Programmable Metal–Organic Complex Arrays with Precisely Controlled Metal Sequences as Tunable Multinuclear Scaffolds

Metal–Organic Complex Arrays (MOCAs) offer a modular framework for creating multinuclear systems with precise control over metal ion identity and sequencing at the molecular scale. This structural accuracy allows researchers to investigate how specific metal arrangements dictate cooperative phenomena, such as catalytic efficiency, electronic interactions, and photophysical responses. Recent breakthroughs in synthetic strategies─including orthogonal protection and periodic metalation─have enabled the fabrication of highly predictable heterometallic structures. This Review explores the fundamental principles of MOCAs’ sequence control, contemporary fabrication techniques, and the relationship between metal placement and emergent properties. Additionally, it examines applications of MOCA in catalysis, sensing, and bioinspired assembly. The discussion concludes by addressing critical future challenges, emphasizing the necessity of expanding compositional diversity and integrating these discrete architectures with functional components to achieve scalable, synergistic performance in advanced materials.