Ir(2-Phenylpyridine)₂(benzene-1,2-dithiolate) Anion as a Diastereoselective Metalloligand and Nucleophile: Stereoelectronic Effect, Spectroscopy, and Computational Study of the Methylated and Aurated Complexes and their Oxygenation Products

Abstract

The anionic complex [Ir(2-phenylpyridine)2(benzene-1,2-dithiolate)](-) ([IrSS](-)) is a nucleophile and metalloligand that reacts with methyl iodide and AuPR3(+) (R = Ph or Et) to form S-methylated complexes (thiother-thiolate and dithiother complexes) and S-aurated complexes, respectively. The reactions are completely diastereselective, producing only the enantiomers ΛS and ΔR or ΛSS and ΔRR. The diastereoselectivity is stereoelectronically controlled by the orientation of the highest occupied molecular orbital (HOMO) of [IrSS](-) arising from filled dπ-pπ antibonding interactions, and the chirality of the iridium ion. Methylation or auration removes the high-energy lone pair of the thiolate S atom, leading to low-lying HOMOs composed mainly of the Ir d-orbital and the 2-phenylpyridine π (ppyπ) orbital. The methylated and aurated complexes can be oxidized by H2O2 or peracid to give sulfinate-thiother, disulfoxide, and sulfinate-sulfoxide complexes, and the oxygenation further stabilizes the HOMO. All the complexes are luminescent, and their electronic spectra are interpreted with the aid of time-dependent density functional theory calculations. The thiother-thiolate complex exhibits ligand(S)-to-ligand(π* of ppy)-charge-transfer/metal-to-ligand-charge-transfer absorption (LLCT/MLCT) and a relatively low-energy (3)LLCT/MLCT emission, while the other complexes display (3)ππ*/MLCT emissions.

η1‐Arene Complexes as Intermediates in the Preparation of Molecular Phosphorescent Iridium(III) Complexes

“…2017, 23,15729 -15737 www.chemeurj.org 2017 Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim to formally spin-forbidden 3 MLCT transitions, causedb yt he large spin-orbit coupling introduced by the iridium center. [28] Complexes 4 and 5 are green emissivea fter photoexcitation in the solid state at room temperature and in 2-methyltetrahydrofurana tr oom temperature and at 77 K, displaying bands centered between 515 and 555 nm. Figure 6s hows the emission spectra and the calculated and experimental wavelengths, lifetimes, and quantumy ields are presented in Ta ble 2.…”

Simple Synthesis of Red Iridium(III) Complexes with Sulfur-Contained Four-Membered Ancillary Ligands for OLEDs

“…Remarkably, all the Ir(III) complexes were prepared under quite mild conditions (5 min at room temperature in tetrahydrofuran) in yields of 48.9-85.5%, owing to the strong coordination capability of sulfur atoms with iridium atoms [24]. All these complexes were characterized by 1 H NMR, 13 C NMR, 9 F NMR, and high-resolution mass spectrometer (HR-MS). Particularly, the single crystals of Ir-2 and Ir-3 were obtained by growing slowly through solvent diffusion from methanol into dichloromethane solutions at room temperature.…”

“…All reagents and chemicals were purchased from commercial sources and used without further purification. 1 H NMR, 13 C NMR and 19 F NMR spectra were measured on a Bruker AM 400 spectrometer (Bruker, Karlsruhe, Germany). High-resolution electrospray mass spectra (HR-MS) were measured on a MTQ III q-TOF (Bruker, Karlsruhe, Germany).…”

“…The following are available online. S10: 13 C NMR spectrum of Ir-1; Figure S11: 13 C NMR spectrum of Ir-2; Figure S12: 13 C NMR spectrum of Ir-3; Figure S13: 19 F NMR spectrum of Ir-1; Figure S14: 19 F NMR spectrum of Ir-2; Figure S15: 19 F NMR spectrum of Ir-3; Table S1: The crystallographic data of Ir-2 and Ir-3; Table S2: Selected bond lengths and angles of Ir-2 and Ir-3; Table S3: Frontier molecular orbital distributions and energy splitting of singlet and triplet states of Ir-3; Table S4: HOMO and LUMO electron cloud density distributions of each fragment of all Ir(III) complexes; Table S5: The reported device performances with Ir(III) complexes based on sulfur-containing four-membered ancillary ligands.…”

“…The S atom has a high affinity and good coordination ability for transition metal ions, which can lead to the synthesis of Ir(III) complexes with sulfur-containing ligands at room temperature [ 11 , 12 ]. Besides, the sulfur atom is able to stabilize metal ions in unusual oxidation states [ 13 , 14 , 15 ]. Therefore, it has a great advantage over the costly traditional way of refluxing the [(C^N) 2 Ir(μ-Cl)] 2 chloride-bridged dimers with cyclometalated or ancillary ligands at high temperature for a long time [ 16 ].…”