title: Electrogenerated chemiluminescence from heteroleptic iridium(III) complexes with multicolor emission.
abstract: Electrogenerated chemiluminescence (ECL) with different emission colors is important in the development of multichannel analytical techniques. In this report, five new heteroleptic iridium(III) complexes were synthesized, and their photophysical, electrochemical, and ECL properties were studied. Here, 2-(2,4-difluorophenyl)pyridine (dfppy, complex 1), 2-phenylbenzo[d]thiazole (bt, complex 2), and 2-phenylpyridine (ppy, complex 3) were used as the main ligands to tune the emission color, while avobenzone (avo) was used as the ancillary ligand. For comparison, complexes 4 and 5 with 2-phenylpyridine and 2-phenylbenzo[d]thiazole as the main ligand, respectively, and acetyl acetone (acac) as the ancillary ligand were also synthesized. All five iridium(III) complexes had strong intraligand absorption bands (π–π*) in the UV region (below 350 nm) and a featureless MLCT (d−π*) transition in the visible 400–500 nm range. Multicolored emissions were observed for these five iridium(III) complexes, including green, orange, and red for complexes 4, 5, 2, 1, 3, respectively. Density functional theory calculations indicate that the electronic density of the highest occupied molecular orbital is entirely located on the C^N ligands and the iridium atom, while the formation of the lowest unoccupied molecular orbital (LUMO) is complicated. The LUMO is mainly assigned to the ancillary ligand for complexes 1 and 3 but to the C^N ligand for complexes 2, 4, and 5. Cyclic voltammetry studies showed that all these complexes have a reversible oxidation wave, but no reduction waves were found in the electrochemical windows of CH2Cl2. The E1/2(ox) values of these complexes ranged from 0.642 to 0.978 V for complexes 3, 4, 2, 5, 1, (in increasing order) and are all lower than that of Ru(bpy)3(2+). Most importantly, when using tripropylamine as a coreactant, complexes 1–5 exhibited intense ECL signals with an emission wavelength centered at 616, 580, 663, 536, and 569 nm, respectively. In addition, complexes 1, 2, and 5 displayed approximately 2, 11, and 214 times higher ECL efficiencies than Ru(bpy)3(2+) under identical conditions.
authors.affiliation: Jiangsu Key Laboratory of Environmental Functional Materials, School of Chemistry, Biology and Material Engineering, Suzhou University of Science and Technology , Suzhou, Jiangsu 215009, P. R. China.
authors.forename: Yuyang
authors.initials: Y
authors.lastname: Zhou
authors.forename: Hongfang
authors.initials: H
authors.lastname: Gao
authors.forename: Xiaomei
authors.initials: X
authors.lastname: Wang
authors.forename: Honglan
authors.initials: H
authors.lastname: Qi
mesh_terms: D003116:Color; D055664:Electrochemical Techniques; D005456:Fluorescent Dyes / Q000138:chemical synthesis / Q000737:chemistry*; D007495:Iridium / Q000737:chemistry*; D049449:Luminescence; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D005456:Fluorescent Dyes; D009942:Organometallic Compounds; D007495:Iridium