20:T532,Reducing CO₂ into fuels via photochemical reactions relies on highly efficient photocatalytic systems. Herein, we report a new and efficient photocatalytic system for CO₂ reduction. Driven by electrostatic attraction, an anionic metal-organic framework Cu-HHTP (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) as host and a cationic photosensitizer [Ru(phen)₃]²⁺ (phen = 1,10-phenanthroline) as guest were self-assembled into a photocatalytic system Ru@Cu-HHTP, which showed high activity for photocatalytic CO₂ reduction under laboratory light source (CO production rate of 130(5) mmol g^-1 h^-1, selectivity of 92.9%) or natural sunlight (CO production rate of 69.5 mmol g^-1 h^-1, selectivity of 91.3%), representing the remarkable photocatalytic CO₂ reduction performance. More importantly, the photosensitizer [Ru(phen)₃]²⁺ in Ru@Cu-HHTP is only about 1/500 in quantity reported in the literature. Theoretical calculations and control experiments suggested that the assembly of the catalysts and photosensitizers via electrostatic attraction interactions can provide a better charge transfer efficiency, resulting in high performance for photocatalytic CO₂ reduction.21:T4b4,Designing a functional, conductive metal-organic framework (cMOF) is highly desired. Substantial efforts have been dedicated to increasing the intralayer conjugation of the cMOFs, while less dedication has been made to tuning the interlayer charge transport of the metal-organic nanosheets for the controllable dielectric property. Here, we construct a series of conductive bimetallic organic frameworks of (Zn_xCu_3-x) (hexahydroxytriphenylene)₂ (ZnCu-HHTP) to allow for fine-tuned interlayer spacing of two-dimensional frameworks, by adjusting the ratios of Zn and Cu metal ions. This approach for atomistic interlayer design allows for the finely control of the charge transport, band structure, and dielectric properties of the cMOF. As a result, Zn3Cu1-HHTP, with an optimal dielectric property, exhibits high-efficiency absorption in the gigahertz microwave range, achieving an ultra-strong reflection loss of -81.62 decibels. This study not only advances the understanding of the microstructure-function relationships in cMOFs but also offers a generic nanotechnology-based approach to achieving controllable interlayer spacing in MOFs for the targeted applications.

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