A nitro-decorated MOF is used for the selective separation of benzene and cyclohexane in both liquid and vapor phases.

Rational synthesis of a series of new heterometallic MOFs was carried out by the judicious choice of the corresponding pivalate complexes [Li₂M₂(piv)₆(py)₂] (M = Zn²⁺, Co²⁺, piv⁻ = pivalate anion and py = pyridine) as a source of secondary building units, {LiM(O₂CR)₃} and an organic tricarboxylate linker as a node defining the dimensionality of the framework by the orientation of the carboxylic group in or out of the central aromatic ring plane. Thus the trimesate (btc³⁻) linker results in 3D srs topology frameworks with intersecting systems or isolated channels, and 1,3,5-benzenetribenzoate (btb³⁻) results in layered hcb isostructural compounds additionally stabilized with H–π interactions between the layers. The layered compounds demonstrate a permanent porosity with a BET surface area of up to 688 m²·g⁻¹ with the possibility of selective gas adsorption (CO₂ over N₂ and CH₄). Zn-Based coordination polymers show notable color changes and drastic (up to 30 times) quenching of luminescence upon inclusion of different nitroaromatics.

Building blocks with low connectivity and no embedded directionality are prone to polymorphism, as demonstrated by the diversity of 4-connected zeolitic nets (>250). As a result, their deployment for design in reticular and isoreticular chemistries remains a challenge. However, the ability to control geometrical peculiarities offers potential to deviate from the assembly of default structures. Here we report the face-directed assembly of >20 isoreticular zeolite-like metal–organic frameworks (ZMOFs) by using polytopic expanding and tightening centring structure-directing agents (cSDAs). The cSDAs are selected with the appropriate geometrical coding information to alter and control the orientation of adjacent supermolecular building blocks. The ZMOFs have an underlying sodalite (sod) topology that is remarkably suited for the rational assembly of multinary materials. In addition to a variety of metal cations (In, Fe, Co and Ni), a diverse range of cSDAs (di-, tri-, tetra-, hexa-, pyridyl or imidazole) are used and combined. Our approach enables isoreticular possibilities at both extremities of the porous materials spectrum: In-sod-ZMOF-102 exhibits small pore aperture suitable for efficient separation, while Fe-sod-ZMOF-320 with 48-Å-wide mesopores exhibits high hydrogen uptake, methane storage working capacity and a high gravimetric working capacity for oxygen.