Long-lived cyclometallated iridium complexes: Synthesis, structure, DFT and photocatalytic aspects

Laha, Paltan; Chandra, Falguni; Husain, Ahmad; Koner, Apurba Lal; Patra, Srikanta

doi:10.1016/j.dyepig.2021.109925

Cited by 9 publications

(8 citation statements)

References 80 publications

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“…The 13 C NMR spectrum of [ 1 ](ClO 4 ) 2 displays three distinct signals at 202.6, 167.1, and 166.9 ppm, which correspond to the binding carbon centers of phpy with ruthenium and ppy with iridium, respectively. A similar type of observation for cyclometalated complexes has also been reported previously. ,,,, This further affirms the Ru–C coordination in complex [ 1 ](ClO 4 ) 2 . The 1 H– 1 H correlation spectroscopy study was conducted (Figure ) to elucidate further the structural aspect of complex [ 1 ](ClO 4 ) 2 .…”

Section: Resultssupporting

confidence: 90%

“…A similar type of observation for cyclometalated complexes has also been reported previously. 55,57,62,64,71 This further affirms the Ru− C coordination in complex [1](ClO 4 ) 2 . The 1 H− 1 H correlation spectroscopy study was conducted (Figure 2) to elucidate further the structural aspect of complex [1]…”

Section: ■ Results and Discussionsupporting

confidence: 68%

“…The N−Ir1−N and N− Ir1−C bond angles are in line with the structurally similar iridium complexes. 23,[55][56][57]62,64 On the other hand, the Ru 1 − N 7 /N 8 /N 9 (tpy) (1.937−2.092 Å) distances are quite shorter than Ru 1 −N 6 (2.65 Å), which is again the trans-directing effect of the phenanthroline C(C31) unit of the phpy ligand. This further confirms the Ru−C coordination of the [Ru(tpy)] unit with the phpy ligand.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Ligands having rigid and flexible frameworks with variable coordination sites are relatively uncommon. 57 In general, Ru center coordinates with polypyridyl ligands through neutral N ∧ N donor sites (Chart 1A). 23 Binding of Ru through anionic N ∧ N ∧ C − /N ∧ C − donor sites of polypyridyl ligands are less common (Chart 1B).…”

Section: ■ Introductionmentioning

confidence: 99%

“…Most of the ligand frameworks used are either rigid or flexible. Ligands having rigid and flexible frameworks with variable coordination sites are relatively uncommon. − The polypyridyl-pyrazine-based 2,3-di(pyridin-2-yl)pyrazino[2,3- f ][1,10] phenanthroline (phpy) ligand offers a rigid framework at the phenanthroline end and flexible donors sites at the pyrazine end. The flexible pyridine donors at the pyrazine end can potentially coordinate with the same/different metals in various coordination modes (Chart ).…”

Section: Introductionmentioning

confidence: 99%

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Asymmetrically Coordinated Heterodimetallic Ir–Ru System: Synthesis, Computational, and Anticancer Aspects

et al. 2023

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Herein, we present an unprecedented formation of a heterodinuclear complex [{(ppy)2IrIII}(μ-phpy){RuII(tpy)}](ClO4)2 {[1](ClO4)2} using terpyridyl/phenylpyridine as ancillary ligands and asymmetric phpy as a bridging ligand. The asymmetric binding mode (N∧N-∩-N∧N∧C–) of the phpy ligand in {[1](ClO4)2} is confirmed by 1H, 13C, 1H–1H correlated spectroscopy (COSY), high-resolution mass spectrum (HRMS), single-crystal X-ray crystallography techniques, and solution conductivity measurements. Theoretical investigation suggests that the highest occupied molecular orbital (HOMO) and the least unoccupied molecular orbital (LUMO) of [1]2+ are located on iridium/ppy and phpy, respectively. The complex displays a broad low energy charge transfer (CT) band within 450–575 nm. The time-dependent density functional theory (TDDFT) analysis suggests this as a mixture of metal-to-ligand charge transfer (MLCT) and ligand-to-ligand charge transfer (LLCT), where both ruthenium, iridium, and ligands are involved. Complex {[1](ClO4)2} exhibits RuIIIrIII/RuIIIIrIII- and RuIIIIrIII/RuIIIIrIV-based oxidative couples at 0.83 and 1.39 V, respectively. The complex shows anticancer activity and selectivity toward human breast cancer cells (IC50; MCF-7: 9.3 ± 1.2 μM, and MDA-MB-231: 8.6 ± 1.2 μM) over normal breast cells (MCF 10A: IC50 ≈ 21 ± 1.3 μM). The Western blot analysis and fluorescence microscopy images suggest that combined apoptosis and autophagy are responsible for cancer cell death.

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