Proton-Induced Reversible Modulation of the Luminescent Output of Rhenium(I), Iridium(III), and Ruthenium(II) Tetrazolate Complexes
| Autor: | Massimiliano Massi, Stefano Stagni, Sara Muzzioli, Paolo Raiteri, Stefano Zacchini, Melissa V. Werrett, Antonio Palazzi, Phillip J. Wright |
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| Přispěvatelé: | M. V. Werrett, S. Muzzioli, P. J. Wright, A. Palazzi, P. Raiteri, S. Zacchini, M. Massi, S. Stagni |
| Jazyk: | angličtina |
| Rok vydání: | 2014 |
| Předmět: |
Inorganic chemistry
chemistry.chemical_element Quantum yield RHENIUM COMPLEXES Protonation Rhenium Ring (chemistry) Ruthenium IRIDIUM COMPLEXES Inorganic Chemistry PROTONATION Crystallography chemistry.chemical_compound RUTHENIUM COMPLEXES chemistry TETRAZOLATE LIGANDS Electrophile LUMINESCENCE Iridium Physical and Theoretical Chemistry Triflic acid |
| Popis: | One of the distinct features of metal-tetrazolate complexes is the possibility of performing electrophilic additions onto the imine-type nitrogens of the coordinated five-membered ring. These reactions, in particular, provide a useful tool for varying the main structural and electronic properties of the starting tetrazolate complexes. In this paper, we demonstrate how the use of a simple protonation-deprotonation protocol enables us to reversibly change, to a significant extent, the light-emission output and performance of a series of Re(I)-tetrazolate-based phosphors of the general formulation fac-[Re(N(∧)N)(CO)3L], where N(∧)N denotes diimine-type ligands such as 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) and L represents a series of different 5-aryl tetrazolates. Indeed, upon addition of triflic acid to these neutral Re(I) complexes, a consistent blue shift (Δλmax ca. 50 nm) of the emission maximum is observed and the protonated species also display increased quantum yield values (4-13 times greater than the starting compounds) and longer decay lifetimes. This alteration can be reversed to the initial condition by further treating the protonated Re(I) complex with a base such as triethylamine. Interestingly, the reversible modulation of luminescent features by the same protonation-deprotonation mechanism appears as a quite general characteristic of photoactive metal tetrazolate complexes, even for compounds in which the 2-pyridyl tetrazolate ligands coordinate the metal center with a bidentate mode, such as the corresponding Ir(III) cyclometalates [Ir(C(∧)N)2L] and the Ru(II) polypyridyl derivatives [Ru(bpy)2L](+). In these cases, the protonation of the starting materials leads to red-shifted and more intense emissions for the Ir(III) complexes, while almost complete quenching is observed in the case of the Ru(II) analogues. |
| Databáze: | OpenAIRE |
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