Just Add the Gold: Aggregation-Induced-Emission Properties of Alkynylphosphinegold(I) Complexes Functionalized with Phenylene–Terpyridine Subunits

Abstract

A series of organometallic complexes containing an alkynylphosphinegold­(I) fragment and a phenylene–terpyridine moiety connected together by flexible linker have been prepared using the specially designed terpyridine ligands. The compounds were studied crystallographically to reveal that all of them contain a linearly coordinated Au­(I) atom and a free terpyridine moiety. The different orientations of the molecules relative to each other in the solid state determine the multiple noncovalent interactions such as antiparallel ππ stacking, CH−π, and CH–Au, but no aurophilic interactions are realized. The organometallic Au­(I) complexes obtained show fluorescence in the solution and dual singlet–triplet emission in the solid state. This means that their photophysical behavior is determined by both intermolecular lattice-defined interactions and Au­(I) atom introduction. Density functional theory computational analysis supported the assignment of emission to intraligand electronic transitions only inside the phenylene–terpyridine part with no Au­(I) involved. In addition, a study of the nature of the excited states for the “dimer” with an antiparallel orientation of the terpyridine fragment showed that this orientation leads to the generation of abstracted singlet and triplet states, lowering their energy in comparison with the monomer complex. Thus, the complexes obtained can be qualified as examples of Au­(I)-containing organometallic aggregation-induced-emission luminogens.

Platinum macrocatalyst for heterogeneous Si–O dehydrocoupling

“…A platinum C , N -cyclometalated complex (PCC) was synthesized via a 3-step procedure including obtaining 2-hydrazinopyridine (Scheme S1, ESI†), its reaction with 3-methoxy-4-(prop-2-yn-1-yloxy)benzaldehyde (prepared by the procedure in ref. 12) and coupling of the obtained product (a Schiff base) with cis -[PtCl 2 (CNXyl) 2 ] (synthesized according to ref. 13) (Scheme 1).…”

Alkynyl Gold(I) Phosphine Complexes: Evaluation of Structure–Activity Relationships for the Alkynyl Ligands on Luminescence and Cytotoxicity

“…Alkynyl gold (I) phosphine complexes are a hot–topic of research on the last two decades due to their fascinating versatility of their luminescent properties, [1–3] as well as their promising potential applications in photoelectronics, [4–9] and chemsensors [10–11] . The linearity of these complexes due to the Au(I) center and the alkynyl moiety makes them suitable for establishing intra‐ or intermolecular contacts, through Au(I)⋯Au(I) contacts, hydrogen bond interactions and other weak interactions, which determine the architecture of the resulting assemblies and corresponding luminescence [1–3] .…”

Dinuclear gold(I) Complexes with Bidentate NHC Ligands as Precursors for Alkynyl Complexes via Mechanochemistry

“…The luminescence properties of these compounds in solution are generally associated with the organic part of the molecule and are associated with LLCT or LMCT transitions, although, in the solid state, the emission properties also depend on the self-assembly of the molecular units. Furthermore, π-π stacking involving the organic part, as well as Au•••Au interactions, play a fundamental role in the isolation of different supramolecular structures or polymorphs, characterized by different emitting properties [10][11][12][13][14].…”