Emissive Metallomesogens Based on 2-Phenylpyridine Complexes of Iridium(III)

Santoro, Amedeo; Prokhorov, Anton M.; Kozhevnikov, Valery N.; Whitwood, Adrian C.; Donnio, Bertrand; Williams, J. A. Gareth; Bruce, Duncan W.

doi:10.1021/ja201245s

Cited by 85 publications

(54 citation statements)

References 24 publications

(23 reference statements)

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“…A four coordinate Pt II square planar metal complex has also been reported with two 2-phenylpyridine and two Cl -ligands (Yoshinari et al 2010). Complexes with substituted 2-phenylpyridine ligands have also been reported (Santoro et al, 2011). Here, we report the structure of a tetrahedrally coordinated Zn 2+ complex which crystallizes in the tetragonal space group I4 1 cd with one half molecule in the asymmetric unit.…”

Section: Methodsmentioning

confidence: 71%

Dichloridobis(2-phenylpyridine-κN)zinc(II)

Sivanesan¹,

Lee²,

Yoon³

2012

Acta Cryst E

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In the title compound, [ZnCl2(C11H9N)2], the Zn2+ cation lies on a twofold axis and is coordinated by two Cl− anions and the N atoms of two 2-phenylpyridine ligands, forming a ZnN2Cl2 polyhedron with a slightly distorted tetrahedral coordination geometry. The dihedral angle between the phenyl ring and the metal-bound pyridine ring is 50.3 (4)° for each 2-phenylpyridine ligand. This arranges the phenyl ring from one ligand in the complex above the pyridine ring of the other resulting in an intramolecular π–π interaction, with a centroid–centroid distance of 3.6796 (17) Å. Weak C—H⋯Cl hydrogen bonds stabilize the crystal packing, linking molecules into chains along the c axis.

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Section: Methodsmentioning

confidence: 71%

Dichloridobis(2-phenylpyridine-κN)zinc(II)

Sivanesan¹,

Lee²,

Yoon³

2012

Acta Cryst E

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“…5 Å. 23,26,27,32,34,40,47 (It is noteworthy that with [Ir(ppy) 2 µ-Cl] 2 -type complexes where the Ir-Ir distances are <4 Å only the less sterically congested rac ΔΔ/ɅɅ diastereomers have been reported to date [15][16][17][18]39,[48][49][50][51][52][53][54][55] ). For 13-16 the diastereomers were separated by fractional crystallization, silica column chromatography, or a combination of the two techniques.…”

Section: Synthesismentioning

confidence: 99%

Synthesis, Diastereomer Separation, and Optoelectronic and Structural Properties of Dinuclear Cyclometalated Iridium(III) Complexes with Bridging Diarylhydrazide Ligands

et al. 2017

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(2017) 'Synthesis, diastereomer separation, and optoelectronic and structural properties of dinuclear cyclometalated iridium(III) complexes with bridging diarylhydrazide ligands. ', Organometallics., 36 (5). pp. 981-993.Further information on publisher's website:https://doi.org/10.1021/acs.organomet.6b00887Publisher's copyright statement:This document is the Accepted Manuscript version of a Published Work that appeared in nal form in Organometallics, copyright c 2017 American Chemical Society after peer review and technical editing by the publisher. To access the nal edited and published work see https://doi.org/10.1021/acs.organomet.6b00887. Additional information:Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. ABSTRACT: A series of diiridium complexes 13-16 bridged by diarylhydrazine ligands and cyclometalated by phenylpyridine or phenylpyrazole ligands was synthesized. In all cases the ɅΔ meso and ɅɅ/ΔΔ rac diastereomers were separated and characterized by single-crystal X-ray diffraction, revealing intramolecular - stacking between arenes of the bridging and cyclometalating ligands. Density functional theory (DFT) calculations show that in general the HOMOs are mainly localized on the iridium centers, the cyclometalating phenyl moieties and the central hydrazide components of the bridging ligands, while the LUMOs are primarily localized on the N-heterocycles (pyridine or pyrazole) of the cyclometalating ligands. This series of complexes, especially with the separated diastereomers, provides an ideal opportunity to study the effects of subtle structural changes on the optoelectronic properties of diiridium systems: significant differences are observed between the rac and meso isomers in some cases. A cyclic voltammetric study of the electrochemical properties of the eight complexes reveals strong intramolecular interactions between the iridium centers. The photophysical properties are reported in solution, and in rigid poly(methyl methacrylate) (PMMA) or 2-methyltetrahydrofuran (2-MeTHF) (at 77 K) matrices where some of the complexes are strongly emissive in the turquoise and green regions (Φ PL 42-68 ±10%) due to matrix-induced restricted intramolecular motion (RIM).

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“…[10][11][12][13][14][15][16] Transition-metal complexes based on, for example, iridium-(III), rhenium(I) and ruthenium(II) are attaining significant interest for application in imaging. [17][18][19][20][21][22][23][24][25][26][27][28] These phosphorescent metal complexes often posses better photophysical properties than organic fluorophores, such as long luminescence lifetimes. [17,27] The long lifetime of transition-metal complexes can be used to discriminate the signal from autofluorescence; that is, the lifetime is generally 100 ns-ms, whereas autofluorescence has a lifetime of 0.1-7 ns.…”

Section: Introductionmentioning

confidence: 99%

Peptide‐Functionalized Luminescent Iridium Complexes for Lifetime Imaging of CXCR4 Expression

et al. 2011

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The chemokine receptor 4 (CXCR4) is over-expressed in 23 types of cancer in which it plays a role in, among others, the metastatic spread. For this reason it is a potential biomarker for the field of diagnostic oncology. The antagonistic Ac-TZ14011 peptide, which binds to CXCR4, has been conjugated to luminescent iridium dyes to allow for CXCR4 visualization. The iridium dyes are cyclometalated octahedral iridium(III) 2-phenylpyridine complexes that can be functionalized with one, two or three targeting Ac-TZ14011 peptides. Confocal microscopy and fluorescence lifetime imaging microscopy (FLIM) showed that the peptide-iridium complex conjugates can be used to visualize CXCR4 expression in tumor cells. The CXCR4 receptor affinity and specific cell binding of the mono-, di- and trimeric peptide derivatives were assessed by using flow cytometry. The three derivatives possessed nanomolar receptor affinity and could distinguish between cell lines with different CXCR4 expression levels. This yields the first example of a neutral iridium(III) complex functionalized with peptides for FLIM-based visualization of a cancer associated membrane receptor.

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Emissive Metallomesogens Based on 2-Phenylpyridine Complexes of Iridium(III)

Cited by 85 publications

References 24 publications

Dichloridobis(2-phenylpyridine-κN)zinc(II)

Dichloridobis(2-phenylpyridine-κN)zinc(II)

Synthesis, Diastereomer Separation, and Optoelectronic and Structural Properties of Dinuclear Cyclometalated Iridium(III) Complexes with Bridging Diarylhydrazide Ligands

Peptide‐Functionalized Luminescent Iridium Complexes for Lifetime Imaging of CXCR4 Expression

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