Dimensional engineering modulation of electron-spin synergy for conductive metal-organic frameworks to boost electromagnetic wave absorption

AbstractConductive metal-organic frameworks (cMOFs) demonstrate remarkable advantages in electromagnetic wave (EMW) absorption, attributed to their designable topological architectures and tailorable conjugated networks. However, the preferential orientation and aligned stacking of low-dimensional systems (1D and 2D) tend to augment EMW reflection and restrict scattering, rendering the construction of efficient multiple loss channels unfeasible, resulting in insufficient overall energy dissipation. This study proposes a method that integrates density functional theory (DFT)-guided design with ordered liquid-phase assembly regulation, successfully fabricating a series of cMOFs with both efficient charge transport and excellent spin polarization, aimed at intensifying energy attenuation with scale-coordinated tuning. The volumetric framework of the Fe-DHBQ-3D (DHBQ represents: 2,5-dihydroxy-1,4-benzoquinone) exhibits enhanced charge transport efficiency and amplified interfacial polarization through a percolating conjugated network, which provides structural support for rapid charge separation and the formation of stable interfacial dipoles. Its coordination environment constrains metal ion spin arrangement to further boost magnetic dipole interactions that significantly reinforce the synergistic ordering and orientational regularity of the spin system. Prominently, its spatial interconnected network establishes full-domain connectivity that overcomes inherent fragmentation and local isolation in directionally extended arrangements, promoting the collaborative unification of the confined space and conjugated scaffold. With the transcending expansion of hierarchies, the effective absorption bandwidth (EAB) increased 5 orders of magnitude, and reflection loss (RL) improved significantly from −1.79 to −30.54 dB. This research not only reveals the structure-dominated energy management mechanism of cMOFs but also provides a general strategy for the efficient design and functional customization of EMW absorption materials.