title: Catalyst accessibility to chemical reductants in metal-organic frameworks.
abstract: A molecular H2-evolving catalyst, [Fe2(cbdt)(CO)6] ([FeFe], cbdt = 3-carboxybenzene-1,2-dithiolate), has been attached covalently to an amino-functionalized MIL-101(Cr) through an amide bond. Chemical reduction experiments reveal that the MOF channels can be clogged by ion pairs that are formed between the oxidized reductant and the reduced catalyst. This effect is lessened in MIL-101-NH-[FeFe] with lower [FeFe] loadings. On longer timescales, it is shown that large proportions of the [FeFe] catalysts within the MOF engage in photochemical hydrogen production and the amount of produced hydrogen is proportional to the catalyst loading.
authors.affiliation: Uppsala University, Department of Chemistry - Ångström Laboratory, Box 523, 751 20 Uppsala, Sweden. sascha.ott@kemi.uu.se.
authors.forename: Souvik
authors.identifier: http://orcid.org/0000-0003-0146-5283
authors.initials: S
authors.lastname: Roy
authors.affiliation: Department of Organic Chemistry, Arrhenius Laboratory, and Berzelii Center EXSELENT, Stockholm University, 10691 Stockholm, Sweden. belen.martin.matute@su.se.
authors.forename: Vlad
authors.initials: V
authors.lastname: Pascanu
authors.affiliation: Uppsala University, Department of Chemistry - Ångström Laboratory, Box 523, 751 20 Uppsala, Sweden. sascha.ott@kemi.uu.se.
authors.forename: Sonja
authors.initials: S
authors.lastname: Pullen
authors.affiliation: Department of Organic Chemistry, Arrhenius Laboratory, and Berzelii Center EXSELENT, Stockholm University, 10691 Stockholm, Sweden. belen.martin.matute@su.se.
authors.forename: Greco
authors.identifier: http://orcid.org/0000-0002-2856-5295
authors.initials: G
authors.lastname: González Miera
authors.affiliation: Department of Organic Chemistry, Arrhenius Laboratory, and Berzelii Center EXSELENT, Stockholm University, 10691 Stockholm, Sweden. belen.martin.matute@su.se.
authors.forename: Belén
authors.initials: B
authors.lastname: Martín-Matute
authors.affiliation: Uppsala University, Department of Chemistry - Ångström Laboratory, Box 523, 751 20 Uppsala, Sweden. sascha.ott@kemi.uu.se.
authors.forename: Sascha
authors.identifier: http://orcid.org/0000-0002-1691-729X
authors.initials: S
authors.lastname: Ott