Luminescent Bis‐Cyclometalated Gold(III) Complexes with Alkynyl Ligands of Hexaphenylbenzene and Hexabenzocoronene Derivatives and Their Supramolecular Assembly. Issue 24 (10th April 2017)

• Record Type: Journal Article
• Authors: Yim, King‐Chin; Au, Vonika Ka‐Man; Wong, Keith Man‐Chung; Yam, Vivian Wing‐Wah
• Is Part Of: Chemistry. Volume 23:Issue 24(2017)
• Page Start: 5772
• Page End: 5786
• Publication Date: 2017-04-10
• Subjects: gold -- luminescence -- pi interactions -- polycycles -- self-assembly; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201606052
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A series of luminescent bis‐cyclometalated gold(III) complexes with different nuclearities and various alkynyl ligands derived from hexaphenylbenzene (HPB) and hexabenzocoronene (HBC) have been synthesized. The energies of the low‐energy metal‐perturbed intraligand (IL) π–π*(R−C^N^C) absorptions of the HPB–alkynyl gold(III) complexes have been fine‐tuned by attaching various substituent groups to the bis‐cyclometalating ligands. Similarly, the metal‐perturbed 3 IL [π→π*(R−C^N^C)] emissions of the complexes show energy shifts according to the electronic nature of the bis‐cyclometalating ligands. On the contrary, the absorption and emission spectra of the HBC–alkynyl gold(III) complex have been assigned as dominated by the IL transitions of the HBC–alkynyl unit, as supported by transient absorption studies. The supramolecular assembly morphologies of the gold(III) complexes have been studied by TEM and SEM, along with comparisons across different complexes based on the molecular structures, and their assembly processes monitored by concentration‐dependent and variable‐temperature 1 H NMR spectroscopy studies. Abstract : Glitters with gold(III) : A new class of luminescent bis‐cyclometalated gold(III) complexes, containing hexa‐ peri ‐hexabenzocoronene or hexaphenylbenzene derivatives in the alkynyl ligands, has been synthesized and characterized (see figure). The complexes undergo supramolecular self‐assembly processes driven by noncovalent interactions. Detailed spectroscopic studies were performed.