Photoinitiated solid-state reactions are known to affect the physical properties of coordination polymers, such as fluorescence and sorption behaviour, and also afford extraordinary architectures (e.g. three-periodic structures with polyorganic ligands). However, the construction of novel photo-sensitive coordination polymers requires an understanding of the factors which govern the mutual disposition of reactive fragments. A series of zinc(II) malonate complexes with 1,2-bis(pyridin-4-yl)ethylene and its photo-insensitive analogues has been synthesized for the purpose of systematic analysis of their underlying nets and mutual disposition of N-donor ligands. The application of a big data-set analysis for the prediction of a variety of possible complex compositions, coordination environments and networks for a four-component system has been demonstrated for the first time. Seven of the nine compounds possess one of the highly probable topologies for their underlying nets; in addition, two novel closely related four-coordinated networks were obtained. Complexes containing 1,2-bis(pyridin-4-yl)ethylene and 1,2-bis(pyridin-4-yl)ethane form isoreticular compounds more readily than those with 4,4 0 -bipyridine and 1,2-bis(pyridin-4-yl)ethylene. The effects of the precursor, either zinc(II) nitrate or zinc(II) acetate, on the composition and dimensionality of the resulting architecture are discussed. For three of the four novel complexes containing 1,2-bis(pyridin-4-yl)ethylene, the single-crystal-to-single-crystal [2 + 2] cycloaddition reactions were carried out. UV irradiation of these crystals afforded either the 0D!1D or the 3D!3D transformations, with and without network changes. One of the two 3D!3D transformations was accompanied by solvent (H 2 O) cleavage.

1,5-Diaryl(heteroaryl)pentenynones show a tendency to crystallize in acentric space groups due to their inclination to form C—H...O hydrogen-bonded chains instead of dimers and thus exhibit nonlinear optical properties. A series of symmetrical α,α′-bis(3-arylprop-2-yn-1-ylidene)cycloalkanones and unsymmetrical α-(furan-2-ylmethylene)-α′-(3-arylprop-2-yn-1-ylidene)cyclohexanones closely related to pentenynones was synthesized, namely 2,5-bis(3-phenylprop-2-yn-1-ylidene)cyclopentanone, C23H16O, 2,5-bis[3-(4-bromophenyl)prop-2-yn-1-ylidene]cyclopentanone, C23H14Br2O, 2,6-bis(3-phenylprop-2-yn-1-ylidene)cyclohexanone, C24H18O, 2,6-bis[3-(4-bromophenyl)prop-2-yn-1-ylidene]cyclohexanone, C24H16Br2O, 4-tert-butyl-2,6-bis(3-phenylprop-2-yn-1-ylidene)cyclohexanone, C28H25O, 4-tert-butyl-2,6-bis[3-(4-methylphenyl)prop-2-yn-1-ylidene]cyclohexanone, C30H30O, 2-(furan-2-ylmethylene)-6-(3-phenylprop-2-yn-1-ylidene)cyclohexanone, C20H16O2, and 6-(3-butylprop-2-yn-1-ylidene)-2-(furan-2-ylmethylene)cyclohexanone, C10H20O2, and investigated by means of X-ray diffraction to understand peculiarities of their supramolecular organization. Four of the eight novel compounds crystallize in acentric space groups. Three of these four compounds contain substituents at the para position of the phenyl ring, which affect the charge density on the H(CPh) atoms and thus stabilize CPh—H...O interactions. The fourth compound realizes the C—H...O hydrogen bonding via H atoms of the furyl ring. The applicability and shortcomings of the Full Interaction Map tool to predict the likelihood of C—H...O and C—H...Br hydrogen-bonded motifs, and the effect of substituents on the phenyl ring on the supramolecular architecture are discussed.