Spectroscopic and redox properties of amine-functionalized K2[OsII(bpy)(CN)4] complexes

Abstract

We report the first examples of amine-functionalized K(2)[Os(II)(bpy)(CN)(4)] (bpy = 2,2'-bipyridine) complexes. The tetracyanoosmate complexes were prepared by UV irradiation (λ = 254 nm) of K(4)[Os(II)(CN)(6)] and primary amine-functionalized bpy ligands in acidic aqueous media. The aqueous solution pH dependences of the spectroscopic and redox properties of 4,4'- and 5,5'-substituted complexes have been investigated. The pendant amine functional groups and coordinated cyanide ligands are basic sites that can be sequentially protonated, thereby allowing systematic tuning of electrochemical and optical spectroscopic properties.

Electronic Structures, Spectroscopy, and Electrochemistry of [M(diimine)(CN-BR3)4]2– (M = Fe, Ru; R = Ph, C6F5) Complexes

“…Heteroleptic (diimine-cyanide) complexes of ruthenium, iron, copper, iridium, rhenium, and osmium , have found use as vapochromic agents, electrochemically reversible oxidants and reductants, phosphors for organic light-emitting diodes, ,, and photooxidants and photoreductants . We and others have shown that octahedral metal cyanides bond with boranes such as boron trifluoride, lowering the σ and π* orbital energies of the cyanide ligand, which weakens metal–carbon bonding and strengthens CN bonding.…”

Trinuclear Ruthenium Clusters as Bivalent Electrochemical Probes for Ligand–Receptor Binding Interactions

“…1 Electrochemical biosensors have been utilized to detect a variety of biomolecules including DNA, antibodies, enzymes, and proteins. 2–14 Despite their growing popularity, a number of challenges remain in improving sensitivity. 15 Many popular biosensors rely on the measurement of changes in impedance that are caused by target binding to the electrode surface.…”

“…Since the development of the first glucose sensors, electrochemical biosensors have gained popularity due to their low cost, ease of use, and remarkable reproducibility . Electrochemical biosensors have been utilized to detect a variety of biomolecules including DNA, antibodies, enzymes, and proteins. − Despite their growing popularity, a number of challenges remain in improving sensitivity . Many popular biosensors rely on the measurement of changes in impedance that are caused by target binding to the electrode surface.…”