New four isomeric chair architectures of 1:1 H-bonded supramolecular complexes were prepared through intermolecular interactions between 4-(2-(pyridin-4-yl)diazenyl-(2-(or 3-)chlorophenyl) 4-alkoxybenzoates and 4-n-alkoxybenzoic acids. The H-bond formation of all complexes was confirmed by differential scanning calorimetry (DSC) and Fourier-transform infrared spectroscopy (FTIR). Mesomorphic characterization was carried by DSC and polarized optical microscopy (POM). It was found that all prepared laterally chloro-substituted supramolecular complexes were nematogenic, and exhibited nematic phase and low melting temperature. The thermal stability of the nematic mesophase observed depends upon the location and spatial orientation of the lateral Cl⁻ atom in as well as the length of terminal chains. Theoretical calculations were carried out within the paradigm of the density functional theory (DFT) in order to establish the molecular conformation for the formed complexes and estimate their thermal parameters. The results of the computational calculations revealed that the H-bonded complexes were in a chair form molecular geometry. Additionally, out of the acquired data, it was possible to designate the influence of the position and orientation of the lateral group as well as the alkoxy chain length on the stability of the nematic phase.

Nonlinear architecture liquid crystalline materials of supramolecular 1:1 H-bonded complexes (I/II and I/III) were prepared through a self-assembly intermolecular interaction between azopyridine (I) and 4-n-alkoxybenzoic acid (II) as well as 4-n-alkoxyphenylazo benzoic acid (III). The H-bond formation of the prepared supramolecular hydrogen bonded (SMHB) complexes was confirmed by Fourier-transform infrared spectroscopy (FT-IR) and differential scanning calorimetry (DSC). Optical and mesomorphic behaviors of the prepared complexes were studied by polarized optical microscopy (POM) as well as DSC. Theoretical calculations were performed by the density functional theory (DFT) and used to predict the molecular geometries of the synthesized complexes, and the results were used to explain the experimental mesomorphic and optical properties in terms of their estimated thermal parameters. Ordinary and extraordinary refractive indices as well as birefringence at different temperatures were investigated for each sample using an Abbe refractometer and modified spectrophotometer techniques. Microscopic and macroscopic order parameters were calculated for individual compounds and their supramolecular complexes.

Cationic cyclopentadienyliron (CpFe⁺) is one of the most fruitful organometallic moieties that has been utilized to mediate the facile synthesis of a massive number of macromolecules. However, the ability of this compound to function as a nucleating agent to improve other macromolecule properties has not been explored. This report scrutinizes the influence of the cationic complex as a novel nucleating agent on the spherulitic morphology, crystal structure, and isothermal and non-isothermal crystallization behavior of the Poly(3-hydroxybutyrate) (PHB) bacterial origin. The incorporation of the CpFe⁺ into the PHB materials caused a significant increase in its spherulitic numbers with a remarkable reduction in the spherulitic sizes. Unlike other nucleating agents, the SEM imageries exhibited a good dispersion without forming agglomerates of the CpFe⁺ moieties in the PHB matrix. Moreover, according to the FTIR analysis, the cationic organoiron complex has a strong interaction with the PHB polymeric chains via the coordination with its ester carbonyl. Yet, the XRD results revealed that this incorporation had no significant effect on the PHB crystalline structure. Though the CpFe⁺ had no effect on the polymer’s crystal structure, it accelerated outstandingly the melt crystallization of the PHB. Meanwhile, the crystallization half-times (t_0.5) of the PHB decreased dramatically with the addition of the CpFe⁺. The isothermal and non-isothermal crystallization processes were successfully described using the Avrami model and a modified Avrami model, as well as a combination of the Avrami and Ozawa methods. Finally, the effective activation energy of the PHB/CpFe⁺ nanocomposites was much lower than those of their pure counterparts, which supported the heterogeneous nucleation mechanism with the organometallic moieties, indicating that the CpFe⁺ is a superior nucleating agent for this class of polymer.