Details

Autor(en) / Beteiligte

• Meyer, Marco
• Prescimone, Alessandro
• Constable, Edwin C
• Housecroft, Catherine E

Titel

Introducing sterically demanding substituents and π-π-interactions into [Cu(P^P)(N^N)] complexes

Ist Teil von

• Dalton transactions : an international journal of inorganic chemistry, 2024-03, Vol.53 (12), p.5453-5465

Ort / Verlag

England: Royal Society of Chemistry

Erscheinungsjahr

2024

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• A series of ten N^N chelating ligands based on a 2,2′-bipyridine (bpy) metal-binding domain and featuring sterically hindering substituents in the 6- and 6,6′-positions has been synthesized and characterized. The ligands have been incorporated into a family of 15 heteroleptic complexes of type [Cu(P^P)(N^N)][PF 6 ] where P^P is the wide bite-angle bisphosphane ligand bis(2(diphenylphosphanyl)phenyl)ether (POP) or (9,9-dimethyl-9 H -xanthene-4,5-diyl)bis(diphenylphosphane) (xantphos). Substituents in several of the N^N ligands ligands possess phenyl rings remotely tethered to enable intra- and intermolecular π-π-interactions in the [Cu(P^P)(N^N)] + cations. Single crystal X-ray structures of 12 complexes are reported. The effects of the functional groups in the bpy ligand on the photophysical properties of the complexes have been studied; solid-state emission maxima range from 518 to 567 nm. Values of the solid-state photoluminescence quantum yields (PLQYs) of the [Cu(P^P)(N^N)][PF 6 ] compounds respond to the nature of the N^N ligand. In general, we observed that the [Cu(P^P)(N^N)] + complexes containing 6,6′-disubstituted complexes with phenyl moieties connected via a CH 2 CH 2 or CH 2 CH 2 CH 2 spacer to the bpy domain have the highest values of PLQY. The most significant compounds are [Cu(POP)((2-PhEt) 2 bpy)][PF 6 ] (PLQY = 67%) and [Cu(POP)((3-PhPr) 2 bpy)][PF 6 ] (PLQY = 72%) where (2-PhEt) 2 bpy = 6,6′-bis(2-phenylethyl)-2,2′-bipyridine and (3-PhPr) 2 bpy = 6,6′-bis(3-phenylpropyl)-2,2′-bipyridine. These PLQY values are among the best performing previously reported families of [Cu(P^P)(N^N)][PF 6 ] compounds. By introducing sterically demanding substituents in the N^N ligand in [Cu(P^P)(N^N)] + , solid-state photoluminescence quantum yields of up to 72% have been achieved.