New classes of tridentate N-donor rhodium(I) complexes have been synthesized and demonstrated to exhibit interesting induced self-assembly behavior by variation of external stimuli, as a result of extensive Rh(I)···Rh(I) interactions, with the assistance of π-π stacking and hydrophobic-hydrophobic interactions. An isodesmic aggregation mechanism has also been identified in the temperature-dependent process. Upon aggregation in acetone solution, the complex molecules form wire-like nanostructures with their shape dependent on the π-conjugation of the tridentate ligands. On the other hand, crystalline needles of rhodium(I) complexes obtained from recrystallization have also been shown to exhibit conductivity on the order of 10(-3) S cm(-1).
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http://dx.doi.org/10.1021/acs.inorgchem.6b00289 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Department of Chemistry, Graduate School of Sciences, Tokyo Metropolitan University, Hachioji, 192-0397, Japan.
Stable neutral metal radicaloid complexes have been synthesized from a modified tetrapyrrolic pigment, bilatriene, with iridium(I) and rhodium(I) cyclooctadiene (COD) synthons. The bilatriene skeleton contains α-linked conjugated pyrrole units, whereas an N-confused analogue used in this work possesses β-linked pyrrole moieties at the terminal, demonstrating a unique metal binding capability. Unprecedentedly, the metal-COD cations are accommodated at the outer nitrogen sites, which induced the formation of open-shell metal-radicaloid species.
View Article and Find Full Text PDFDalton Trans
January 2025
Ruđer Bošković Institute, Bijenička c. 54, HR-10000 Zagreb, Croatia.
This publication describes monodentate phosphine and oxazoline ligands attached to an amino acid ester and the application of their supramolecularly assembled rhodium(I) or iridium(I) complexes in asymmetric catalysis. The major feature of these complexes is the transmission of chirality from distant hydrogen bonded amino acids to the prochiral catalytic metal center ("backdoor induction"). The generated homoleptic and heteroleptic rhodium(I) or iridium(I) precatalysts were studied by NMR, UV-VIS and CD spectroscopy as well as X-ray single crystal diffraction.
View Article and Find Full Text PDFJ Phys Chem Lett
October 2024
Department of Chemistry, University of Warsaw, Żwirki i Wigury 101, 02-089 Warsaw, Poland.
The rare observation of transient Rh···Rh excimer formation in a single crystal is reported. The estimated excited-state lifetime at 100 K is 2 ns, which makes it the shortest-lived small-molecule species caught experimentally using the laser-pump/X-ray-probe time-resolved Laue method. Upon excitation with 390 nm laser light, the intermolecular Rh···Rh distance decreases from 3.
View Article and Find Full Text PDFRSC Adv
August 2024
Institute of Inorganic Chemistry, Leipzig University Johannisallee 29 D-04103 Leipzig Germany
Homotrinuclear complexes of the -symmetric tris(ferrocenyl)arene-based tris-phosphanes 1a-d with ruthenium(ii) ([1a-d(Ru)]) and rhodium(i) ([1a-d(Rh)]) were prepared and fully characterised. Complexes [1a-d(Ru)] and [1a-d(Rh)] are electrochemically active. The nature of the arene core in 1a-d ranging from benzene, 1,3,5-trifluorobenzene and mesitylene to -triazine allows to fine-tune the exact oxidation potentials for tailoring the electrochemical response.
View Article and Find Full Text PDFA new neutral triazole-based N-heterocyclic carbene rhodium(I) complex [RhCl(CH)(CHN)], has been synthesized and structurally characterized. The complex crystallizes with two mol-ecules in the asymmetric unit. The central rhodium(I) atom has a distorted square-planar coordination environment, formed by a cyclo-octa-1,5-diene (COD) ligand, an N-heterocyclic carbene (NHC) ligand, and a chlorido ligand.
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