm. The Ru-based units of the complexes present different emission intensities due to differing steric hindrance at the coordination sites of the two bridging ligands. The Os(μ-LL')Ru dinuclear complexes present weaker emission intensity than their parent monometallic complexes (μ-LL')Ru. These results indicate that the emission of Os(μ-LL')Ru dinuclear complexes is quenched by the Os(II)-based units.
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http://dx.doi.org/10.1039/d2dt03709b | DOI Listing |
Chem Commun (Camb)
January 2025
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
The diiridium complexes of lithium-ion endohedral fullerene Li@C were synthesised in high yields. X-ray crystallography revealed the η:η-coordination of Li@C and the disorder of the Li ion over two sites close to the coordinated carbons. C NMR study suggested the presence of dynamic behaviour haptotropic rearrangements.
View Article and Find Full Text PDFDalton Trans
January 2025
Laboratory for Molecular & Functional Design, Department of Engineering, Nara Women's University, Nara 630-8506, Japan.
Rational molecular design afforded fluorescent Cd sensors based on bisquinoline derivatives. Introduction of three methoxy groups at the 5,6,7-positions of the quinoline rings of BQDMEN (,'-bis(2-quinolylmethyl)-,'-dimethylethylenediamine) resulted in the reversal of metal ion selectivity in fluorescence enhancement from zinc to cadmium. Introduction of bulky alkyl groups and an ,-bis(2-quinolylmethyl)amine structure, as well as replacement of one of the two tertiary amine binding sites with an oxygen atom and the use of a 1,2-phenylene backbone significantly improved the Cd specificity.
View Article and Find Full Text PDFInorg Chem
December 2024
Department of Chemistry, The Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218, United States.
The nonheme iron(II) complexes containing a fluoride anion, Fe(BNPAO)(F) () and [Fe(BNPAOH)(F)(THF)](BF) (), were synthesized and structurally characterized. Addition of dioxygen to either or led to the formation of a fluoride-bridged, dinuclear iron(III) complex [Fe(BNPAO)(F)(μ-F)] (), which was characterized by single-crystal X-ray diffraction, H NMR, and elemental analysis. An iron(II)(iodide) complex, Fe(BNPAO)(I) (), was prepared and reacted with O to give the mononuclear complex -Fe(BNPAO)(OH)(I) ().
View Article and Find Full Text PDFInorg Chem
December 2024
Department of Chemistry, The Hong Kong University of Science and Technology, Kowloon, Hong Kong 999077, China.
Anilido-oxazoline-ligated iron complexes, including bis(anilido-oxazolinate) iron(II), mononuclear iron(II) alkyl and aryloxide, as well as the dinuclear analogues, were synthesized, and their catalytic performance on ring-opening polymerization (ROP) has been studied. Transmetalation of FeCl(THF) with in situ-generated anilido-oxazolinate lithium afforded the bis(anilido-oxazolinate) iron complexes and . Half-sandwich anilido-oxazolinate iron trimethylsilylalkyl complexes and could be synthesized in good yields via taking pyridine as an L-type ligand.
View Article and Find Full Text PDFActa Crystallogr E Crystallogr Commun
October 2024
Department of Chemistry, KU Leuven, Biomolecular Architecture, Celestijnenlaan 200F, Leuven (Heverlee), B-3001, Belgium.
Two new zinc(II) complexes, tri-ethyl-ammonium di-chlorido-[2-(4-nitro-phen-yl)-4-phenyl-quinolin-8-olato]zinc(II), (CHN){Zn(CHNO)Cl] (), and bis-(tri-ethyl-ammonium) {2,2'-[1,4-phenyl-enebis(nitrilo-methyl-idyne)]diphenolato}bis-[di-chlorido-zinc(II)], (CHN)[Zn(CHNO)Cl] (), were synthesized and their structures were determined using ESI-MS spectrometry, H NMR spectroscopy, and single-crystal X-ray diffraction. The results showed that the ligands 2-(4-nitro-phen-yl)-4-phenyl-quinolin-8-ol () and ,'-bis-(2-hy-droxy-benzyl-idene)benzene-1,4-di-amine () were deprotonated by tri-ethyl-amine, forming the counter-ion EtNH, which inter-acts an N-H⋯O hydrogen bond with the ligand. The Zn atoms have a distorted trigonal-pyramidal () and distorted tetra-hedral () geometries with a coord-ination number of four, coordinating with the ligands N and O atoms.
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