For 2 Th , formation of a quadruply-stranded [Pd2(2 Th )4] 4+ cage was concluded based on NMR (e.g. downfield shifts of the ortho-pyridyl protons, Fig. ), diffusion-orientated spectroscopy (DOSY; RS ≈ 12 Å) and ESI-MS data (Fig. ). For 2 DBF , following initial dissolution, a precipitate was observed to form. After filtration, 1 H NMR analysis of the solution revealed the internally-directed ortho-isoquinoline proton to be shifted significantly upfield relative to the free ligand (Fig. ), indicative of π-stacking. The NMR data, in combination with ESI-MS, were congruent with formation of a helical Pd2L4 assembly. A broad and messy 1 H NMR spectrum was observed at room temperature from the self-assembly mixture with 2 Ph , with DOSY suggesting formation of at least two species (RS ≈ 11 and 13 Å). At 80 °C the 1 H NMR spectrum sharpened dramatically to reveal a set of predominant signals (Fig. ). Upfield shifts of some signals relative to the ligand (Fig. ) were consistent with a helical Pd2L4 architecture. This was supported by ESI-MS, from which additional signals for a Pd3L6 assembly could also be seen (Fig. -92). Thus, a mixture of species, including a Pd2L4 cage and a Pd3L6 assembly, appeared to have formed.