Synthesis and Characterization of a Series of Novel Heptanuclear Trigonal‐Prismatic Polyhedra with Different Edge‐Ligands

Five novel heptanuclear trigonal‐prismatic polyhedra, Na 4 [PrNi 6 (Gly) 9 ( μ 3 ‐OH) 3 (H 2 O) 6 ]⋅(ClO 4 ) 7 ( 1 ), Na 2 [PrNi 6 (Gly) 8 ( μ 3 ‐OH) 3 ( μ 2 ‐OH 2 )(H 2 O) 6 ]⋅(ClO 4 ) 6 ⋅(H 2 O) 2 ( 2 ), Na[DyNi 6 (Gly) 7 ( μ 3 ‐OH) 3 ( μ 2 ‐OH 2 ) 2 (H 2 O) 6 ]⋅(ClO 4 ) 6 ⋅H 2 O ( 3 ), [SmNi 6 (Gly) 6 ( μ 3 ‐OH) 3 Cl 3 (H 2 O) 6 ]⋅Cl 3 ⋅(H 2 O) 9 ( 4 ), and [ErNi 6 (Gly) 6 ( μ 3 ‐OH) 3 Cl 3 (H 2 O) 6 ]⋅Cl 3 ⋅(H 2 O) 9 ( 5 ), were synthesized through self‐assembly and characterized by X‐ray structure analysis. Complex 1 crystallizes in the trigonal P3 space group ( a = b =18.1121(2), c =11.987(0) Å, and Z =2). Complex 2 belongs to the triclinic P $\bar 1$ space group ( a =16.0145(3), b =20.58650(10), c =20.8452(3) Å, α =78.0590(10), β =67.9200(10), γ =68.1540(10)°, and Z =4). Complex 3 belongs to the monoclinic P2(1)/m space group ( a =14.9863(3), b =13.533, c =15.6171(3) Å, β =116.8970(10)°, and Z =2). Complexes 4 and 5 are isomorphous ( 4 : trigonal, P $\bar 3$ ; a = b =11.8661(4), c =18.2034(10) Å, Z =2; 5 : a = b =11.9001(5), c =18.1229(11) Å, Z =2). A Ln 3+ ion is in the center of the prism formed by six nickel atoms. It coordinates to nine oxygen atoms. Its coordination polyhedron may be best described as a tricapped trigonal prism. The five complexes all have a core of [LnNi 6 (Gly) 6 ( μ 3 ‐OH) 3 (H 2 O) 6 ] 6+ and were obtained through the edge‐ligand exchange of the three μ 2 ‐OH 2 ligands of [LnNi 6 (Gly) 6 ( μ 3 ‐OH) 3 (H 2 O) 6 ( μ 2 ‐OH 2 ) 3 ] 6+ partly or wholly by glycine or Cl − . Magnetic measurements reveal that 1 and 4 exhibit antiferromagnetic interaction, while 5 exhibits a ferromagnetic interaction.