In the last part of this discussion, we will connect the photophysical and photochemical properties of the CMP with that of the molecular compounds. The steady state and time-resolved emission properties of PyrBpyCMP and Cp*Rh@PyrBpyCMP have been reported by us in a previous study . Briefly, both materials exhibit a dual emission band. A first emission around 490 nm and corresponding to an excitation band centred at 375 nm and second emission extending from 500 nm to 750 nm and associated with an excitation spectrum with a band edge at 525 nm. In our previous paper, we described the first emission as localized of the PyrBpy chromophe (LE) and the second red-shifted contribution has been assigned to an internal charge transfer (ICT) emission involving a more pronounce charge transfer from the pyrene to the surrounding bipyridine moieties. From the emission properties of the molecular ligand Pyr2Bpy and for the molecular complex reported in this work, we can clearly correlate the LE emission bands of PyrBpyCMP to the emission of pyrenebipyridine-pyrene conformation similar to that of the MICT state of the Pyr2Bpy molecular ligand (470 nm) and the ICT emission to that of a molecular conformation similar to that of the TICT state (650 nm) from the ligand part of the molecular complex, respectively. We notice however that the lifetime of the emission for PyrBpyCMP are significantly shorter that for the molecular compounds. Notably for the LE emission of the polymer, we found in MeCN and MeCN:TEOA a lifetime of 110 ps, in comparison to lifetimes above 700 ps for the molecular Pyr2Bpy ligand (2.4 ns in MeCN, 1.4 ns in THF and 0.7 ns in THF:TEOA). This shows that the spatial arrangement of the polymer favours the internal conversion processes in comparison with the free molecular ligand. This can be understood by the fact that the 3D arrangement in the polymers induces some torsion around the pyrene -bipyridine bond.