The ultrafast time-resolved spectroscopy in the fs-ps time scale is a method of choice to characterize the initial charge separation and transfer processes governing the photochemical activity of the MOF materials. Here we are reporting femtosecond UV-Vis transient absorption investigations of the excited states of the Pyr2Bpy molecular ligand, of the Cp*Rh@Pyr2Bpy complex, as model building block of the pyrene-bipyridine conjugated microporous polymer (PyrBpy-CMP) and of its corresponding Rh metallated catalysts Cp*Rh@PyrBpyCMP, respectively. The investigated compounds are shown in Scheme 1. The experiments were notably carried-out in acetonitrile:triethanolamine solution to elucidate the reaction between the excited states of the different compounds and the amine under the same reactive conditions of ref. . These pump-probe measurements have been completed by steady state absorption and emission spectroscopy and by time-resolved emission measurements.