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Chirality control over the formation of Ni(II) complexes with chiral thiophosphorylated thioureas was achieved via breaking the symmetry of nickel coordination geometry by the introduction of the pyridine ligand, while centrosymmetric meso-complexes are formed from racemic ligands in case of square-planar nickel coordination. Centrosymmetric heterochiral arrangement is observed in crystals of ligands themselves through N–H⋅⋅⋅S hydrogen bonds in intermolecular dimers. Molecular homochirality in tetragonal pyramidal complexes is further transferred to supramolecular homochiral arrangement via key–lock steric interactions.

New racemic and enantiopure N-phosphorylated thioureas bearing 1phenylethyl or tetrahydronaphthalenyl fragments were synthesized. According to NMR data assisted by DFT calculations, the preferred conformation is stabilized by an intramolecular hydrogen bond. This form in solution is in equilibrium with dimeric N− H•••S hydrogen-bonded associates, the population depending on the concentration. In the crystalline phase the low-energy conformation with an intramolecular H-bond is realized only in the racemic tetrahydronaphthalenyl derivative. In most crystals various types of intermolecular hydrogen bonding are observed, accompanied by the formation of infinite linear chains or helical structures. Due to the conformational lability of compounds and competitive intermolecular H-bonding, multiple polymorphic modifications are formed. Therefore, crystallization of enantiopure 1-phenylethyl derivatives from various solvents results in concomitant polymorphs at room temperature. One of them undergoes reversible two-step phase transitions from the high-symmetry I4 1 space group (Z′ = 1, no disorder) via the P4 1 space group (Z′ = 6) to the monoclinic P2 1 space group (Z′ = 16) accompanied by drastic concerted conformational changes. Notably, the optimization of the crystal packing is observed upon phase transitions with a gradual reduction of the void space in the unit cell from 4.5% to 0.8%. This is a rare case of several high-Z′ polymorphs for one compound, with chirality playing an important role.

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Mononuclear and polymeric Co(II) complexes were obtained with enantiopure and racemic N-thiophosphorylated thioureas with the metal to ligands ratio 1:2. To control the stereochemistry of the complexes synthesized from racemic...

A high‐yield and simple synthesis of certain aminomethylisatins bearing dye fragments via the Mannich reaction of isatin with amino‐containing azobenzenes was reported. It was found that the absence of electron‐donating groups in azo‐dye molecule prevents aminomethylation of isatin. The effect of the incorporation of an isatin moiety with an azobenzene dye in one molecule on its absorption and electrochemical behavior was studied using UV spectroscopy and cyclic voltammetry.

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