Phosphorescent Tris-cyclometalated Pt(IV) Complexes with Mesoionic N-Heterocyclic Carbene and 2-Arylpyridine Ligands

[Image: see text] The synthesis, structure, photophysical properties, and electrochemistry of the first series of Pt(IV) tris-chelates bearing cyclometalated aryl-NHC ligands are reported. The complexes have the general formula [Pt(trz)(2)(C∧N)](+), combining two units of the cyclometalated, mesoionic aryl-NHC ligand 4-butyl-3-methyl-1-phenyl-1H-1,2,3-triazol-5-ylidene (trz) with a cyclometalated 2-arylpyridine [C∧N = 2-(2,4-difluorophenyl)pyridine (dfppy), 2-phenylpyridine (ppy), 2-(p-tolyl)pyridine (tpy), 2-(2-thienyl)pyridine (thpy), 2-(9,9-dimethylfluoren-2-yl)pyridine (flpy)], and presenting a mer arrangement or metalated aryls. They exhibit a significant photostability under UV irradiation and long-lived phosphorescence in the blue to yellow color range, arising from (3)LC excited states involving the C∧N ligands, with quantum yields of up to 0.34 in fluid solution and 0.77 in the rigid matrix at 298 K. The time-dependent density functional theory (TD-DFT) calculations reveal that nonemissive, deactivating excited states of ligand-to-metal charge-transfer (LMCT) character are pushed to high energies as a consequence of the strong σ-donating ability of the carbenic moieties, making the Pt(trz)(2) subunit an essential structural component that enables efficient emissions from the chromophoric C∧N ligands, with potential application for the development of different Pt(IV) emitters with tunable properties.