Abstract
By using cyclohexane‐1,2‐diamine (chxn), Ni(ClO~4~)~2~⋅6H~2~O and Na~3~[Mo(CN)~8~]⋅4H~2~O, a 3D diamond‐like polymer {[Ni^II^(chxn)~2~]~2~[Mo^IV^(CN)~8~]⋅8H~2~O}~n~ (1) was synthesised, whereas the reaction of chxn and Cu(ClO~4~)~2~⋅6H~2~O with Na~3~[M^V^(CN)~8~]⋅ 4H~2~O (M=Mo, W) afforded two isomorphous graphite‐like complexes {[Cu^II^(chxn)~2~]~3~[Mo^V^(CN)~8~]~2~⋅2H~2~O}~n~ (2) and {[Cu^II^(chxn)~2~]~3~[W^V^(CN)~8~]~2~⋅2H~2~O}~n~ (3). When the same synthetic procedure was employed, but replacing Na~3~[Mo(CN)~8~]⋅4H~2~O by (Bu~3~NH)~3~[Mo(CN)~8~]⋅4H~2~O (Bu~3~N=tributylamine), {[Cu^II^(chxn)~2~Mo^IV^(CN)~8~][Cu^II^(chxn)~2~]⋅ 2H~2~O}~n~ (4) was obtained. Single‐crystal X‐ray diffraction analyses showed that the framework of 4 is similar to 2 and 3, except that a discrete [Cu(chxn)~2~]^2+^ moiety in 4 possesses large channels of parallel adjacent layers. The experimental results showed that in this system, the diamond‐ or graphite‐like framework was strongly influenced by the inducement of metal ions. The magnetic properties illustrate that the diamagnetic [Mo^IV^(CN)~8~] bridges mediate very weak antiferromagnetic coupling between the Ni^II^ ions in 1, but lead to the paramagnetic behaviour in 4 because [Mo^IV^(CN)~8~] weakly coordinates to the Cu^II^ ions. The magnetic investigations of 2 and 3 indicate the presence of ferromagnetic coupling between the Cu^II^ and W^V^/Mo^V^ ions, and the more diffuse 5d orbitals lead to a stronger magnetic coupling interaction between the W^V^ and Cu^II^ ions than between the Mo^V^ and Cu^II^ ions.