Understanding Electrogenerated Chemiluminescence Efficiency in Blue-Shifted Iridium(III)-Complexes: An Experimental and Theoretical Study

• Published in: Chemistry : a European journal Vol. 20; no. 12; pp. 3322 - 3332
• Main Authors: Barbante, Gregory J., Doeven, Egan H., Kerr, Emily, Connell, Timothy U., Donnelly, Paul S., White, Jonathan M., Lópes, Thais, Laird, Sarah, Wilson, David J. D., Barnard, Peter J., Hogan, Conor F., Francis, Paul S.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 17.03.2014; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Subjects: Chemiluminescence; Chemistry; density functional calculations; Efficiency; electrochemiluminescence; electrochemistry; Energy gap; Energy management; iridium; Ligands; luminescence; Molecular orbitals; Reaction kinetics; Strategy; Thermodynamics; iridium; density functional calculations; electrochemiluminescence; luminescence; electrochemistry
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201304500

Compared to tris(2‐phenylpyridine)iridium(III) ([Ir(ppy)3]), iridium(III) complexes containing difluorophenylpyridine (df‐ppy) and/or an ancillary triazolylpyridine ligand [3‐phenyl‐1,2,4‐triazol‐5‐ylpyridinato (ptp) or 1‐benzyl‐1,2,3‐triazol‐4‐ylpyridine (ptb)] exhibit considerable hypsochromic shifts (ca. 25–60 nm), due to the significant stabilising effect of these ligands on the HOMO energy, whilst having relatively little effect on the LUMO. Despite their lower photoluminescence quantum yields compared with [Ir(ppy)3] and [Ir(df‐ppy)3], the iridium(III) complexes containing triazolylpyridine ligands gave greater electrogenerated chemiluminescence (ECL) intensities (using tri‐n‐propylamine (TPA) as a co‐reactant), which can in part be ascribed to the more energetically favourable reactions of the oxidised complex (M+) with both TPA and its neutral radical oxidation product. The calculated iridium(III) complex LUMO energies were shown to be a good predictor of the corresponding M+ LUMO energies, and both HOMO and LUMO levels are related to ECL efficiency. The theoretical and experimental data together show that the best strategy for the design of efficient new blue‐shifted electrochemiluminophores is to aim to stabilise the HOMO, while only moderately stabilising the LUMO, thereby increasing the energy gap but ensuring favourable thermodynamics and kinetics for the ECL reaction. Of the iridium(III) complexes examined, [Ir(df‐ppy)2(ptb)]+ was most attractive as a blue‐emitter for ECL detection, featuring a large hypsochromic shift (λmax=454 and 484 nm), superior co‐reactant ECL intensity than the archetypal homoleptic green and blue emitters: [Ir(ppy)3] and [Ir(df‐ppy)3] (by over 16‐fold and threefold, respectively), and greater solubility in polar solvents. Into the blue: Theoretical and experimental studies reveal the most effective strategies for the design of blue‐shifted iridium(III) complexes for efficient electrogenerated chemiluminescence. Stabilisation of the HOMO while only moderately stabilising the LUMO increases the energy gap, thus ensuring favourable thermodynamics and kinetics for the reaction leading to the excited state (see figure).