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Issue 20, 2009
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Ruthenium polypyridine complexes of tris-(2-pyridyl)-1,3,5-triazine—unusual building blocks for the synthesis of photochemical molecular devices

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Abstract

The mononuclear compounds bis-(2,2′-bipyridine)ruthenium(II)-(tris(2-pyridyl)triazine) [(bpy)2Ru(tpt)](PF6)21 and bis-(4,4′-di-tert-butyl-2,2′-bipyridine)ruthenium(II)-(tris(2-pyridyl)triazine) [(tbbpy)2Ru(tpt)](PF6)22 have been synthesised and fully characterised. The attempted syntheses of heterodinuclear complexes with the tris(2-pyridyl)triazine (tpt) ligand as bridging ligand and various palladium(II)- and platinum(II)-dichloro complexes using the ruthenium complexes as starting materials resulted in a partial hydrolysis of the triazine based bridging ligand in case of 2 and an unselective decomposition in case of 1. Compound 2 reacts with Pd(DMSO)2Cl2 and Pt(DMSO)2Cl2 substituting three ligands from the metal centres of these precursors with partial hydrolysis of the triazine moiety of the bridging ligand yielding the dinuclear complexes bis-(4,4′-di-tert-butyl-2,2′-bipyridine)ruthenium(II)-N-((picolinamido)(pyridin-2-yl)methylene)picolinamide)chloro-palladium(II) [(tbbpy)2Ru(tptO)PdCl](PF6)23 and bis-(4,4′-di-tert-butyl-2,2′-bipyridine) ruthenium(II)-N-((picolinamido)(pyridin-2-yl)methylene)picolinamide)chloro-platinum(II) [(tbbpy)2Ru(tptO)PtCl](PF6)24. The newly formed bridging ligand coordinates in a bidentate fashion at the ruthenium centre and acts as a tridentate ligand for the second metal centre. The structures of all the complexes have been fully characterised and their photophysical properties are reported. A similar reaction sequence using the (4′-(p-bromophenyl)-2,2′:6′,2″-terpyridine)ruthenium(II)-(tris(2-pyridyl)triazine) complex [(BrPhtpy)Ru(tpt)](PF6)25 and Pd(CH3CN)2Cl2 as starting materials did not yield the hydrolysed bridging ligand but the expected dinuclear complex [(BrPhtpy)Ru(tpt)PdCl2](PF6)26 suggesting that the coordination of two pyridine rings of the tpt by the ruthenium centre is essential for the stabilisation of the tpt frame work. Preliminary investigations show that the dinuclear ruthenium-palladium and -platinum complexes are not active catalysts in the light-driven hydrogen production.

Graphical abstract: Ruthenium polypyridine complexes of tris-(2-pyridyl)-1,3,5-triazine—unusual building blocks for the synthesis of photochemical molecular devices

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Publication details

The article was received on 16 Dec 2008, accepted on 27 Mar 2009 and first published on 22 Apr 2009


Article type: Paper
DOI: 10.1039/B822550H
Citation: Dalton Trans., 2009,0, 4012-4022
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    Ruthenium polypyridine complexes of tris-(2-pyridyl)-1,3,5-triazine—unusual building blocks for the synthesis of photochemical molecular devices

    M. Schwalbe, M. Karnahl, H. Görls, D. Chartrand, F. Laverdiere, G. S. Hanan, S. Tschierlei, B. Dietzek, M. Schmitt, J. Popp, J. G. Vos and S. Rau, Dalton Trans., 2009, 0, 4012
    DOI: 10.1039/B822550H

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