VOCs Adsorption and Exchange Properties in Bispidine‐Based Mn(II) 1D CPs Made of Orthogonally Oriented Linear Chains

The combination of bispidine ligand L1 and Mn(II) produces CP 1‐MeCN with a one‐dimensional (1D) architecture unprecedented for bispidine‐based CPs. Single‐crystal X‐ray diffraction (SC‐XRD) reveals a robust framework of orthogonally oriented ribbon‐like chains in the tetragonal space group P 4 2 2 1 2 with solvent‐filled perpendicularly intersecting channels that account for about 30% of the unit‐cell volume. Volatile organic compound (VOC) exchange on SC proceeds via clean SC‐to‐SC transformations with nitrobenzene (NB), chlorobenzene (ClBz), and 1,2‐dichlorobenzene (DCB), but not with toluene (Tol). The corresponding microcrystalline powder, 1‐MeCN Pwd , and its thermally generated evacuated amorphous phase, 1‐amorph Pwd , were tested as well. In particular, 1‐amorph Pwd adsorbs ca. 1.6–1.9 mmol/g of aromatic NB, ClBz, and DCB (but only 0.7 for Tol) and up to 2.5 mmol/g of MeCN, under saturated vapor conditions at r.t. Although these uptake capacities are comparable to those of previously reported bispidine‐based CP sorbents, the preservation of the orthogonal chain packing motif upon guest uptake and the distinct interaction mechanism with the tested VOCs highlight a different role of chain topology and packing in governing sorption and offer new design criteria for the development of novel VOC‐capturing materials.