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Unusual azobenzene/bipyridine palladacycles: structural, dynamical, photophysical and theoretical studies

Juribašić, Marina; Ćurić, Manda; Molčanov, Krešimir; Matković-Čalogović, Dubravka; Babić, Darko (2010) Unusual azobenzene/bipyridine palladacycles: structural, dynamical, photophysical and theoretical studies. Dalton Transactions, 39 (37). pp. 8769-8778. ISSN 1477-9226

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Two types of Pd(II) azobenzene/bipyridine complexes with unusual coordination mode of azobenzenes, PdCl{(mu-Cl)(mu-R1C6H3N=NC6H3R2)}Pd(bpy) 1a-4a and [(bpy)PdCl(mu-NH2C6H3N=NC6H4)-Pd(bpy)]Cl 3b were formed by the reaction of dicyclopalladated azobenzenes (DMF)PdCl(mu-R1C6H3N=NC6H3R2)PdCl(DMF) with excess of bpy, where bpy=2,2'-bipyridine; R2=H andR1=H (1), CH3 (2), NH2 (3) or R1=N(CH3)2 and R2=NO2 (4). Neutral species 1a-4a were obtained in acetone, while in DMSO or MeOH the ionic complex 3b was produced. When dissolved, 3b decomposes to 3a and free bpy; however in DMSO upon addition of bpy 3b crystallizes again. X-ray structures of all complexes confirmed breaking of one Pd-N bond in the initial precursors, thus allowing rotation of one phenyl ring and positioning of both Pd atoms on the same side of the azobenzene ligand. Two Pd atoms are connected by the azobenzene ligand and in neutral complexes additionally by the Cl-bridge. In all complexes in the solid-state azobenzenes act simultaneously as monodentate C- and bidentate C,N-donors while bpy acts as bidentate donor. Variable-temperature 1H NMR experiments established that structures of 1a-4a in DMF and DMSO at ambient temperature are not consistent with solid-state structures due to the fast exchange of one of the bpy nitrogen atoms bound to the Pd atom with solvent molecules. Theoretical studies confirmed the experimental structures as the most stable isomers. Photoabsorption and photoemission properties of the new complexes have been measured and photoabsorption is rationalized by time dependent DFT calculations. The presence of bpy significantly increases the intensity of fluorescence either in the solution (4a) or in the solid state (3a, 4a, 3b) at ambient temperature.

Item Type: Article
Uncontrolled Keywords: paladacycles; azobenzene; bipyridine; fluorescence
Subjects: NATURAL SCIENCES > Chemistry > Physical Chemistry
NATURAL SCIENCES > Chemistry > Inorganic Chemistry
Divisions: Division of Physical Chemistry
Project titleProject leaderProject codeProject type
Dizajn, sinteza i svojstva organskih liganada i njihovih metalnih kompleksa[124246] Ćurić, Manda098-0982915-2950MZOS
Protein-ligand međudjelovanja na atomnoj razini[77430] Luić, Marija098-1191344-2943MZOS
Strukturno istraživanje bioloških makromolekula metodom rentgenske difrakcije[108862] Matković-Čalogović, Dubravka119-1193079-1084MZOS
Depositing User: Darko Babić
Date Deposited: 23 Oct 2012 14:05
DOI: 10.1039/c0dt00018c

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