On filtering of the results, six precursor combinations were identified as 'hits' where the automated HRMS analysis identified the targeted topological mass ions as major species and automated 1 H NMR analysis identified high conversion with <1% residual aldehyde remaining. However, while the automated HRMS analysis identifies any targeted MNLN or M2X3 assemblies, the latter M2X3 species may also form from fragmentation of larger topologies during the analysis. For example, a M2L3 mass ion may be from a helicate or mesocate structure, but may A fully red box is indicative of the ideal outcome from the automated analysis, where a reaction has <1% aldehyde remaining and a target structure has been identified as a major peak in the HRMS. also be a fragment of an M4L4 tetrahedron or higher-order architecture. In addition, as alluded to above, full consumption of the aldehyde does not necessarily indicate the formation of a MOC topology and could instead simply indicate complete conversion to the tri-imine ligand. Therefore, the 1 H NMR spectra of the hits were manually interpreted further to determine the reaction outcome in relation to the number of species formed, and subsequently correlated with the identified topologies from the mass spectra to identify the major assemblies that had formed (Table ). Overall, this yielded three MOCs with a Tsymmetric M4L4 structure, but with different ligand and counterion components, (Zn4(A1)4.(NTf2)8, Zn4(A1)4.(BF4)8 and Zn4(A3)4.(BF4)8, referred to as cage 1, cage 2 and cage 3, respectively (Figure ). These three cages were subsequently taken forward and manually scaled-up using the same reaction conditions for full characterization (Supporting Information S3).