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NMR spectroscopy and DFT calculations of a self-assembled arene ruthenium rectangle obtained from a combination of coordination and hydrogen bonds

, Appavoo, Divambal, Raja, Nandhagopal, Deschenaux, Robert, Therrien, Bruno, Carnevale, Diego

The hydrogen-bonded arene ruthenium metalla-rectangle, [(p-cymene) 2Ru2(OOnOO)(UPy)2]24+ , obtained from 1-(4-oxo-6-undecyl-1,4-dihydropyrimidin-2-yl)-3-(pyridin-4- ylmethyl)urea (UPy) and the dinuclear arene ruthenium clip (p-cymene) 2Ru2(OOnOO)Cl2 (OOnOO = 2,5-dioxido-1,4- benzoquinonato), is investigated by means of solution-phase NMR spectroscopy. Rotating frame nuclear Overhauser effect measurements are used to probe the H- bond network that drives the UPy self-assembly as well as the full rectangular supramolecular system. An effective distance that takes into account both intra-and intermolecular polarization-transfer pathways is utilised for data analysis. The experimental findings are corroborated by DFT calculations of NMR parameters and internuclear distances, thus confirming the formation of a very stable tetranuclear metalla-assembly.

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Synthesis and characterization of fullerene-pyridyl arene ruthenium complexes

, Appavoo, Divambal, Deschenaux, Robert, Therrien, Bruno

Association of [60]fullerene with arene ruthenium moieties has been achieved for the first time. Two fullerenopyrrolidine derivatives (Npyr-C60) were synthesized via a 1,3-dipolar cycloaddition, and coordinated to arene ruthenium complexes to form two half-sandwich complexes of the general formula (p-cymene)RuCl2(Npyr-C60). The coordination of the fullerenopyrrolidines to the arene ruthenium unit was evidenced by NMR spectroscopy and mass spectrometry, thus confirming the formation of these novel arene ruthenium complexes.