Enthalpy‐Driven Topological Programming of (TPMS)‐Like Carbon Networks

Deterministic control over pore topology remains a central bottleneck in porous carbons, limiting the ability to translate molecular design into predictable electromagnetic attenuation and coupled thermal functions. Herein, we introduce an enthalpy-driven topological programming paradigm in which the bond-enthalpy of energetic N-N' fragments acts as a quantitative dial to steer self-propagating reconstruction of coordination frameworks into a continuous sequence of (TPMS)-like bicontinuous architectures. This programmable topology simultaneously establishes impedance-matched, multi-scattering pathways for wave ingress and concentrates heterogeneous interfaces that promote coupled dielectric and magnetic dissipation via vortex-like magnetic textures and interfacial charge accumulation. As a result, the optimized Co@1,2,3,4-NC delivers a minimum reflection loss of -53.97 dB with an effective absorption bandwidth of 7.84 GHz at 15 wt% loading. Beyond electromagnetic performance, the same bicontinuous topology suppresses heat transport by intensifying phonon scattering across hierarchical boundaries, enabling an ultralight and hydrophobic aerogel prototype that integrates electromagnetic shielding with thermal insulation. More broadly, bond-enthalpy-encoded topology control provides a transferable route to program bicontinuous porous networks across material chemistries, bridging thermodynamic driving forces with topological invariants for multifunctional matter.