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Mixing an aqueous solution of K 8 [Nb 6 O 19 ]⋅16H 2 O with a DMSO/H 2 O solution of Cu(ClO 4 ) 2  · 6 H 2 O and cyclen at room temperature afforded crystallization of blue crystals of [(Cu(cyclen)) 6 Nb 6 O 19 ]⋅[ClO 4 ] 4 ·≈4H 2 O after slow evaporation of the solvents. The crystal structure contains the Lindqvist anion [Nb 6 O 19 ] 8–  which is covalently expanded by six symmetry-related [Cu(cyclen)] 2+  complexes via Nb- μ  2 -O-Cu bridges yielding the positively charged [(Cu(cyclen)) 6 Nb 6 O 19 ] 4+  cluster shell. The ClO 4  −  anions and crystal water molecules reside in the empty spaces of the packed clusters. The compound shows two electronic d-d transitions at energetic positions explaining the blue color.

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Decoration of the [Nb 6 O 19 ] 8–  cluster shell with six Cu 2+ -centred complexes generates the [(Cu(cyclen)) 6 Nb 6 O 19 ] 4+  moiety: room temperature synthesis, crystal structure and selected properties