Phosphorescent platinum(ii) complexes bearing pentafluorosulfanyl substituted cyclometalating ligands

Abstract

The first examples of phosphorescent platinum(ii) complexes bearing pentafluorosulfanyl (–SF5) substituted cyclometalating ligands (C^N) are reported.

Amine–borane complex-initiated SF5Cl radical addition on alkenes and alkynes

“…Considering the wide range of trifluoromethylated compounds of interest, the synthesis of their SF 5 -analogs has become a trend to increase the properties of these valuable molecules [9]. Due to the unique properties, the SF 5 group has been used in various fields of chemistry, including pharmaceuticals [10][11][12][13][14][15][16], agrochemistry [17][18][19][20], and materials sciences [21][22][23][24][25][26]. The applications have, however, been limited by the poor synthetic accessibility of SF 5 -containing molecules.…”

Dual-Emissive Bis(diphenylphosphino)amine Platinum Complexes: Structural, Reactivity, Photophysical, and Theoretical Investigations

“…Regiochemistry is a determining factor in possible orientations which cause intermolecular and intermolecular interactions. , If assemblies adopt a syn orientation, where both the metal centers and cyclometalated ligands are arranged in an overlapping mode, the formation of an MMLCT excited state is predicted. In an anti orientation where the cyclometalated ligands are directed away from each other, the π–π interactions are maximized …”

“…In an anti orientation where the cyclometalated ligands are directed away from each other, the π−π interactions are maximized. 15 The bis(diphenylphosphino)amine (dppa) ligand is an attractive ligand for at least two reasons: it is isoelectronic with bis(diphenylphosphino)methane (dppm) but possesses different structural (dppa has a 3°smaller mean value for the bite angle in its chelating mode relative to the dppm bite angle (72.5°), on the basis of an analysis of Cambridge Structural Database (CSD) search results) and electronic properties. Similarly to dppm, the dppa could have various structural reactivities, as a monodentate, chelating, or bridging ligand, 16−18 but it can be easily derivatized on the nitrogen.…”

A SF5 Derivative of Triphenylphosphine as an Electron-Poor Ligand Precursor for Rh and Ir Complexes

“…In addition, phenyl groups with SF 5 moieties at both meta and para positions exhibit a stronger electron-withdrawing effect according to Hammett constants (σ m = 0.61, σ p = 0.68), when compared with a fluorine substituent ( F = 0.45, R = −0.39, σ m = 0.34, σ p = 0.06) or the trifluoromethyl group ( F = 0.38, R = 0.16, σ m = 0.43, σ p = 0.54) [ 21 ]. Despite the increasing interest on SF 5 -containing compounds described in literature and their applications as building blocks in many fields such as agrochemical, medicinal, or materials chemistry [ 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 ], SF 5 derivatized ligands in transition metal complexes are still rare [ 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 ]. Examples mainly focus on C^N cyclometalated ligands which contain the SF 5 moiety in their phenyl rings in order to stabilize iridium(III) [ 34 , 35 , 36 , 37 ] or platinum(II) [ 38 ] complexes with optoelectronic properties.…”