Insight into the Oriented Growth of Surface-Attached Metal–Organic Frameworks: Surface Functionality, Deposition Temperature, and First Layer Order Jin-Liang Zhuang Martin Kind Claudia M. Grytz Frederic Farr Martin Diefenbach Samat Tussupbayev Max C. Holthausen Andreas Terfort 10.1021/jacs.5b03948.s001 https://acs.figshare.com/articles/journal_contribution/Insight_into_the_Oriented_Growth_of_Surface_Attached_Metal_Organic_Frameworks_Surface_Functionality_Deposition_Temperature_and_First_Layer_Order/2154340 The layer-by-layer growth of a surface-attached metal–organic framework (SURMOF), [Cu<sub>2</sub>­(F<sub>4</sub>bdc)<sub>2</sub>­(dabco)] (F<sub>4</sub>bdc = 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 [Cu<sub>2</sub>(F<sub>4</sub>bdc)<sub>2</sub>(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 Cu<sub>2</sub>-paddle wheel units, which requires significant thermal activation, as supported by quantum-chemical calculations. 2015-07-01 00:00:00 Surface Functionality surface functionality surface chemistry crystal orientation apical position layer order rearrangement processes Oriented Growth Cu surface characterization techniques F 4bdc deposition temperature Particular attention Deposition Temperature SURMOF