Control of dimensionality in Manganese Coordination Polymers using rigid tetrahedral-shaped [1.1.1.1]metacyclophane ligands bearing benzoate coordinating sites: From homochiral 1D to 3D diamond-like structures

Solvothermal synthesis involving tetrasubstituted carboxylic derivatives of [1.1.1.1]metacyclophane (1–2) bearing rigid phenyl spacer, that inherently adopt the 1,3-Alternate conformation, with Manganese salts (acetate and nitrate) led to new 1D and 3D coordination polymers: {13-Mn9O3(CH3COO)6(C5H5N)12} (13-Mn9) and {2-Mn2(C3H7NO)2} (2-Mn2), respectively. The X-ray diffraction analysis revealed that: (i) ligand 1, containing meta-benzoate coordinating sites, forms a 1D chiral helicoidal Coordination Polymer (13-Mn9) with trinuclear metallic clusters (MnIIMnIII2(μ3-O)) acting as linear connection nodes; (ii) ligand 2, bearing para-benzoate moieties forms, a 3D diamond-like Coordination Polymer (2-Mn2) presenting Mn(II) polymeric chains bridged by tetrahedral-shaped ligand. The obtained Mn-based compounds are the first examples of coordination polymers based on tetrasubstituted [1.1.1.1]metacyclophane ligands bearing carboxylate coordinating groups. [Display omitted] •Tetrasubstituted carboxylic derivatives of [1.1.1.1]metacyclophane adopting the 1,3-Alternate conformation•Mn based Coordination Polymers•Influence of the localisation of carboxylate coordinating group on the dimensionality of the formed Coordination Polymer•MnIIMnIII2(μ3-O) based 1D Coordination Polymer•Diamond-like Mn(II) Coordination Polymer