Synthesis of Porphyrin Derivatives Bearing Six Carboxylic Acids for the Formation of Three‐Dimensional Hydrogen‐Bonded Network Structures

we synthesized a series of porphyrin derivatives with six carboxylic acid groups to explore their potential in forming hydrogen-bonded networks (YSHs). By systematically varying the position and structure of these carboxylic acid groups, we observed distinct types of hydrogen-bonded frameworks, including two- and three-dimensional networks. Using single-crystal X-ray crystallography, we confirmed that these derivatives form YSHs with unique structural properties influenced by carboxylic acid positioning and π-π interactions. The 1_Zn derivative forms a robust 3D hydrogen-bonded network stabilized by π-π stacking interactions, while the 2_Ni derivative, with no such stacking, exhibits reduced stability and collapses upon solvent removal. Structural variations like the terphenylene and biphenyl linkers in 3_Zn and 4_Zn lead to flexible frameworks, while the 5_Zn dimer forms two distinct structures depending on the solvent environment. Our findings reveal that careful control over carboxylic acid orientation and linker structure enables the design of diverse hydrogen-bonded networks with tunable stability and dimensionality. These insights advance our understanding of supramolecular assembly principles in porphyrin-based materials and offer new pathways for developing high-performance frameworks for applications in catalysis, sensing, and materials science.