2021

Bulatova, Margarita

This thesis shows the successful application of noncovalent interactions (NCIs) in crystal engineering. Various NCIs were applied to obtain 10 novel self-assembled metallopolymeric structures: [PtI2COD]· CHI3, [PtI2COD]· 0.5I2, [PtBr2COD]· 0.5I2, [PtCl2COD]· I2, [PtI2COD]· 1.5FIB, [PtBr2COD]· 2FIB, [PtCl2COD]· 2FIB, trans-[PdI2(CNXyl)2]· I2, trans-[PtI2(CNXyl)2]· I2, and KI· 1,1’-bis(pyridin-4-ylmethyl)-2,2’-biimidazole. Several polymer geometries such as 0D, 1D, 2D, and 3D were achieved by fine-tuning the NCIs within the structures. Dependence of the structural organization on the relative strength of the NCI was considered, as well as the impact of the cooperative effect of multiple NCIs. Single crystal X-ray diffraction was used to study NCIs in the solid-state structures experimentally. Modern computational techniques were used to further study the NCIs and their influence on the structure including analysis of electrostatic surface potential (ESP), NCIplot, quantum theory of atoms in molecules (QTAIM), and ESP/electron density (ED) minima analysis. This thesis is divided into 3 parts. The first part provides a brief introduction to crystal engineering, noncovalent interactions, and applications of crystal engineering to the synthesis of metallopolymers. The second part briefly explains the specific methods and techniques used to study NCI. The last part summarizes the contribution of the author’s work in the field of NCIs. This thesis shows the close relation of the dimensionality of a self-assembled metallopolymer with the strongest noncovalent interaction and that it is also influenced by the cooperativity effect of weaker interactions. Keywords: crystal engineering, noncovalent interactions, halogen bonding, bifurcated bonding, metal-involved noncovalent interactions, platinum(II) complex, palladium(II) complex, ESP, ELF, NCIplot, supramolecular metallopolymers.