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Size Matters: From Two‐Dimensional Au I –Tl I Metallopolymers to Molecular Complexes by Simple Variation of the Steric Demand
Author(s) -
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.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201805984
Subject(s) - steric effects , cluster (spacecraft) , crystallography , photoluminescence , singlet state , substituent , chemistry , metal , stereochemistry , materials science , physics , atomic physics , organic chemistry , optoelectronics , computer science , excited state , programming language
Bis(acetylido) aurates(I) and thallium(I) trifluoromethylsulfonates were used to synthesize Au I –Tl I 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 [Tl 2 Au 3 ]. 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.