Assembly of Heterometallic Silver(I)-Copper(I) Alkyl-1,3-diynyl Clusters via Inner-Core Expansion.
New tetranuclear supramolecular precursors [(R-C≡C-C≡C)Ag]4(R =iPr,tBu, and chx) are employed to construct a series of heterometallic silver(I)-copper(I) alkyl-1,3-diynyl cluster complexes (1-9) that bear a common CuAg3core (normally trigonal-planar, but can be distorted to pyramidal) consolidated by cupro-argentophilic interaction under 3.12 Å, as found in 1 and 2. The photophysical properties of the multinuclear supramolecular precursors and selected complexes have been investigated. The present results strongly suggest that the assembly of medium-nuclearity clusters 3 to 9 is initiated by accretion of additional Ag(I) ions by the ubiquitous CuAg3template through argentophilic (<3.4 Å) interaction, with cooperative cuprophilic enhancement (<2.76 Å) in the case of compound 9. To our knowledge, the present study provides the first report of conversion of a Group 11 homonuclear cluster into a heteronuclear one of higher nuclearity via inner-core expansion.
Department of Chemistry and Center of Novel Functional Molecules, The Chinese University of Hong Kong , Shatin, New Territories, Hong Kong SAR, People's Republic of China.|Department of Chemistry, Hong Kong Baptist University , Kowloon, Hong Kong SAR, People's Republic of China.
Sam C K
SCK
Hau
Institute of Molecular Functional Materials (Areas of Excellence Scheme, University Grants Committee, Hong Kong) and Department of Chemistry, The University of Hong Kong , Pokfulam Road, Hong Kong, People's Republic of China.
Margaret C-L
MC
Yeung
Institute of Molecular Functional Materials (Areas of Excellence Scheme, University Grants Committee, Hong Kong) and Department of Chemistry, The University of Hong Kong , Pokfulam Road, Hong Kong, People's Republic of China.
Vivian W-W
VW
Yam
Department of Chemistry and Center of Novel Functional Molecules, The Chinese University of Hong Kong , Shatin, New Territories, Hong Kong SAR, People's Republic of China.
Thomas C W
TCW
Mak