Construction of Rhodium(I) and Gold(I) Macrocycles by Transferring a Phosphine-Functionalized 4,5-Diazafluorenide Ligand from Its Copper(I) N-Heterocyclic Carbene Complex

We report the synthesis and characterization of a phosphine-functionalized 4,5-diazafluorene ligand, 9-(2-(diphenylphosphino)­ethyl)-4,5-diazafluorene (L_pH), and its Cu­(IPr) complex (IPr = <i>N,N</i>′-bis­(2,6-diisopropylphenyl)­imidazol-2-ylidene) [Cu­(IPr)­L_p] (<b>2a</b>), which exhibits a monomeric structure in solution but dimerizes in the solid state. Compound <b>2a</b> reacts with Rh­(PPh₃)₃Cl, [Rh­(COD)­Cl]₂, Au­(SMe₂)­Cl, and Au­(IPr)Cl to form the macrocyclic complexes [Rh­(PPh₃)­L_p]₂ (<b>2b</b>), [Rh­(COD)­L_p]₂ (<b>2c</b>), and [AuL_p]₂ (<b>2d</b>) and the mononuclear complex [Au­(IPr)­L_p] (<b>2f</b>), respectively, via ligand transfer. Although <b>2b</b>–<b>d</b>,<b>f</b> could also be synthesized from the deprotonated ligand L_p^– and the corresponding metal starting materials directly, the reactions require longer time and give lower yields. The reaction between L_pH and Au­(SMe₂)Cl gives Au­(L_pH)₂Cl (<b>2e</b>) exclusively

Construction of Rhodium(I) and Gold(I) Macrocycles by Transferring a Phosphine-Functionalized 4,5-Diazafluorenide Ligand from Its Copper(I) N-Heterocyclic Carbene Complex

We report the synthesis and characterization of a phosphine-functionalized 4,5-diazafluorene ligand, 9-(2-(diphenylphosphino)­ethyl)-4,5-diazafluorene (L_pH), and its Cu­(IPr) complex (IPr = <i>N,N</i>′-bis­(2,6-diisopropylphenyl)­imidazol-2-ylidene) [Cu­(IPr)­L_p] (<b>2a</b>), which exhibits a monomeric structure in solution but dimerizes in the solid state. Compound <b>2a</b> reacts with Rh­(PPh₃)₃Cl, [Rh­(COD)­Cl]₂, Au­(SMe₂)­Cl, and Au­(IPr)Cl to form the macrocyclic complexes [Rh­(PPh₃)­L_p]₂ (<b>2b</b>), [Rh­(COD)­L_p]₂ (<b>2c</b>), and [AuL_p]₂ (<b>2d</b>) and the mononuclear complex [Au­(IPr)­L_p] (<b>2f</b>), respectively, via ligand transfer. Although <b>2b</b>–<b>d</b>,<b>f</b> could also be synthesized from the deprotonated ligand L_p^– and the corresponding metal starting materials directly, the reactions require longer time and give lower yields. The reaction between L_pH and Au­(SMe₂)Cl gives Au­(L_pH)₂Cl (<b>2e</b>) exclusively

Syntheses, Structures, and Luminescent Properties of Dipyridylamine-Functionalized Anthracene and Its Complexes

A novel multidentate ligand with 2,2′-dipyridylamine functionalities, 1,8-bis­[4-(2,2′-dipyridylamino)­phenylacetylenyl]­anthracene (<b>1</b>), has been synthesized through a double Sonogashira coupling reaction and characterized by NMR spectroscopic, elemental, and X-ray diffraction analyses. Compound <b>1</b> can bind to either one metal center as a tetradentate ligand or two metal centers as a double-bidentate ligand. In the double-bidentate mode, the distance between the two metal centers may vary significantly. Compound <b>1</b> displays bright blue luminescence in the solid state and in solution with a quantum efficiency of 64% relative to 9,10-diphenylanthracene. While the dirhodium complex of <b>1</b> shows no luminescence, the two zinc complexes of <b>1</b> display blue luminescence with quantum efficiencies slightly lower than that of <b>1</b>. Organic light-emitting devices (OLEDs) using <b>1</b> as the emitter show a maximum current efficiency of 7 cd/A

Syntheses, Structures, and Luminescent Properties of Dipyridylamine-Functionalized Anthracene and Its Complexes

A novel multidentate ligand with 2,2′-dipyridylamine functionalities, 1,8-bis­[4-(2,2′-dipyridylamino)­phenylacetylenyl]­anthracene (<b>1</b>), has been synthesized through a double Sonogashira coupling reaction and characterized by NMR spectroscopic, elemental, and X-ray diffraction analyses. Compound <b>1</b> can bind to either one metal center as a tetradentate ligand or two metal centers as a double-bidentate ligand. In the double-bidentate mode, the distance between the two metal centers may vary significantly. Compound <b>1</b> displays bright blue luminescence in the solid state and in solution with a quantum efficiency of 64% relative to 9,10-diphenylanthracene. While the dirhodium complex of <b>1</b> shows no luminescence, the two zinc complexes of <b>1</b> display blue luminescence with quantum efficiencies slightly lower than that of <b>1</b>. Organic light-emitting devices (OLEDs) using <b>1</b> as the emitter show a maximum current efficiency of 7 cd/A