| Summary: | A combination of 4-styrylpyridine (spy) and 1-adamantanecarboxylic acid (Hadc) was employed in the assembly reactions with Zn(II) and Cu(II) nitrates. The photoreactivity of the products was compared and discussed on the basis of the structure–function relationship. Zinc(II) complex <b>1</b> is a trinuclear species of type [Zn<sub>3</sub>(spy)<sub>2</sub>(adc)<sub>6</sub>] in which three zinc(II) atoms are linearly arranged, with two adjacent zinc(II) atoms linked by three bridging carboxylates. Two spy ligands occupy both terminal positions, yielding the overall structure of a six-bladed windmill. Copper(II) complex <b>2</b>, [Cu(spy)<sub>2</sub>(adc)<sub>2</sub>][Cu<sub>2</sub>(spy)<sub>2</sub>(adc)<sub>4</sub>]·2DMF, is an inorganic cocrystal comprising a mononuclear complex with a <i>trans</i> square planar geometry and a dinuclear complex with a paddle-wheel structure. In the photoreaction experiments characterized by <sup>1</sup>H NMR spectroscopy, the zinc(II) complex was found to be photoinert, while the copper(II) complex was photoreactive to form a cyclobutene ring via the [2+2] photodimerization between two spy ligands, resulting in the preparation of a one-dimensional chain as a coordination polymer. The separations of the C=C bond pair obtained from the crystal structures for both products also support their photoreactivity. For example, the spy ligands from two adjacent monocopper(II) complexes are aligned in a head-to-tail manner with the separation of 3.899 Å between the C=C bond pair, satisfying the so-called Schmidt criteria (<4.2 Å). However, no other products satisfy this condition.
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