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Anion-controlled assembly of Ag(I) coordination polymers based on cis/trans-bis(acetylacetone)-1,4-cyclohexanediimine ligands: syntheses, structures, and solid-state luminescence

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Two isomorphic acetylacetone-based complexes: trans-bis(acetylacetone)-1,4cyclohexanediimine (TBAC) and cis-bis(acetylacetone)-1,4-cyclohexanediimine (CBAC) were designed to promote complex formation on reaction with AgX (X = , , , , and ) and were employed to generate nine silver coordination polymers (CPs), {[Ag(TBAC)]·2H2O·BF4}n (1), [Ag(TBAC)0.5(NO3)]n (2), [Ag2(TBAC)2(ClO4)2]n (3), [Ag(TBAC)(CF3SO3)(H2O)]n (4), {[Ag(TBAC)2]·SbF6}n (5), {[Ag(CBAC)]·BF4}n (6), {[Ag(CBAC)(H2O)]·ClO4}n (7), {[Ag(CBAC)(H2O)]·CF3SO3}n (8), and {[Ag(CBAC)(H2O)]·SbF6}n (9) that exhibit structural and topological diversity as determined by single-crystal X-ray diffraction analyses. The complexes were further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Complex 1 exhibited a 3-D (4,4)-connected pts topology with the Schläfli symbol of (42·84). The anions in 2 are μ 2-bridging linkers, connecting the 1-D [Ag(TBAC)0.5]n chains to 2-D (3,4)-connected nets. In 3, TBAC is a tridentate ligand to bind Ag(I) ions to form a 1-D ladder-like supramolecular structure. Complex 4 has 2-D (3,3)-connected nets where both Ag(I) ions and TBAC ligands are 3-connected nodes. Complex 5 has a 1-D fishbone chain structure where some of the TBAC moieties are bidentate. The cis-isomer, CBAC, gives similar (3,3)-connected networks where the Ag(I) ions and CBAC ligands are 3-connected nodes in the resultant 69. Although the host networks in 69 are supramolecular isomers, structural comparisons revealed that use of cis- and trans-isomers of the ligand and different counterions significantly influence the structures. The luminescent properties of all complexes and ligands were investigated.
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Keywords: Bis(acetylacetone)cyclohexanediimine; ion-controlled; luminescent property; silver coordination polymers; structure diversity

Document Type: Research Article

Affiliations: 1: Department of Chemistry, Guizhou Medical University, Guiyang, China 2: Key Laboratory of Macrocyclic and Supramolecular Chemistry, Guizhou University, Guiyang, China 3: School of Chemistry, The University of Sydney, Sydney, Australia 4: CSIRO Manufacturing Flagship, Lindfield, Australia

Publication date: January 17, 2016

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