Kinetically Controlled Self-Assembly of Phosphorescent Au-III Aggregates and Ligand-to-Metal-Metal Charge Transfer Excited State: A Combined Spectroscopic and DFT/TDDFT Study

Wan, Qingyun1,2; Xia, Jiuxu3; Lu, Wei3; Yang, Jun1,2; Che, Chi-Ming1,2,4

2019-07-24

10.1021/jacs.9b04007

Journal of the American Chemical Society   影响因子和分区

0002-7863

1520-5126

Metallophilic interactions in d(10)-d(10)(Au-I-Au-I)/d(8)-d(8)(Pt-II-Pt-II, Rh-I-Rh-I, Ir-I-Ir-I) complexes have been widely studied for decades, and metal metal (M M) bonding character has been revealed in both the ground and excited states. These M M closed-shell interactions are appealing driving forces for the self-assembly of supramolecular/polymeric systems, providing luminescent properties distinctly different from those of the corresponding monomer. However, reports on attractive interactions between two Au-III complex cations are scarce in the literature. Herein is described a series of pincer-type cationic Au-III complexes with different auxiliary ligands, among which the Au-III allenylidene complex displays a close Au-Au contact of 3.367 A between neighboring molecules in its X-ray crystal structure; Au-III-isocyanide complexes show a broad red-shifted absorption band and prominent phosphorescence upon aggregation that was influenced by an attractive Au-III-Au-III bonding interaction in the excited state; and Au-III-acetylene complexes can undergo living supramolecular polymerization upon varying the counteranion. The nature of the emissive excited state(s) of the Au-III aggregates is assigned to a mixture of major 3[pi-pi*] and minor (LMMCT)-L-3 (ligand-to-metal metal charge transfer) states based on combined spectroscopic and DFT/TDDFT studies. The morphology of the Au-III aggregates is highly dependent on the concentration and nature of the counteranion. A qualitative model has been applied to account for the concentration- and counteranion-dependent kinetics of the supramolecular polymerization process.

SCI ; EI ; IC

英语

NI期刊

其他

Basic Research Program-Shenzhen Fund[JCYJ20160229123546997] ; Basic Research Program-Shenzhen Fund[JCYJ20170412140251576] ; Basic Research Program-Shenzhen Fund[JCYJ20170818141858021]

Chemistry

Chemistry, Multidisciplinary

WOS:000477787400033

AMER CHEMICAL SOC

20193307322918

Aggregates ; Binary alloys ; Cationic polymerization ; Charge transfer ; Complexation ; Crystal structure ; Excited states ; Gold alloys ; Iridium compounds ; Ligands ; Living polymerization ; Phosphorescence ; Platinum metals ; Red Shift ; Self assembly ; Supramolecular chemistry

Highway Engineering:406 ; Precious Metals:547.1 ; Light/Optics:741.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Polymerization:815.2 ; Atomic and Molecular Physics:931.3 ; Crystal Lattice:933.1.1 ; Materials Science:951

Web of Science

1.Univ Hong Kong, Dept Chem, Pokfulam Rd, Hong Kong, Peoples R China
2.Univ Hong Kong, State Key Lab Synthet Chem, Pokfulam Rd, Hong Kong, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
4.HKU Shenzhen Inst Res & Innovat, Shenzhen 518057, Peoples R China

Wan, Qingyun,Xia, Jiuxu,Lu, Wei,et al. Kinetically Controlled Self-Assembly of Phosphorescent Au-III Aggregates and Ligand-to-Metal-Metal Charge Transfer Excited State: A Combined Spectroscopic and DFT/TDDFT Study[J]. Journal of the American Chemical Society,2019,141(29):11572-11582.

Wan, Qingyun,Xia, Jiuxu,Lu, Wei,Yang, Jun,&Che, Chi-Ming.(2019).Kinetically Controlled Self-Assembly of Phosphorescent Au-III Aggregates and Ligand-to-Metal-Metal Charge Transfer Excited State: A Combined Spectroscopic and DFT/TDDFT Study.Journal of the American Chemical Society,141(29),11572-11582.

Wan, Qingyun,et al."Kinetically Controlled Self-Assembly of Phosphorescent Au-III Aggregates and Ligand-to-Metal-Metal Charge Transfer Excited State: A Combined Spectroscopic and DFT/TDDFT Study".Journal of the American Chemical Society 141.29(2019):11572-11582.