PHD Thesis

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Browsing PHD Thesis by Author "BENALI-CHERIF Rim"

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    Synthesis, characterization, and applications of polymorphs, Metal- Organic Frameworks (MOFs), and organic-inorganic hybrid compounds based on nitrogen bases: Towards new materials with physicochemical properties
    (2026) BENALI-CHERIF Rim
    This thesis investigates polymorphism in molecular solids and the structural chemistry of hybrid organic-inorganic compounds and organometallic complex through integrated experimental characterization (single-crystal X-ray diffraction, spectroscopy) and computational methods (density functional theory, Hirshfeld surface analysis). The research comprises three parts. Part One explores polymorphism through three model systems. A new triclinic polymorph of copper (II) diacetate monohydrate (space group P-1) was discovered which is consider as a Metal-Organic Framework (MOF) , exhibiting the smallest HOMO-LUMO gap among known forms and enhanced chemical reactivity. A new monoclinic polymorph of cytosinium gallate (space group P2₁) demonstrated stronger hydrogen bonding and π-π stacking with pharmaceutical relevance. A third polymorphic form of a rhodanine derivative (space group P2₁/c) revealed that polymorphism can arise primarily from packing variations with minimal electronic perturbation. Part Two reports the synthesis of N,N-dimethyl-4-[(Z)-(4-oxo-2-sulfanylidene-1,3thiazolidin-5-ylidene)methyl]anilinium bromide, a hybrid compound with a 2.53 eV HOMOLUMO gap and spatial separation of frontier orbitals, establishing donor-acceptor characteristics for potential applications in charge-transfer materials. Part Three characterizes a new cobalt(II) benzoylacetonate complex [Co(bzac)₂] with square-planar CoO₄ geometry (space group P2₁/n) exhibiting acicular morphology driven by strong π-π stacking, establishing structure-morphology correlations. This work demonstrates that polymorphism is ubiquitous across diverse chemical systems and that polymorphic differences produce measurable variations in electronic structure, stability, and packing relevant to pharmaceuticals, catalysis, and materials science. The integrated experimental-computational methodology provides a framework for rational materials design and crystal engineering.