Syntheses, Crystal Structures, and Photoluminescence of a Series of Iridium(III) Complexes Containing the Pentafluorosulfanyl Group

Abstract

Eight neutral iridium(III) complexes (Ir1−Ir8) containing an electronwithdrawing pentafluorosulfanyl (−SF 5 ) group on cyclometalated ligands with different ancillary ligands were synthesized and investigated. 2-(3/4-(Pentafluorosulfanyl)phenyl)pyrimidine (for Ir1 and Ir2), 1-(3/4-(pentafluorosulfanyl)phenyl)isoquinoline (for Ir3 and Ir4), and 2-(3/4-(pentafluorosulfanyl)phenyl)pyridine (for Ir5−Ir8) were chosen as cyclometalated ligands and 2,2,6,6-tetramethylheptane-3,5-dione (for Ir1−Ir4), tetraphenylimidodiphosphinate (for Ir5 and Ir6), and bis(diphenylphorothioyl)amide (for Ir7 and Ir8) were used as ancillary ligands. The crystal structures of Ir1, Ir3, Ir4, Ir6, and Ir8 also confirmed the identities of these complexes. Complexes Ir1, Ir2, and Ir5−Ir8 exhibit sky blue to green emissions (480−533 nm) with high photoluminescence quantum efficiency yields up to 94.7% in CH 2 Cl 2 solution at room temperature. Complexes Ir3 and Ir4 are red phosphors (λ max = 607 nm, Φ = 76.8% for Ir3 and λ max = 627 nm, Φ = 49.2% for Ir4, respectively). Theoretical calculations were carried out to provide a further study of the orbital distributions and electronic states of eight Ir(III) complexes. Additionally, ion detection studies reveal that Ir2 has the potential for detecting Hg 2+ ion.

Ring-Expansion Strategy for α-Aryl Azahelicene Construction: Building Blocks for Optoelectronic Materials

“…In the various elegant synthetic methods for azahelicence preparation, two main strategies are usually adopted (Scheme a): the first is to construct C–C bonds of N-heterocycle-containing precursors, via a cross-coupling, oxidative coupling, hydroarylation of alkynes, or organocatalytic approach . The second is to build a new C–N bond for de novo N-heterocycle construction, including transition-metal-catalyzed aza­[2 + 2 + 2] cycloadditions. , It is obvious that the development of new practical methods for azahelicene synthesis is highly desirable yet still challenging.…”

Crystal structure of caesium tetramethyldithioimidodiphosphinate

“…The monoanionic ligands have been investigated as ligands for both main-group elements (Silvestru & Drake, 2001;Woollins, 1996) and transition metals (Rudler et al, 1997). The widespread interest in dichalcogenoimidodiphosphinates stems from their potential uses as lanthanide shift reagents (Rudler et al, 1997), industrial catalysts (Leung et al, 2000;Yamazaki et al, 2020), luminescent materials (Ma et al, 2019) as well as in metal extraction processes (du Preez et al, 1992). As part of our ongoing research on dichalcogenoimidodiphosphinate anions, we report herein the synthesis and crystallographic study of the title compound (I).…”

Synthesis and Structural Optimization of Iridium(III) Solvent Complex for Electrochemiluminescence Labeling of Histidine-Rich Protein and Immunoassay Applications for CRP Detection

“…Obviously, the following labeling performances (including emission color and quantum efficiency) largely relied on the on-site-formed emissive complex of Ir­(ppy) 2 (His) + (His represents the histidine residues of the biomolecules, such as peptides and proteins). It is well known that the emission color and quantum efficiency are seriously related to the main ligand of the iridium­(III) complex. , Specifically, the luminescence performances of the on-site-formed iridium­(III) complex, i.e., Ir­(C ∧ N) 2 (His) + , could be optimized by changing the main ligand of the original complex of Ir­(C ∧ N) 2 (solvent) 2 + (solvent is MeCN, H 2 O, or DMSO). Herein, three iridium­(III) solvent complexes with different C ∧ N bidentate ligands (shown in Figure ) have been rationally designed and successfully synthesized in this work.…”

“…It is well known that the emission color and quantum efficiency are seriously related to the main ligand of the iridium(III) complex. 25,26 Specifically, the luminescence performances of the on-siteformed iridium(III) complex, i.e., Ir(C ∧ N) 2 (His) + , could be optimized by changing the main ligand of the original complex of Ir(C ∧ N) 2 (solvent) 2 + (solvent is MeCN, H 2 O, or DMSO). Herein, three iridium(III) solvent complexes with different C ∧ N bidentate ligands (shown in Figure 1) have been rationally designed and successfully synthesized in this work.…”