The dimetallic [M₂(bpy)₂(NO₃)₂](NO₃)₂ moieties (M = Pd(II) or Pt(II)) react preferentially at the pyrazolyl end of the pyridyl-pyrazole ligand, giving rise to dimetallic corners. Subsequently, the dimetallic corner building blocks featuring two pyridine donors are coordinated by monometallic [M(bpy)(NO₃)₂] moieties (M = Pd(II) or Pt(II)) to form homo- or hetero-metallomacrocycles.

Three hexametal-organic cages [(N^N)₆Pd₆L₂]⁶⁺ with syn, syn, syn conformation were synthesized via the coordination of tris(4-(1H-pyrazol-3-yl)phenyl)amine ligands and [(N^N)₂Pd₂(NO₃)₂](NO₃)₂ dimetallic corners (N^N = 2,2′-bipyridine for 1; 4,4′-dimethylbipyridine for 2; 1,10-phenanthroline for 3). These hexametal-organic cages exhibit anion sensing toward HSO₃ ⁻ in aqueous solution via fluorescent titration and NMR spectroscopy studies.

Organo-heterometallic supramolecular cages are formed from Fe^III ions and dimetallic corners arising from a 3-(3,5-dimethyl-pyrazol-4-yl)pentane-2,4-dione ligand by programmable self-assembly.

By employing different diimine complexes and a naphthanoimidazolate (L¹) or benzoimidazolate (L²) anion ligand as linker, a series of trimetallo-macrocycles have been synthesized through a directed self-assembly approach that involves spontaneous deprotonation of the ligands in aqueous solution. Some compounds, namely, [M₃L₃](NO₃)₃ (M = (18-crown-6-phen)Pt, 1 or 7; (15-crown-5-phen)Pt, 2; (benzo-24-crown-8-phen)Pt, 8; (benzo-24-crown-8-phen)Pd, 9; (15-crown-5-phen)Pd, 4 or 11; (18-crown-6-phen)Pd, 3 or 10; (dmbpy)Pd, 6 or 14; (bpy)Pd, 5 or 13; (bpy)Pt, 12; (N4-Phen)Pd, 15) were synthesized. In all of these compounds, the L¹or L² anion ligands are in a syn, syn, syn orientation which result in a bowl-like cavity that can serve as a host to bind the methyl of a solvent CH₃CN within the naphthanoimidazolate or benzoimidazolate-built cavity through C–H⋯π hydrogen bonds in the crystal state. The structures are characterized by elemental analysis, ¹H NMR, ESI-MS, and in the cases of 4a, 11, 13, and 14a by single-crystal X-ray diffraction analysis.

By employing dipalladium corners [(bpy)₂Pd₂(NO₃)₂](NO₃)₂ or [(phen)₂Pd₂(NO₃)₂](NO₃)₂ (where bpy = 2,2′-bipyridine and phen = 1,10-phenanthroline) to bridge ferrocene-based dipyrazole ligand (L¹1) and m-phenylene-based dipyrazole ligands (L^2–32–3) in aqueous solution, a series of positively-charged [M₄L₂]⁴⁺ metallomacrocycles were obtained. Their structures were characterized by ¹H NMR, electrospray ionization mass spectrometry (ESI-MS), elemental analysis, and single crystal X-ray diffraction analysis for 1·4NO₃ ({[(bpy)Pd]₄L¹1₂}(NO₃)₄) and 4·4NO₃ ({[(phen)Pd]₄L²2₂}(NO₃)₄). In their single crystal structures, NO₃ ⁻ anions are located at the dipalladium corners by C–H⋯O hydrogen bonds. Importantly, the anion-sensing properties of ferrocene functionalized [Pd₄Fe₂] hetero-metallomacrocycle 1 were investigated in acetonitrile by SWV, CV and NMR analysis, showing promise for Br⁻ sensing.