The F(Q)s for both samples collected after cooling back to room temperature from the last experimental temperature (258 °C) provided evidence of recrystallization back to the original structure in each case (Fig. ). Pair distribution functions (PDF), D(r)s, were extracted from the F(Q)s after appropriate data corrections using experimental pycnometric densities (Table ). The variable temperature PDFs of [TBuA][Mn(dca)3] (Fig. , full dataset in Fig. ) demonstrate a reduction in the strength of the peaks and troughs above 10 Å at 190 °C, consistent with liquid-like atom-atom correlations above the framework Tm. No further substantial changes were observed, up to the maximum temperature of the experiment at 258 °C. A similar scenario is observed in the PDFs of [TPnA][Mn(dca)3] (Fig. ), with the disappearance of strong peaks in the correlations above 10 Å at temperatures above the Tm observed in DSC measurements.