Interpenetration of a three-dimensional Cu(I) coordination framework controlled by adjusting the symmetry of its secondary building unit

• Complex 1 and 2 are distinct structural characteristic: twofold interpenetrating diamondlike framework for 1 and a noncatenated structure based on infinite[Cu(SCN)]n chains for 2.
• The symmetry matching of their secondary building unit (SBU) are of particular importance to control their degree of interpenetration.
• Tetrakis(3-pyridyloxymethylene) methane (L) can be served as a good candidate for the construction of MOFs due to its specific tetrahedral configuration and flexible conformation.

Two new coordination polymers based on CuX (X = SCN, I) and L have been successfully prepared by solvothermal reactions: [Cu4I4L] (1) and [Cu4(SCN)4L] (2) (L = tetrakis(3-pyridyloxymethylene)methane), exhibiting a doubly-fold interpenetrating diamondlike framework for 1 and a noncatenated structure with infinite[Cu(SCN)]n chains for 2. Their structural analysis shows the symmetry matching of their secondary building unit (SBU) can effectively control their degree of interpenetration.

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