| Summary: | The synthesis and structural characterization of six dicyanamido-cadmium(II) complexes are reported: <i>catena</i>-[Cd(μ<sub>1,3</sub>-dca)(μ<sub>1,5</sub>-dca)(3-ampy)] (<b>1</b>), <i>catena</i>-[Cd<sub>3</sub>(μ<sub>1,3,5</sub>-dca)<sub>2</sub>(μ<sub>1,5</sub>-dca)<sub>4</sub>(pyNO)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (<b>2</b>), <i>catena</i>-{Cd(H<sub>2</sub>O)<sub>2</sub>(μ<sub>1,5</sub>-dca)<sub>2</sub>](2,6-lut-NO)} (<b>3</b>), <i>catena</i>-[Cd(Me<sub>2</sub>en)(μ<sub>1,5</sub>-dca)<sub>2</sub>] (<b>4</b>), <i>catena</i>-[Cd(Me<sub>4</sub>en)(μ<sub>1,5</sub>-dca)<sub>2</sub>] (<b>5</b>), and [Cd(1,8-damnp)<sub>2</sub>(dca)<sub>2</sub>] (<b>6</b>), where dca = dicyanamide anion, 3-ampy = 3-aminopyridine, pyNO = pyridine-N-oxide, 2,6-lut-NO = 2,6-lutidine-N-oxide, Me<sub>2</sub>en = N,N-dimethyl-ethylenediamine, Me<sub>4</sub>en = N,N,N′,N′-tetramethyl-ethylenediamine, and 1,8-damnp = 1,8-diaminonaphthaline. The coordination polymers have different dimensionalities: <b>1</b> and <b>5</b> form 3D networks structures; <b>3</b> and <b>4</b> form polymeric 1D chains and 1DD double chains, respectively. Ribbons of three fused polymeric chains are observed in <b>2</b>. In <b>6</b>, the mononuclear complex units form a hydrogen-bonded supramolecular 3D network. In the coordination polymer compounds, the dca linkers display three bonding modes: the most common μ<sub>1,5</sub>-dca and the least popular μ<sub>1,3</sub>- and μ<sub>1,3,5</sub>-dca bonding. The luminescence emission and thermal properties of the complexes were investigated.
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