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4'-Functionalized 2,2':6',2''-terpyridines as the N^N domain in [Ir(C^N)2(N^N)][PF6] complexes

Ris, D. P. and Schneider, G. E. and Ertl, C. D. and Kohler, E. and Müntener, T. and Neuburger, M. and Constable, E. C. and Housecroft, C. E.. (2016) 4'-Functionalized 2,2':6',2''-terpyridines as the N^N domain in [Ir(C^N)2(N^N)][PF6] complexes. Journal of organometallic chemistry, 812. pp. 272-279.

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Abstract

The cyclometallated iridium(III) complexes [Ir(ppy)2(NˆN)][PF6] (Hppy = 2-phenylpyridine) with NˆN = 4′-chloro-2,2′:6′,2″-terpyridine (1), 4′-methoxy-2,2′:6′,2″-terpyridine (2), 4′-ethoxy-2,2′:6′,2″-terpyridine (3), 4′-methylthio-2,2′:6′,2″-terpyridine (4), 4′-phenylthio-2,2′:6′,2″-terpyridine (5) and 4′-dimethylamino-2,2′:6′,2″-terpyridine (6) are reported including the single crystal structures of 2{[Ir(ppy)2(1)][PF6]}·0.6Et2O·CH2Cl2, [Ir(ppy)2(5)][PF6]·0.5CH2Cl2 and [Ir(ppy)2(6)][PF6]. The single crystal structure of [Ir(ppy)2(3)]Cl·2H2O·MeCN is also reported. In each complex, the 2,2′:6′,2″-terpyridine (tpy) ligand binds to the metal centre in a bidentate fashion with the non-coordinated pyridine ring folded into the coordination sphere and engaging in a pyridine–phenyl π-stacking interaction. Solution NMR spectra are consistent with hindered rotation of the non-coordinated pyridine ring at 298 K, with intra-cation CH…N(pyridine) hydrogen bond formation between adjacent [ppy]– and tpy ligands. Trends in the electrochemical HOMO–LUMO gaps and emission maxima of the complexes (in CH2Cl2 solution) are consistent with the electron-withdrawing or releasing properties of the 4′-tpy substituent; in degassed solution, [Ir(ppy)2(6)][PF6] has a quantum yield of 24.8% and emission lifetime of 441 ns, while the other complexes exhibit significantly lower quantum yields and shorter lifetimes.
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 Constable, Edwin Charles and Ris, Daniel and Schneider, Gabriel and Ertl, Cathrin and Kohler, Emanuel and Müntener, Thomas and Neuburger, Markus
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Elsevier
ISSN:0022-328X
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:06 Oct 2016 09:35
Deposited On:21 Jun 2016 13:59

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