A.J. Wilkinson
Luminescent Complexes of Iridium(III) Containing N∧C∧N-Coordinating Terdentate Ligands
Wilkinson, A.J.; Puschman, H.; Howard, J.A.K.; Foster, C.E.; Williams, J.A.G.
Authors
H. Puschman
J.A.K. Howard
C.E. Foster
Professor Gareth Williams j.a.g.williams@durham.ac.uk
Professor
Abstract
A family of bis-terdentate iridium(III) complexes is reported which contain a cyclometalated, NCN-coordinating 1,3-di(2-pyridyl)benzene derivative. This coordination mode is favored by blocking competitive cyclometalation at the C4 and C6 positions of the ligand. Thus, 1,3-di(2-pyridyl)-4,6-dimethylbenzene (dpyxH) reacts with IrCl3·3H2O to generate a dichlorobridged dimer [Ir(dpyx-N,C,N)Cl(-Cl)]2, 1. This dimer is cleaved by DMSO to give [Ir(dpyx)(DMSO)Cl2], the X-ray crystal structure of which is reported here, confirming the NCN coordination mode of dpyx. The dimer 1 can also be cleaved by a variety of other ligands to generate novel classes of mononuclear complexes. These include charge-neutral bis-terdentate complexes of the form [Ir(NCN)(CNC)] and [Ir(NCN)(CNO)], by reaction of 1 with CNC-coordinating ligands (e.g., 2,6-diphenylpyridine and derivatives) and CNO-coordinating ligands (based on 6-phenylpicolinate), respectively. Treatment of 1 with terpyridines leads to dicationic complexes of the type [Ir(NCN)(NNN)]2+, while 2-phenylpyridine gives [Ir(dpyx-NCN)(ppy-C,N)Cl]. All of the charge-neutral complexes are luminescent in fluid solution at room temperature. Assignment of the emission to charge-transfer excited states with significant MLCT character is supported by DFT calculations. In the [Ir(NCN)(CNC)] class, fluorination of the CNC ligand at the phenyl 2' and 4' positions leads to a blue-shift in the emission and to an increase in the quantum yield (max = 547 nm, = 0.41 in degassed CH3CN at 295 K) compared to the nonfluorinated parent complex (max = 585 nm, = 0.21), as well as to a stabilization of the compound with respect to photodissociation through cleavage of mutually trans Ir-C bonds. [Ir(dpyx-NCN)(ppy-C,N)Cl] is an exceptionally bright emitter: = 0.76, max = 508 nm, in CH3CN at 295 K. In contrast, the [Ir(NCN)(CNO)] complexes are much less emissive, shown to be due to fast nonradiative decay of the excited state, probably involving reversible Ir-O bond cleavage. The [Ir(NCN)(NNN)]2+ complexes are very feeble emitters even at 77 K, probably due to the almost exclusively interligand charge-transfer nature of the lowest-energy excited state in these complexes.
Citation
Wilkinson, A., Puschman, H., Howard, J., Foster, C., & Williams, J. (2006). Luminescent Complexes of Iridium(III) Containing N∧C∧N-Coordinating Terdentate Ligands. Inorganic Chemistry, 45(21), 8685-8699. https://doi.org/10.1021/ic061172l
Journal Article Type | Article |
---|---|
Publication Date | Oct 1, 2006 |
Deposit Date | May 3, 2007 |
Journal | Inorganic Chemistry |
Print ISSN | 0020-1669 |
Electronic ISSN | 1520-510X |
Publisher | American Chemical Society |
Peer Reviewed | Peer Reviewed |
Volume | 45 |
Issue | 21 |
Pages | 8685-8699 |
DOI | https://doi.org/10.1021/ic061172l |
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