NDLI: Luminescent cyanometallates based on phenylpyridine-Ir(III) units: solvatochromism, metallochromism, and energy-transfer in Ir/Ln and Ir/Re complexes

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Weinstein, Julia A. Ward, Michael D. Hunter, Christopher A. Jennison, Petter Ali, Noorshida Mohd Macleod, Voirrey L. Sazanovich, Igor V.
Description	Author Affiliation: Ali NM ( Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, UK.)
Abstract	$[Ir(ppy)_{2}(CN)_{2}]^{−}$ (ppy = anion of 2-phenylpyridine ) and some substituted derivatives have been investigated for their ability to interact with additional metal cations , both in solution and the solid state, via the externally-directed cyanide lone pairs, and to act as energy-donors in the resulting assemblies. $[Ir(ppy)_{2}(CN)_{2}]^{−}$ is slightly solvatochromic, showing a blue-shift of the lowest energy absorption manifold in water compared to organic solvents , and the solubilised $^{t}Bu-substituted$ analogue $[Ir(^{t}Buppy)_{2}(CN)_{2}]^{−}$ $[^{t}Buppy$ = anion of $2-(4-^{t}Bu-phenyl)pyridine]$ is also metallochromic with coordination of the cyanide lone pairs to two M(II) cations in MeCN (M = Ba, Zn) resulting in blue-shifts of the lowest-energy absorption and emission maxima. These effects are however modest because of (i) the presence of only two cyanide groups, and (ii) the fact that the lowest-energy excited state has a substantial $^{3}LC$ component and is therefore not purely charge-transfer in nature. Crystallisation of $[Ir(ppy)_{2}(CN)_{2}]^{−}$ as its $(PPN)^{+}$ salt in the presence of excess of lanthanide(III) salts leads to formation of assemblies based on Ir–CN–Ln bonds, which generate in the solid state either $Ir_{2}Ln_{2}(μ-CN)_{4}$ square assemblies or linear trinuclear species with Ir–CN–Ln–NC–Ir cores. In the $Ir_{2}Eu_{2}(μ-CN)_{4}$ and $Ir_{2}Nd_{2}(μ-CN)_{4}$ complexes the Ir-based emission is substantially quenched due to energy-transfer to lower-lying f–f states of these lanthanide ions. In addition reaction of $[Ir(F_{2}ppy)_{2}(CN)_{2}]^{−}$ $[F_{2}ppy$ = cyclometallating anion of 2-(2,4-difluorophenyl)pyridine ] with $[Re(phen)(CO)_{3}(MeCN)][PF_{6}]$ in solution affords dinuclear IrRe and trinuclear $IrRe_{2}$ species in which $\{Re(phen)(CO)_{3}\}$ units are attached to the N-donor termini of one or both of the cyanide groups; these complexes have been structurally characterised and display quantitative Ir→Re energy-transfer, showing luminescence only from the Re(I) terminus on excitation of the Ir(III) unit.
ISSN	14779226
Issue Number	8
Journal	Dalton Trans.
Volume Number	41
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2012-02-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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