Structural and optical properties of new cyclometalated Ru(II) derived compounds

Finck, Sidonie; Issenhuth, Jean‐Thomas; Despax, Stéphane; Sirlin, Claude B.; Pfeffer, Michel; Poidevin, Corentin; Gourlaouen, Christophe; Boeglin, Alex; Daniel, Chantal

doi:10.1016/j.jorganchem.2013.08.032

Cited by 17 publications

(12 citation statements)

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“…The Ru–N bond lengths involving the two bipyridine ligands and the bridging ligand are within the normal range (2.04–2.07 Å) of what is expected for such bonds in [Ru(bpy) 2 (phenanthroline)] 2+ type complexes. 102 , 103 The Cu–N distances are 2.00–2.06 Å, in good agreement with bond lengths reported for related mononuclear CuHETPHEN complexes. 66 , 70 , 71 …”

Section: Resultssupporting

confidence: 87%

Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy

et al. 2018

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Section: Resultssupporting

confidence: 87%

Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy

et al. 2018

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“…It is well-known that, in a simplified picture, the highest occupied orbitals in a pseudo-octahedral Ru(II) polypyridyl complex mainly consist of the ruthenium t 2g d orbitals while the lowest occupied orbitals typically correspond to π* orbitals localized on the ligands. , Therefore, the lowest intense absorption band is expected to be of metal to ligand charge transfer (MLCT) character stemming from electronic transitions from the t 2g manifold to the empty ligand lowest-lying orbitals and leading to the population of a singlet state of MLCT nature under light irradiation. A simple way to red shift the MLCT absorption energy is, therefore, to decrease the HOMO–LUMO gap by an ad-hoc functionalization of the ligands.…”

Section: Resultsmentioning

confidence: 99%

Rationally Designed Long-Wavelength Absorbing Ru(II) Polypyridyl Complexes as Photosensitizers for Photodynamic Therapy

et al. 2020

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The utilization of photodynamic therapy (PDT) for the treatment of various types of cancer has gained increasing attention over the last decades. Despite the clinical success of approved photosensitizers (PSs), their application is sometimes limited due to poor water solubility, aggregation, photodegradation, and slow clearance from the body. To overcome these drawbacks, research efforts are devoted toward the development of metal complexes and especially Ru(II) polypyridine complexes based on their attractive photophysical and biological properties. Despite the recent research developments, the vast majority of complexes utilize blue or UV-A light to obtain a PDT effect, limiting the penetration depth inside tissues and, therefore, the possibility to treat deep-seated or large tumors. To circumvent these drawbacks, we present the first example of a DFT guided search for efficient PDT PSs with a substantial spectral red shift toward the biological spectral window. Thanks to this design, we have unveiled a Ru(II) polypyridine complex that causes phototoxicity in the very low micromolar to nanomolar range at clinically relevant 595 nm, in monolayer cells as well as in 3D multicellular tumor spheroids.

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“…Whereas the TD‐DFT method is appropriate for describing lowest electronic excited states in a number of second‐ and third‐row transition metal complexes its use for first‐row transition metal complexes is more questionable . Indeed, describing on the same footing MLCT and MC excited states is a real challenge for computational chemistry.…”

Section: Resultsmentioning

confidence: 99%

Excited‐State Reactivity of [Mn(im)(CO)₃(phen)]⁺: A Structural Exploration

et al. 2018

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The electronic excited state reactivity of [Mn(im)(CO)3(phen)]+ (phen = 1,10‐phenanthroline; im = imidazole) ranging between 420 and 330 nm have been analyzed by means of relativistic spin–orbit time‐dependent density functional theory and wavefunction approaches (state‐average‐complete‐active‐space self‐consistent‐field/multistate CAS second‐order perturbation theory). Minimum energy conical intersection (MECI) structures and connecting pathways were explored using the artificial force induced reaction (AFIR) method. MECIs between the first and second singlet excited states (S1/S2‐MECIs) were searched by the single‐component AFIR (SC‐AFIR) algorithm combined with the gradient projection type optimizer. The structural, electronic, and excited states properties of [Mn(im)(CO)3(phen)]+ are compared to those of the Re(I) analogue [Re(im)(CO)3(phen)]+. The high density of excited states and the presence of low‐lying metal‐centered states that characterize the Mn complex add complexity to the photophysics and open various dissociative channels for both the CO and imidazole ligands. © 2018 Wiley Periodicals, Inc.

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Structural and optical properties of new cyclometalated Ru(II) derived compounds

Cited by 17 publications

References 65 publications

Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy

Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy

Rationally Designed Long-Wavelength Absorbing Ru(II) Polypyridyl Complexes as Photosensitizers for Photodynamic Therapy

Excited‐State Reactivity of [Mn(im)(CO)₃(phen)]⁺: A Structural Exploration

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Structural and optical properties of new cyclometalated Ru(II) derived compounds

Cited by 17 publications

References 65 publications

Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy

Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy

Rationally Designed Long-Wavelength Absorbing Ru(II) Polypyridyl Complexes as Photosensitizers for Photodynamic Therapy

Excited‐State Reactivity of [Mn(im)(CO)3(phen)]+: A Structural Exploration

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Excited‐State Reactivity of [Mn(im)(CO)₃(phen)]⁺: A Structural Exploration