Abstract
Four different ruthenium(ii) complexes were incorporated into the metal–organic framework (MOF) UiO-67 using three different synthetic strategies: premade linker synthesis, postsynthetic functionalization, and postsynthetic linker exchange. One of these complexes was of the type (N–N)3Ru2+, and three of the complexes were of the type (N–N)2(N–C)Ru+, where N–N is a bipyridine-type ligand and N–C is a cyclometalated phenylpyridine-type ligand. The resulting materials were characterized by PXRD, SC-XRD (the postsynthetic functionalization MOFs), N2 sorption, TGA-DSC, SEM, EDS, and UV-Vis spectroscopy, and were digested in base for subsequent 1H NMR analysis. The absorption profiles of the MOFs that were functionalized with cyclometalated Ru(ii) complexes extend significantly further into the visible region of the spectrum compared to the absorption profiles of the MOFs that were functionalized with the non-cyclometalated reference, (N–N)3Ru2+.
Highlights
Metal–organic frameworks (MOFs) have gained increasing interest in recent years due to the versatility these materials have shown in applications, and the potential they represent for the future development
As mentioned in the introduction, complexes 1–4 are in this work attempted incorporated into the MOF UiO-67 using three different synthetic methods: premade linker synthesis,[16,18,39,40] postsynthetic functionalization,[20,21,41,42,43,44] and postsynthetic linker exchange[23,45,46,47,48] (Fig. 1)
For comparison to the previous reports on the same materials, 1-Pre has been reported with Ru : Zr ratios of 0.015 and 0.0086 (with the use of UV-Vis spectroscopy, by digesting the MOF and subsequently recording the optical densities at 448 nm of the solution in order to quantify the concentration of the Ru(II) complex).18 1-Func has been reported with a Ru : Zr ratio as high as 0.15, in which case UiO-67 with as much as 25% bpydc was used for the synthesis.[19]
Summary
Metal–organic frameworks (MOFs) have gained increasing interest in recent years due to the versatility these materials have shown in applications, and the potential they represent for the future development. As mentioned in the introduction, complexes 1–4 are in this work attempted incorporated into the MOF UiO-67 using three different synthetic methods: premade linker synthesis,[16,18,39,40] postsynthetic functionalization,[20,21,41,42,43,44] and postsynthetic linker exchange[23,45,46,47,48] (Fig. 1).
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