Rational Monomer Design and Self-Assembly Control for the Development of 2D Supramolecular Materials and Multicomponent Assemblies

[eng] This thesis explores the interplay between molecular design and self-assembly control in the formation of two-dimensional (2D) supramolecular polymers and liquid-crystalline materials. For this purpose, we rely on different molecules as building blocks including organic chromophores and macrocycles functionalized with hydrogen bonding (H-bonding) units and/or solubilizing chains. The resulting molecules were initially designed to self-assemble in organic solvents but also to form liquid-crystalline phases in solid state. In chapter 1 we studied the self-assembly behavior of hydrogen bonded (H-bonded) urea macrocycles. In which a newly developed H-bonding urea macrocycle with bulky solubilizing pendant groups, self-assembles into one-dimensional (1D) or 2D structures depending on the presence or absence of solvent. The 2D structures are the result of a H-bonded brick-like interaction pattern. In chapter 2 we unveiled the intriguing self-assembly landscape of a newly developed cyanine dye. This cyanine compound self-assembles into a nanoparticle-like H-type aggregate, that evolves into a second H-type aggregate with a nanosheet morphology. Apart from this route, there is a hidden pathway to form a 2D J-type aggregate. This study allowed us to control the formation of the desired polymorph by sample manipulation. In chapter 3 we designed a multicomponent system consisting of a mixture of two tailored compounds forming an axial columnar liquid crystal. The two complementary compounds, based on tris(p-phenylenevinylene) (TPV) and tris(p-phenyleneethynylene) (TPE) were substituted with a bis-pyridine and di-acid respectively, and self-assembled into an unprecedented columnar liquid crystal with a precise co-assembly of the two components. This thesis provides novel tools for the development of supramolecular materials. A central contribution lies in the molecular design of 2D supramolecular assemblies, a research area that has remained scarcely explored within the field. Moreover, the work introduces an unprecedented strategy for constructing two-component materials with precise control of the assembly processes at both the macroscopic and molecular levels. While molecular programming has served as the key approach to develop these materials, this thesis also reveals the fundamental role of kinetic and thermodynamic control in achieving the desired architectures. Altogether, the advances presented here are expected to inspire further research and significantly contribute to the development of functional self-assembled materials.