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The versatile metalloligand [{HC≡CC(NDipp)2}2Au2] (dipp = 2,6-diisopropylphenyl) was converted into early-late heterotetrametallic complexes [{ClCp2MC≡CC(NDipp)2}2Au2] (M = Ti, Zr). These compounds show photoluminescence with either remarkably different (Ti) or similar (Zr) features as compared to related solely coinage metal containing acetylide amidinate complexes. [ABSTRACT FROM AUTHOR]

The synthesis of linear symmetric ethynyl‐ and acetylide‐amidinates of the coinage metals is presented. Starting with the desilylation of the complexes [{Me3SiC≡CC(NDipp)2}2M2] (Dipp=2,6‐diisopropylphenyl) (M=Cu, Au) it is demonstrated that this compound class is suitable to serve as a versatile metalloligand. Deprotonation with n‐butyllithium and subsequent salt metathesis reactions yield symmetric tetranuclear gold(I) acetylide complexes of the form [{(PPh3)AuC≡CC(NDipp)2}2M2] (M=Cu, Au). The corresponding Ag complex [{(PPh3)AuC≡CC(NDipp)2}2Ag2] was obtained by a different route via metal rearrangement. All compounds show bright blue or blue‐green microsecond long phosphorescence in the solid state, hence their photophysical properties were thoroughly investigated in a temperature range of 20–295 K. Emission quantum yields of up to 41 % at room temperature were determined. Furthermore, similar emissions with quantum yields of 15 % were observed for the two most brightly luminescent complexes in thf solution. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The ligand [{Me3SiC≡CC(NDipp)2}Li(thf)3] (Dipp = 2,6-diisopropylphenyl) was used for salt metathesis reactions with [AuCl(tht)] (tht = tetrahydrothiophene) to obtain the dinuclear alkyne functionalized bisamidinate [{Me3SiC≡CC(NDipp)2}2Au2]. This compound serves as a building block for the polynuclear carbide bridged gold(i) amidinate complex [Au8{μ3-(η1:η2-C≡C)}2(Me3SiC≡CC(NDipp)2)4(tht)2], which is the first gold(i) complex with a μ3-η1:η2 carbide coordination. Both gold(i) compounds show distinct aurophilic interactions and are remarkably stable at ambient conditions. Photophysical investigations revealed intense luminescence with notable high quantum yields both in the solid state and in solution. [ABSTRACT FROM AUTHOR]

Cover Feature: Efficient Blue Phosphorescence in Gold(I)-Acetylide Functionalized Coinage Metal Bis(amidinate) Complexes (Chem. Eur. J. 70/2020) Keywords: acetylide; amidinate; desilylation; gold; luminescence EN acetylide amidinate desilylation gold luminescence 16564 16564 1 12/18/20 20201215 NES 201215 B The synthesis of linear symmetric ethynyl- and acetylide- amidinates b of the coinage metals is presented. Acetylide, amidinate, desilylation, gold, luminescence. [Extracted from the article]