Publication: Phosphorescent Tris-cyclometalated Pt(IV) Complexes with Mesoionic N‐Heterocyclic Carbene and 2‐Arylpyridine Ligands
Authors
Vivancos Ureña, Ángela ; Bautista, Delia ; González Herrero, Pablo
item.page.secondaryauthor
item.page.director
Publisher
publication.page.editor
publication.page.department
DOI
https://doi.org/10.1021/acs.inorgchem.2c02039
item.page.type
info:eu-repo/semantics/article
Description
Abstract
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 3LC 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.
publication.page.subject
Citation
Inorganic Chemistry 2022, 61, 12033−12042
item.page.embargo
Collections
Ir a Estadísticas
Sin licencia Creative Commons.