title: Insight into the Oriented Growth of Surface-Attached Metal-Organic Frameworks: Surface Functionality, Deposition Temperature, and First Layer Order.
abstract: The layer-by-layer growth of a surface-attached metal-organic framework (SURMOF), [Cu2(F4bdc)2(dabco)] (F4bdc = tetrafluorobenzene-1,4-dicarboxylate and dabco = 1,4-diazabicyclo-[2.2.2]octane), on carboxylate- and pyridine-terminated surfaces has been investigated by various surface characterization techniques. Particular attention was paid to the dependency of the crystal orientation and morphology on surface functionality, deposition temperature, and first layer order. For the fully oriented deposition of SURMOFs, not only a suitable surface chemistry but also the appropriate temperature has to be chosen. In the case of carboxylate-terminated surfaces, the expected [100] oriented [Cu2(F4bdc)2(dabco)] SURMOF can be achieved at low temperatures (5 °C). In contrast, the predicted [001] oriented SURMOF on pyridine-terminated surface was obtained only at high deposition temperatures (60 °C). Interestingly, we found that rearrangement processes in the very first layer determine the final orientation (distribution) of the growing crystals. These effects could be explained by a surprisingly hampered substitution at the apical position of the Cu2-paddle wheel units, which requires significant thermal activation, as supported by quantum-chemical calculations.
authors.affiliation: †Institute of Inorganic and Analytical Chemistry, University of Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt, Germany.|‡School of Chemistry and Materials, Guizhou Normal University, Guiyang, 550001, P. R. China.|§State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, P. R. China.
authors.forename: Jin-Liang
authors.initials: JL
authors.lastname: Zhuang
authors.affiliation: †Institute of Inorganic and Analytical Chemistry, University of Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Kind
authors.affiliation: †Institute of Inorganic and Analytical Chemistry, University of Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt, Germany.
authors.forename: Claudia M
authors.initials: CM
authors.lastname: Grytz
authors.affiliation: †Institute of Inorganic and Analytical Chemistry, University of Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt, Germany.
authors.forename: Frederic
authors.initials: F
authors.lastname: Farr
authors.affiliation: †Institute of Inorganic and Analytical Chemistry, University of Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Diefenbach
authors.affiliation: †Institute of Inorganic and Analytical Chemistry, University of Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt, Germany.
authors.forename: Samat
authors.initials: S
authors.lastname: Tussupbayev
authors.affiliation: †Institute of Inorganic and Analytical Chemistry, University of Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt, Germany.
authors.forename: Max C
authors.initials: MC
authors.lastname: Holthausen
authors.affiliation: †Institute of Inorganic and Analytical Chemistry, University of Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Terfort