Crystal Engineering and Photomagnetic Studies of CN-Bridged Coordination Polymers Based on Octacyanidometallates(IV) and [Ni(cyclam)](2+)

[Image: see text] A series of new CN-bridged coordination networks of different dimensionality and topology was obtained through the modification of reaction conditions between [Ni(cyclam)](2+) (cyclam = 1,4,8,11-tetraazacyclotetradecane) and [W(CN)(8)](4–). The factors determining the reaction pathway are temperature and addition of the LiCl electrolyte. The products include three negatively charged frameworks incorporating Li(+) guests: the 1D Li(2)[Ni(cyclam)][W(CN)(8)]·6H(2)O (1) straight chain, the 1D Li(2)[Ni(cyclam)][W(CN)(8)]·2H(2)O (2) zigzag chain, and the 2D Li(2)[Ni(cyclam)](3)[W(CN)(8)](2)·24H(2)O (3) honeycomb-like network, as well as the 3D two-fold interpenetrating [Ni(cyclam)](5)[Ni(CN)(4)][W(CN)(8)](2)·11H(2)O (4) network and the 1D [Ni(cyclam)][Ni(CN)(4)]·2H(2)O (5) chain, which result from partial decomposition of the starting complexes. Together with the previously characterized 3D [Ni(cyclam)](2)[W(CN)(8)]·16H(2)O (6) network, they constitute the largest family of CN-bridged coordination polymers obtained from the same pair of building blocks. All compounds exhibit paramagnetic behavior because of the separation of paramagnetic nickel(II) centers through the diamagnetic polycyanidometallates. However, the presence of the photomagnetically active octacyanidotungstate(IV) ions allowed observation of the magnetic superexchange after the violet light excitation (405 nm) for compound 3, which constitutes the first example of the photomagnetic effect in a Ni(II)–[W(IV)(CN)(8)] system. The photomagnetic investigations for fully hydrated and dehydrated sample of 3, as well as for the isostructural octacyanidomolybdate(IV)-based network are discussed.