Stepwise Guest Exchange in a Cluster-Supported Three-Dimensional Host

Reactions of [Et4N]2[MoS4(CuCN)2]·H2O with bis-(4-pyridyl)propane (bpp) and [Cu(MeCN)4][ClO4] in aniline produced [MoS4Cu4(bpp)2(CN)2]·1.5(aniline) (1a). 1a consists of a new three-dimensional [MoS4Cu4]-supported open coordination polymer which has a relatively large channel with a volume of ca. 618 Å3 per unit cell. 1a underwent a two-step host–guest process in which the aniline molecules residing in its channels could be partly exchanged with MeCN molecules in 3d and then completely with dimethylformamide molecules in a month, forming {[MoS4Cu4(bpp)2(CN)2]·(aniline)·(MeCN)}n (1b) and {[MoS4Cu4(bpp)2(CN)2]·(DMF)·(MeCN)}n (1c), respectively.