MOFs, COFs, and HOFs

Metal-organic, covalent-organic, and hydrogen-bonded organic frameworks (MOFs, COFs, and HOFs, respectively) share reticular design but differ in bonding hierarchies that govern stability, processability, and device performance. We take an interaction-energy-centric view linking bond energies (Hydrogen bond ∼10–40 kJ mol⁻¹; metal–ligand coordination ∼90–350 kJ mol⁻¹; covalent linkages ∼300–600 kJ mol⁻¹) and hard/soft acid/base (HSAB) matching to practical choices of framework, synthesis route, and post-synthetic modification. Solution-based (solvothermal/hydrothermal, microwave, interfacial) and non-solution-based (mechanochemical, vapor-based, electrochemical) routes are compared through synthesis to property maps (such as modulator-controlled defect densities in Zr-MOFs; reversible to irreversible linkage conversion in COFs; cooperative π-π/H-bonding to stabilize HOFs). Characterization is organized by decision need (structure; surface/porosity; imaging; thermal/electrochemical; computation), with notes on when microcrystal electron diffraction (MicroED) resolves low-crystallinity systems impractical for single-crystal X-ray diffraction (SCXRD). Across applications (energy storage/conversion, separation, sensing, catalysis, biomedicine), 2–4 flagship studies per area that identify the bottleneck, quantify the gain, and explain why a given framework class succeeds, or fails, relative to the others are retained. Broader coverage is moved to curated tables/SI. Web of Science (WoS)–derived bibliometrics underpin radar charts (Methods disclosed) for transparent weighting of technique and application trends. The result is a comparative playbook, interaction-energy design rules, stability maps, and cross-framework scorecards to select the right framework, route, and characterization for a target specification while clarifying where COFs and HOFs still lag behind for industrial translation.