Tuning Oxyquinolate Non‐Innocence at the Ruthenium Polypyridyl Core

Zhao, Helen C.; Fu, Bi Li; Schweinfurth, David; Harney, Joseph P.; Sarkar, Biprajit; Tsai, Ming Kang; Rochford, Jonathan

doi:10.1002/ejic.201300373

Cited by 17 publications

(24 citation statements)

References 66 publications

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“…Over the years, many studies have been performed focusing on the non-innocent character of different metal complexes both from an experimental and theoretical point of view. [34][35][36][37][38][39][40][41] In 2006, Wada and co-workers demonstrated how the oxidation state of the dioxo ligand in a given metal-coligand environment depends on the nature of its substituents. 42 More specifically, the authors investigated a series of [Ru(OAc)(dioxolene)(terpy)] complexes with dioxo ligands carrying electron withdrawing (EWG) or electron donating (EDG) groups.…”

Section: Introductionmentioning

confidence: 99%

“…42 compounds were investigated in depth. As described in the literature, [34][35][36][37][38][39][40][41] the variation of the electron density on the dioxo ligand leads to the modification of its oxidation state when bound as a ligand. The different oxidation states of the dioxo ligands have a strong bearing on the physical properties of the complexes, affecting, among other parameters, their electronic structures and hence the charge state.…”

Section: Introductionmentioning

confidence: 99%

“…Driven by the promising properties unveiled for Ru-sq, we undertook a structure–activity relationship (SAR) study, keeping the same Ru(II) polypyridyl core (i.e., Ru(DIP) 2 ) but substituting the catechol-type dioxo ligand. Over the years, many studies have been performed that focus on the noninnocent character of different metal complexes from both experimental and theoretical points of view. − In 2006, Wada and co-workers demonstrated how the oxidation state of the dioxo ligand in a given metal-coligand environment depends on the nature of its substituents . More specifically, the authors investigated a series of [Ru(OAc)(dioxolene)(terpy)] complexes with dioxo ligands carrying electron-withdrawing (EWG) or electron-donating (EDG) groups .…”

Section: Introductionmentioning

confidence: 99%

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Increasing the Cytotoxicity of Ru(II) Polypyridyl Complexes by Tuning the Electronic Structure of Dioxo Ligands

et al. 2020

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Due to the great potential expressed by an anticancer drug candidate previously reported by our group, namely, Ru-sq ([Ru(DIP)2(sq)](PF6) (DIP: 4,7-diphenyl-1,10phenanthroline, sq: semiquinonate ligand), we describe in this work a structure-activity relationship (SAR) that involves a broader range of derivatives resulting from the coordination of different catecholate-type dioxo ligands to the same Ru(DIP)2 core. More in detail, we chose catechols carrying either electron-donating or electronwithdrawing groups EDG or EWG and investigated the physico-chemical and biological properties of their complexes. Several pieces of experimental evidences demonstrated that the coordination of catechols bearing EDGs led to deep red positively charged complexes 1-4 in which the preferred oxidation state of the dioxo ligand is the uninegatively charged semiquinonate. Complexes 5 and 6, on the other hand, are blue/violet neutral complexes, which carry an EWG substituted dinegatively charged catecholate ligand. The biological investigation of complexes 1-6 led to the conclusion that the difference in their physico-chemical properties has a strong impact on their biological activity. Thus, complexes 1-4 expressed much higher cytotoxicities than complexes 5 and 6. Complex 1 constitutes the most promising compound of the series and was selected for a more in-depth biological investigation. Apart from its remarkably high cytotoxicity (IC50 = 0.07-0.7 µM in different cancerous cell lines) complex 1 was taken up by HeLa cells very efficiently by a passive transportation mechanism. Moreover, its moderate accumulation in several cellular compartments (i.e. nucleus, lysosomes, mitochondria and cytoplasm) is extremely advantageous in the search of a potential drug with multiple modes of action. Further DNA metalation and metabolic studies pointed to the direct interaction of complex 1 with DNA and to the severe impairment of the mitochondrial function. Multiple targets, together with its 4 outstanding cytotoxicity, make complex 1 a valuable candidate in the field of chemotherapy research. Noteworthy, a preliminary biodistribution study on healthy mice demonstrated the suitability of complex 1 for further in vivo studies.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Increasing the Cytotoxicity of Ru(II) Polypyridyl Complexes by Tuning the Electronic Structure of Dioxo Ligands

et al. 2020

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“…Given that the complexes contain two carbonyl ligands of the highest order in the spectrochemical series, no obvious absorption was observed in the visible region (Supplementary Materials Figure S3). However, intense polypyridyl-centered π-π* intraligand transitions were observed in the UV region [24]. Table 1 summarizes the structural parameters of a series of [Ru(pynp)(NˆN)(CO) 2 ] 2+ complexes.…”

