title: Controlled nucleation and growth of pillared paddlewheel framework nanostacks onto chemically modified surfaces.
abstract: The nucleation and growth of metal-organic frameworks onto functional surfaces stands to facilitate the utility of these supramolecular crystalline materials across a wide range of applications. Here, we demonstrate the solvothermal nucleation and growth of a pillared paddlewheel porphyrin framework 5 (PPF-5) onto semiconductor surfaces modified with carboxylic acids. Using versatile diazonium and catechol chemistries to modify silicon and titania surface chemistries, we show that solvothermally grown PPF-5 selectively nucleates and grows as stacked crystalline sheets with preferential (001), (111), and (110) crystallographic orientations. Furthermore, variations in the synthesis temperature produce modified stack morphologies that correlate with changes in the surface-nucleated PPF-5 photoluminescence.
authors.affiliation: Sandia National Laboratories , Albuquerque, New Mexico 87185, United States.
authors.forename: Dara
authors.initials: D
authors.lastname: Van Gough
authors.forename: Timothy N
authors.initials: TN
authors.lastname: Lambert
authors.forename: David R
authors.initials: DR
authors.lastname: Wheeler
authors.forename: Mark A
authors.initials: MA
authors.lastname: Rodriguez
authors.forename: Michael T
authors.initials: MT
authors.lastname: Brumbach
authors.forename: Mark D
authors.initials: MD
authors.lastname: Allendorf
authors.forename: Erik D
authors.initials: ED
authors.lastname: Spoerke