Finally, automated HRMS peak detection and assignment was developed as part of the automated data analysis workflow to identify mass ions corresponding to the different potential POC species in the mass spectra. However, this was a non-trivial problem to solve since the main mass ion (m/z, 100%) for a doubly charged species is identical to that of a singly charged species of half the size (for example, a doubly charged Tri 8 Di 12 species has the same calculated mass ion as a singly charged Tri 4 Di 6 species). Therefore, to account for screening of multi-charged species, identification of the spacing between peaks in the isotopic distribution was also included. For example, detection of 0.5 m/z peak separation would be required to differentiate between a doubly charged species and a singly charged species. In addition, HRMS cannot differentiate between a Tri 8 Di 12 species and a catenated Tri 4 Di 6 species, both of which would have the same mass. Therefore, we opted to screen for the discrete building block assemblies that would constitute full reactivity of all functionalities, namely [2+3], [4+6], [6+9] and [8+12], over the specific Tri 2 Di 3 , Tri 4 Di 6 , Tri 6 Di 9 , and Tri 8 Di 12 topologies. Overall, this meant that analysis of the HRMS data through file pre-processing and topological outcome assignment was the most challenging of the three experimental characterisation methods to automate.