Section: Characterization Of Complexesmentioning

confidence: 99%

Coordination Chemistry of Ru(II) Complexes of an Asymmetric Bipyridine Analogue: Synergistic Effects of Supporting Ligand and Coordination Geometry on Reactivities

et al. 2019

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The reactivities of transition metal coordination compounds are often controlled by the environment around the coordination sphere. For ruthenium(II) complexes, differences in polypyridyl supporting ligands affect some types of reactivity despite identical coordination geometries. To evaluate the synergistic effects of (i) the supporting ligands, and (ii) the coordination geometry, a series of dicarbonyl–ruthenium(II) complexes that contain both asymmetric and symmetric bidentate polypyridyl ligands were synthesized. Molecular structures of the complexes were determined by X-ray crystallography to distinguish their steric configuration. Structural, computational, and electrochemical analysis revealed some differences between the isomers. Photo- and thermal reactions indicated that the reactivities of the complexes were significantly affected by both their structures and the ligands involved.

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“…The physico-chemical and biological properties of these compounds were investigated in depth. As described in the literature, [34][35][36][37][38][39][40][41] the variation of the electron density on the dioxo ligand leads to the modification of its oxidation state when bound as a ligand. The different oxidation states of the dioxo ligands have a strong bearing on the physical properties of the complexes, affecting, among other parameters, their electronic structures and hence the charge state.…”

Section: Introductionmentioning

confidence: 99%

Increasing the Cytotoxicity of Ru(II) Polypyridyl Complexes by Tuning the Electronic Structure of Dioxo Ligands

Notaro¹,

Jakubaszek²,

Rotthowe³

et al. 2019

Preprint

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<div>Due to the great potential expressed by an anticancer drug candidate previously reported by our group, namely Ru-sq ([Ru(DIP)2(sq)](PF6) (DIP: 4,7-diphenyl-1,10-phenanthroline, sq: semiquinonate ligand), we describe in this work a structure-activity relationship (SAR) that involves a broader range of derivatives resulting from the coordination of different catecholate-like dioxoligands to the same Ru(DIP)2 core. More in detail, we chose catechols carrying either electron-donating or electronwithdrawing groups EDG or EWG and investigated the physico-chemical and biological properties of their complexes. Several pieces of experimental evidences demonstrated that the coordination of catechols bearing EDGs led to deep red positively charged complexes 1–4 in which the preferred oxidation state of the dioxoligand is the uninegatively charged semiquinonate. Complexes 5 and 6, on the other hand, are blue/violet neutral complexes which carry an EWG substituted dinegatively charged catecholate ligand. The biological investigation of complexes 1–6 led to the conclusion that the difference in their physico-chemical properties has a strong impact on their biological activity. Thus, complexes 1–4 expressed much higher cytotoxicities than complexes 5 and 6. Complex 1 constitutes the most promising compound of the series and was selected for a more in-depth biological investigation. Apart from its remarkably high cytotoxicity (IC50 = 0.07–0.7 μM in different cancerous cell lines) complex 1 was taken up by HeLa cells very efficiently by a passive transportation mechanism. Moreover, its moderate accumulation in several cellular compartments (i.e. nucleus, lysosomes, mitochondria and cytoplasm) is extremely advantageous in the search of a potential drug with multiple modes of action. Further DNA metalation and metabolic studies pointed to the direct interaction of complex 1 with DNA and to the severe impairment of the mitochondrial function. Multiple targets, together with its outstanding cytotoxicity, make complex 1 a valuable candidate in the field of chemotherapy research.</div>

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Tuning Oxyquinolate Non‐Innocence at the Ruthenium Polypyridyl Core

Cited by 17 publications

References 66 publications

Increasing the Cytotoxicity of Ru(II) Polypyridyl Complexes by Tuning the Electronic Structure of Dioxo Ligands

Increasing the Cytotoxicity of Ru(II) Polypyridyl Complexes by Tuning the Electronic Structure of Dioxo Ligands

Coordination Chemistry of Ru(II) Complexes of an Asymmetric Bipyridine Analogue: Synergistic Effects of Supporting Ligand and Coordination Geometry on Reactivities

Increasing the Cytotoxicity of Ru(II) Polypyridyl Complexes by Tuning the Electronic Structure of Dioxo Ligands

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