Designing functional metal–organic frameworks through synthesis–structure–interface coupling: toward structure–property relationships

Metal–organic frameworks (MOFs) are versatile porous materials whose structure and functionality can be tuned through coordination chemistry. Their performance is governed not only by framework topology but also by the coupled effects of synthesis conditions, defect chemistry, and interfacial structure across multiple length scales. In this review, we introduce a unified synthesis–structure–interface–property framework that treats these factors as interdependent variables controlling adsorption, mass transport, and interfacial interactions in MOF systems. We examine how intrinsic modifications, including defect engineering, multimetallic node incorporation, and linker functionalization, regulate coordination environments, surface chemistry, and pore accessibility, and extend these concepts to confinement effects and interface-driven hybrid architectures such as MOF–MOF, metal oxide–MOF, MOF–carbon, MOF–COF, and MOF–MXene systems. By linking synthetic control to defect landscapes and interfacial organization, we establish general principles governing reactivity, transport, and stability, with particular emphasis on the interplay between surface chemistry and structural heterogeneity and the resulting trade-offs between activity, robustness, and reproducibility. Current limitations in predictive synthesis, interfacial characterization, and structure–property correlation are discussed, highlighting the need for operando and multiscale approaches to resolve dynamic behaviour under working conditions. This perspective provides a framework for advancing MOF-based materials in catalysis, separations, and energy-related applications.