title: Nanoscale Synthesis of Two Porphyrin-Based MOFs with Gallium and Indium.
abstract: Two porphyrin-based metal-organic frameworks (MOFs) containing gallium or indium, [Ga2(OH)2(H2TCPP)]·3DMF·3H2O (Ga-PMOF) and [In2(OH)2(H2TCPP)]·3DMF·4H2O (In-PMOF) (H6TCPP = 4-tetracarboxyphenylporphyrin), were discovered using high-throughput methods. The structure was refined by the Rietveld-method starting from the structure model of Al-PMOF, [Al2(OH)2(H2TCPP)]. The new PMOFs exhibit BET surface areas between 1150 and 1400 m(2) g(-1) and are also porous toward CO2 (Ga-PMOF, 15.2 wt %; In-PMOF, 12.9 wt %). They are thermally stable in air up to 330 °C, but show limited chemical stabilities toward acids and bases. In order to achieve size control, different synthesis routes were investigated, i.e., batch synthesis at different temperatures (yield: In-PMOF-bs-th 96%, Ga-PMOF-bs-th 87%), ultrasound-assisted synthesis (yield: In-PMOF-bs-us 85%), and continuous-flow synthesis (yield: Ga-PMOF-cf 71%). By using these different methods we could control the nucleation rate and the crystal size. The crystal sizes were found to vary about 60 to 160 nm and 70 to 130 nm for Ga- and In-PMOF, respectively, which was proven by dynamic light scattering (DLS), powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) measurements.
authors.affiliation: Institute of Inorganic Chemistry, Christian-Albrechts-Universität , Max-Eyth Straße 2, D-24118 Kiel, Germany.
authors.forename: Timo
authors.initials: T
authors.lastname: Rhauderwiek
authors.affiliation: Institute of Inorganic Chemistry, Christian-Albrechts-Universität , Max-Eyth Straße 2, D-24118 Kiel, Germany.
authors.forename: Steve
authors.initials: S
authors.lastname: Waitschat
authors.affiliation: Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU) , Butenandtstraße 5-13, D-81377 Munich, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Wuttke
authors.affiliation: Department of Chemistry, University of Oslo , N-0371 Oslo, Norway.
authors.forename: Helge
authors.initials: H
authors.lastname: Reinsch
authors.affiliation: Department of Chemistry and Center for NanoScience (CeNS), University of Munich (LMU) , Butenandtstraße 5-13, D-81377 Munich, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Bein
authors.affiliation: Institute of Inorganic Chemistry, Christian-Albrechts-Universität , Max-Eyth Straße 2, D-24118 Kiel, Germany.
authors.forename: Norbert
authors.initials: N
authors.lastname: Stock