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Issue 45, 2010
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Two-photon luminescence from polar bis-terpyridyl-stilbene derivatives of Ir(III) and Ru(II)

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Four structurally related iridium(III) and ruthenium(II) complexes bearing two polar terpyridylstilbene derived chromophores 4-(4-{2-[4-(methoxy)phenyl]ethenyl}phenyl)-2,2′-6′,2′′-terpyridine (ttpyeneanisole) and 4-(4-{2-[phenyl]ethenyl}phenyl)-2,2′-6′,2′′-terpyridine (tpystilbene) have been synthesised and characterised in the solid state and in solution. In the solid state, the dihedral angle subtending the pyridyl and tolyl groups of 27.1° in the Ir(III) complex [Ir(ttpyeneanisole)2]·3PF6 is more acute than in the Ru(II) derivative [Ru(tpystilbene)2]·2PF6 (35.5°), indicating the presence of a greater degree of π-delocalisation across the terpyridine unit in the former compound. Their luminescence properties in fluid solution have been investigated following both resonant and non-resonant excitation. We have shown that each of the complexes undergoes two-photon excitation when excited in the near infrared (740 to 820 nm), with two-photon absorption cross sections in the range 11–67 × 10−50 cm4 s photon−1. The larger cross sections for the Ir(III) complexes reflect the differences observed in the solid state. This work therefore demonstrates that such complexes are promising as luminescent markers for 3D imaging and illustrates that simple functionalisation of the chromophores and the choice of metal can lead to marked enhancements in the two-photon cross sections (σ2) compared to those of simpler heteroleptic polypyridyl based derivatives.

Graphical abstract: Two-photon luminescence from polar bis-terpyridyl-stilbene derivatives of Ir(iii) and Ru(ii)

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The article was received on 29 Jun 2010, accepted on 03 Sep 2010 and first published on 13 Oct 2010

Article type: Paper
DOI: 10.1039/C0DT00750A
Citation: Dalton Trans., 2010,39, 10837-10846
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    Two-photon luminescence from polar bis-terpyridyl-stilbene derivatives of Ir(III) and Ru(II)

    L. S. Natrajan, A. Toulmin, A. Chew and S. W. Magennis, Dalton Trans., 2010, 39, 10837
    DOI: 10.1039/C0DT00750A

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