Sticking and patching: tuning and anchoring cyclometallated ruthenium(II) complexes

Ertl, C. D. and Ris, D. P. and Meier, S. C. and Constable, E. C. and Housecroft, C. E. and Neuburger, M. and Zampese, J. A.. (2015) Sticking and patching: tuning and anchoring cyclometallated ruthenium(II) complexes. Dalton transactions, 44. pp. 1557-1570.

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Official URL: http://edoc.unibas.ch/dok/A6337520

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A series of [Ru(bpy)2(C^N)][PF6] (HC^N = 2-phenylpyridine derivative) complexes functionalized in the cyclometallating C^N phenyl ring with F, Me, OMe, CO2Me, S(t)Bu, SO2Me (ligands H1-H6) or in the C^N pyridine ring with 4-CO2Me or 4-C6H4P(O)(OEt)2 substituents (ligands H7 or H9) have been prepared and characterized; representative crystal structures confirm the structural features of the complexes. When the C^N ligand contains a CO2H substituent (ligand H28), deprotonation in addition to cyclometallation occurs to give a neutral, zwitter-ionic complex [Ru(bpy)2(8)]. The synthesis of the cationic complexes requires addition of a silver(i) salt (AgPF6 or AgBF4) to abstract Cl(-) from cis-[Ru(bpy)2Cl2] and (1)H NMR spectroscopic data are consistent with interactions between Ag(+) and the coordinated C^N ligand in [Ru(bpy)2(C^N)](+). The absorption spectra of [Ru(bpy)2(C^N)][PF6] (C^N = 1-6) are similar, but the introduction of the anchoring domains in [Ru(bpy)2(C^N)][PF6] with C^N = 7 or 9 enhances the absorption response; the greatest influence is observed in [Ru(bpy)2(9)](+) with the introduction of the 4-C6H4P(O)(OEt)2 substituent. Trends in emission and electrochemical behaviours of the complexes are interpreted in terms of the influence of the electronic properties of the C^N ligand substituents on the energies of the HOMO which is localized on the C^N ligand and Ru centre. This study provides an optimized synthetic route to the phosphonate ester derivative [Ru(bpy)2(9)][PF6], designed to anchor to a semiconductor surface; this complex also exhibits the most favourable absorption properties among the complexes studied.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Constable)
05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Housecroft)
UniBasel Contributors:Housecroft, Catherine Elizabeth and Ertl, Cathrin and Constable, Edwin Charles and Neuburger, Markus and Zampese, Jennifer Ann
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
Note:Publication type according to Uni Basel Research Database: Journal article
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edoc DOI:
Last Modified:31 Dec 2015 10:56
Deposited On:06 Feb 2015 09:59

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