Structural Diversity Ranging from Oligonuclear Complexes to 1‐D and 2‐D Coordination Polymers Generated by Tetrasubstituted Adamantane and Spirobifluorene Derivatives

Using tetrahedral and tetragonal spacers, seven new complexes have been obtained: [Co(hfac) 2 (L 1 ) 0.5 ] 1 , [Cu 2 (hfac) 4 L 2 ] 2 , [Co(hfac) 2 L 2 ] 3 , [Co(hfac) 2 (L 2 ) 0.5 ] · 8H 2 O 4 , [AgL 2 ](SbF 6 ) · CH 3 COOC 2 H 5 5 , [Mn(hfac) 2 (L 3 ) 0.5 ] 6 , [Zn(OAc) 2 (L 3 ) 0.5 ] 7 , {L 1 = 1,3,5,7‐tetrakis(4‐cyanophenyl)adamantane, L 2 = 2,2′,7,7′‐tetracyano‐9,9′‐spirobifluorene and L 3 = 2,2′,7,7′‐tetra(4‐pyridyl)‐9,9′‐spirobifluorene, Hhfac = hexafluoroacetylacetone}. Compound 1 exhibits a 2‐D grid‐like structure with the tetradentate spacer acting as a 4‐connecting ligand. The 2,2′,7,7′‐tetrasubstituted‐spirobifluorene derivatives connect the {M II (hfac) 2 } entities into a binuclear complex ( 2 ), a linear chain ( 3 ) and diamond chains ( 4 , 6 ). The cis or trans configuration of the metal nodes influences the overall topology (M II = Cu II , Co II , Mn II ). Similarly, a 1‐D double chain topological motif results by linking zinc ions and L 3 in compound 7 . Compound 5 is a 2‐D coordination polymer featuring a layered framework with square cavities. Compound 5 undergoes a reversible single‐crystal‐to‐single‐crystal process, with removal of the solvent molecules (ethyl acetate). The luminescence properties of compounds 5 , 7 have been investigated and reveal blue emission with maxima at 402 and 483 nm, respectively. The dynamic magnetic properties and EPR spectrum of 1 have been investigated, revealing the occurrence of slow relaxation of the magnetization that most likely involves a Raman process.