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The formation and stability of (arene)Cr(CO) 3 species inside two highly porous materials—UiO-66, which is a recently synthesized metal−organic framework, and a cross-linked poly(styrene-co-divinylbenzene) resin—are investigated in detail by means of complementary spectroscopic techniques and theoretical calculations. In particular, Fourier transform infrared (FT-IR), ultraviolet-visible (UV−vis), and X-ray absorption near-edge structure (XANES) spectroscopies, coupled with theoretical calculations, allow the formation of the (arene)Cr(CO) 3 species to be followed in situ, starting from the Cr(CO) 6 precursor, monitoring the changes in the vibrational and electronic properties of the materials. EXAFS spectroscopy gives the structural evidence of the functionalized unities. Finally, the photoinduced reactivity of Cr(CO) 3 in UiO-66 is also explored, by following the substitution of one CO ligand with a N 2 molecule. The overall presented data would become the starting point for the development of a systematic procedure for investigating functionalized porous matrices.
Chavan et al. (Wed,) studied this question.