Solution‐Processable and Programmable Al ₈ Macrocycles for Advanced Dielectrics: Uniting High Permittivity, Minimal Loss, and Robust Moisture Resistance

Abstract The development of polymer composite dielectrics exhibiting high dielectric constant, low dielectric loss, and excellent environmental stability is essential for enhancing field‐effect transistor (FET) performance and reliability. While conventional high‐κ materials like Al 2 O 3 suffer from surface hydrolysis‐induced polarization inhomogeneity, we present herein a molecular engineering solution through solution‐processable and structurally programmable Al 8 macrocycles. By employing computationally guided metal center and macrocycle surface engineering, we achieved highly efficient synthesis of solution‐processable Al 8 ‐based dielectric materials. The resulting series of 10 structurally programmed Al 8 macrocycles creates tailored electronic microenvironments, delivering exceptional dielectric properties: a threefold enhancement in dielectric constant compared to pure polymer matrices, remarkably low dielectric loss (tan δ = 0.064), and superior humidity resistance versus conventional Al 2 O 3 fillers. This work establishes a comprehensive materials paradigm that simultaneously optimizes the critical dielectric parameters (κ, tan δ, and moisture resistance) while demonstrating the versatility of cluster molecular design.