Size Matters: From Two‐Dimensional AuI–TlI Metallopolymers to Molecular Complexes by Simple Variation of the Steric Demand

• Published in: Chemistry : a European journal 2019-03, Vol.25 (15), p.3799-3808
• Main Authors: Seifert, Tim P., Knoefel, Nicolai D., Feuerstein, Thomas J., Reiter, Kevin, Lebedkin, Sergei, Gamer, Michael T., Boukis, Andreas C., Weigend, Florian, Kappes, Manfred M., Roesky, Peter W.
• Format: Article
• Language: English
• Subjects: Ambient temperature; Chemistry; Clusters; dimensional control; Dimers; gold; luminescence; metallophilicity; Metals; Molecular chains; NMR; Nuclear magnetic resonance; Photoluminescence; Photons; Spectrometry; Thallium
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201805984

Bis(acetylido) aurates(I) and thallium(I) trifluoromethylsulfonates were used to synthesize AuI–TlI metallopolymers, displaying novel and unusual structural motifs of the metal–metal backbones in the solid state: a discrete molecular cluster, 1D chains of interconnected dimers, tetramers, or dodecamers of Au–Tl units, and a 2D‐plane network, consisting of alternating edge‐linked (AuTl)6 and (AuTl)4 cycles. The formation of the different architectures was primarily controlled by the steric demand of the acetylide‐substituent groups. Thus, the bulkiest 2,6‐diisopropylphenyl derivative yielded a molecular cluster [Tl2Au3]. Most compounds showed bright visible photoluminescence with quantum yields of up to 25 % at ambient temperature. The color of the emitted light significantly differs with the network structure. Furthermore, theoretical studies of singlet excitations in the molecular cluster, as well as NMR and mass‐spectrometric investigations of the fragmentation of the metallopolymers in solution are described in detail. Bigger for better or worse: Luminescent AuI–TlI metallopolymers, displaying novel and unusual structural motifs of the metal–metal backbones in the solid state, are reported.