Details

Autor(en) / Beteiligte

• Del Río, M Pilar
• Villarroya, B Eva
• López, José A
• Geer, Ana M
• Lahoz, Fernando J
• Ciriano, Miguel A
• Tejel, Cristina

Titel

Mixed-Valence Tetrametallic Iridium Chains

Ist Teil von

• Chemistry : a European journal, 2023-09, Vol.29 (52), p.e202301438

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2023

Quelle

Wiley-Blackwell Journals

Beschreibungen/Notizen

• Neutral [X-{Ir2}-{Ir2}-X] (X = Cl, Br, SCN, I) and dicationic [L-{Ir2}-{Ir2}-L]2+ (L = MeCN, Me2CO) tetrametallic iridium chains made by connecting two dinuclear {Ir2} units ({Ir2} = [Ir2(μ-OPy)2(CO)4], OPy = 2-pyridonate) by an iridium-iridium bond are described. The complexes exhibit fractional averaged oxidation states of +1.5 and electronic delocalization along the metallic chain. While the axial ligands do not significantly affect the metal-metal bond lengths, the metallic chain has a significant impact on the iridium-L/X bond distances. The complexes show free rotation around the unsupported iridium-iridium bond in solution, with a low-energy transition state for the chloride chain. The absorption spectra of these complexes show characteristic bands at 438-504 nm, which can be fine-tuned by varying the terminal capping ligands.