Since this work focuses on the properties of the PPh3-based macroligand under varying crosslinking conditions, we wanted to evaluate the alterations of the polyphosphine framework during catalytic application. Therefore, we investigated the catalysts after the recycling experiments with nitrogen physisorption and FTIR. Physisorption isotherms (Fig. and Table ) demonstrate the preservation of the porous structure of SA-P-BP-Ru, while Fe-P-BP-Ru loses a minor proportion of its microporosity and the spent Al-P-BP-Ru catalyst owns only two third of its initial pore volume. This degradation of the macroligands can be due to thermal and swelling tensions of the porous frameworks or the rearrangement of the flexible building units in the solvated state. The extent of the loss of porosity is in alignment with the thermal stability of the respective frameworks in TGA analysis. FTIR experiments of the catalysts after three catalytic runs suggest the occurrence of structural changes (Fig. ). The shape of the IR-spectrum of Fe-P-BP-Ru remains mainly unchanged, whereas the P=O vibration band (1179 cm -1 ) strengthens in Al-P-BP-Ru, resulting from oxidation processes during catalysis. In addition, the catalytic application causes a more pronounced peak at 2975 cm -1 in the spent Al-P-BP-Ru, which can be assigned to the aliphatic C-H vibration of the alkyl bridges. An even stronger emerging of the aliphatic C-H vibration bands (2800 cm -1 -2980 cm -1 ) happens for SA-P-BP-Ru, complemented by the signal of the CH2 deformation vibration (1378 cm -1 ), which was not observable in the pristine macroligand. Moreover, new vibrational modes of the spent SA-P-BP-Ru are present at 1462 cm -1 and 1035 cm -1 , indicating the presence of oxygen-containing moieties in the macroligand.