Aggregation of phosphorescent Pd(ii) and Pt(ii) complexes with lipophilic counter-anions in non-polar solvents. Issue 17 (3rd April 2023)

• Record Type: Journal Article
• Authors: Zhou, Ning; Zou, Chao; Suo, Sa; Liu, Yuliang; Lin, Jinqiang; Zhang, Xiaobao; Shi, Minglin; Chang, Xiaoyong; Lu, Wei
• Is Part Of: Dalton transactions. Volume 52:Issue 17(2023)
• Page Start: 5503
• Page End: 5513
• Publication Date: 2023-04-03
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d2dt03415h
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Phosphorescent isostructural Pd(ii ) and Pt(ii ) aggregates involving metallophilic interactions in nonpolar achiral/chiral solvents have been extensively studied. Abstract : Phosphorescent cationic tridentate C^N^N (HC^N^N = 6-(2-R2, 4-R1 -phenyl)-2, 2′-bipyridine; R1 = R2 = H or F, or R1 = OMe, R2 = H) cyclometallated Pd(ii ) complexes with an N, N -dimethyl-imidazol-allenylidene ancillary ligand (L) and their corresponding Pt(ii ) congeners have been synthesized and characterized, following the previously reported preparation of the complex [Pd(6-phenyl-2, 2′-bipyridine)L] + . For these cationic Pd(ii )/Pt(ii ) complexes with 2, 3, 4-tris(dodecyloxy)benzenesulfonate (LA − ) counter-anions in mixed CH2 Cl2 /toluene solvents, uniform square flake or fibre-like aggregates were formed. Corresponding multicolour phosphorescence with obvious metal–metal-to-ligand charge transfer (MMLCT) features gradually changed from red to NIR by manipulating the various fractions of Pd/Pt species. Circular dichroism (CD) and circularly polarized luminescence (CPL) derived from the fibre-like Pd aggregates of [Pd(6-(2, 4-difluorophenyl)-2, 2′-bipyridine)L] + in chiroptical CH2 Cl2 /limonene solvents were achieved with an isodesmic aggregation mode. Dispersive metallophilic interactions are claimed to be the driving force for these photo-functional aggregates.