Strong Solid‐State Phosphorescence of 1,2‐Telluraplatinacycles Incorporated into Rigid Dibenzobarrelene and Triptycene Skeletons

Abstract

Four‐ and five‐membered 1,2‐telluraplatinacycles incorporated into dibenzobarrelene and triptycene skeletons were synthesized by the reaction of bis(dibenzobarrelenyl) ditelluride and bis(triptycyl) ditelluride, respectively, with [Pt(η2‐norbornene)(PPh3)2] in the presence of PPh3. These complexes emit strong, orange phosphorescence in the solid state at room temperature (λem = 622–676 nm). Ligand‐exchange reactions of a five‐membered telluraplatinacycle with bidentate phosphine ligands gave a series of derivatives that emitted a range of colors (blue to orange, λem = 507–596 nm) with high emission quantum yields (max. ΦF = 0.93) in the solid state at room temperature, for which vapoluminescence was observed.

Synthesis of Ferrocenyl-Substituted Organochalcogenyldichlorogermanes

“…We have decided to use the 9-triptycyl (Trp) group as a steric protection group, as the simple synthesis of the corresponding dichalcogenides (1a,b) has already been reported [11][12][13]. The treatment of an ether solution of TrpSeSeTrp (1a) [11] with SO2Cl2 at room temperature afforded the corresponding selenenyl chloride, TrpSeCl (2a), as a stable crystalline compound (Scheme 2).…”

“…The treatment of an ether solution of TrpSeSeTrp (1a) [11] with SO2Cl2 at room temperature afforded the corresponding selenenyl chloride, TrpSeCl (2a), as a stable crystalline compound (Scheme 2). In a similar fashion, TrpTeCl (2b) was obtained from the reaction of TrpTeTeTrp (1b) [12,13] with SO2Cl2. The molecular structures of TrpSeCl (2a) and TrpTeCl (2b) were unambiguously determined by X-ray diffraction (XRD) analyses, which delivered C-Ch-Cl angles of 99.93(6)° (Ch = Se) and 96.38(9)° (Ch = Te), as well as Ch-Cl bond lengths of 2.1860(7) Å (Ch = Se) and 2.348(1) Å (Ch = Te).…”

“…Solvents were purified using the Ultimate Solvent System (Glass Contour Company, CA, USA) [17]. 1 H, 13 C, 77 Se, and 125 Te NMR spectra were measured on JEOL 300 or 400 MHz spectrometers (JEOL, Tokyo, Japan). Signals arising from residual C 6 D 5 H (7.15 ppm) in C 6 D 6 and CHCl 3 (7.25 ppm) in CDCl 3 were used as an internal standard for the 1 H NMR spectra, while signals of C 6 D 6 (128.0 ppm) and CDCl 3 (77.0 ppm) where used to reference the 13 C NMR spectra.…”

“…Elemental analyses were carried out at the Microanalytical Laboratory, Institute for Chemical Research, Kyoto University. Dichalcogenides 1a and 1b [11][12][13] as well as chlorogermylenoid 4 [7] were prepared according to literature procedures.…”

Moving Beyond Boron-Based Substituents To Achieve Phosphorescence in Tellurophenes

“…[25][26][27] A number of structurally novel luminescent (predominantly fluorescent) tellurium complexes have also been synthesized recently. [28][29][30][31][32][33][34][35][36][37] Particularly salient examples include the tellurium-containing dibenzobarrelenes prepared by Ishii and coworkers, 33 and fluorescent xanthyliumbased tellurones reported by Detty and coworkers. 31 Thus far, published tellurophene emitters from our laboratories each share a common structural motif: namely, the presence of proximal BPin substituents at the 2-and/or 5-positions of a tellurophene (or benzotellurophene) ring.…”