Liquid-phase epitaxy of multicomponent layer-based porous coordination polymer thin films of [M(L)(P)0.5] type: Importance of deposition sequence on the oriented growth

Denise Zacher*, Kirill Yusenko, Angèlique Bétard, Sebastian Henke, Mariusz Molon, Tatjana Ladnorg, Osama Shekhah, Björn Schüpbach, Teresa Dea Losa Arcos, Michael Krasnopolski, Mikhail Meilikhov, Jörg Winter, Andreas Terfort, Christof Wöll, Roland A. Fischer

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

133 Scopus citations

Abstract

The progressive liquid-phase layer-by-layer (LbL) growth of anisotropic multicomponent layer-based porous coordination polymers (PCPs) of the general formula [M(L)(P)0.5] (M: Cu2+, Zn2+; L: dicarboxylate linker; P: dinitrogen pillar ligand) was investigated by using either pyridyl- or carboxyl-terminated self-assembled monolayers (SAMs) on gold substrates as templates. It was found that the deposition of smooth, highly crystalline, and oriented multilayer films of these PCPs depends on the conditions at the early growth cycles. In the case of a two-step process with an equimolar mixture of L and P, growth along the [001] direction is strongly preferred. However, employing a three-step scheme with full separation of all components allows deposition along the [100] direction on carboxyl-terminated SAMs. Interestingly, the growth of additional layers on top of previously grown oriented seeding layers proved to be insensitive to the particular growth scheme and full retention of the initial orientation, either along the [001] or [100] direction, was observed. This homo- and heteroepitaxial LbL growth allows full control over the orientation and the layer sequence, including introduction of functionalized linkers and pillars. One layer at a time: The stepwise liquid-phase layer-by-layer growth of anisotropic, multicomponent layer-based porous coordination polymers (PCPs) of the general formula [M(L)(P) 0.5] (M: Cu2+, Zn2+; L: dicarboxylate linker, P: dinitrogen pillar ligand) was investigated by using either pyridyl- or carboxyl-terminated self-assembled monolayers as templates. Highly oriented PCP multilayers were selectively grown along the [100] and [001] directions (see figure).

Original languageEnglish (US)
Pages (from-to)1448-1455
Number of pages8
JournalChemistry - A European Journal
Volume17
Issue number5
DOIs
StatePublished - Feb 1 2011

Keywords

  • metal-organic frameworks
  • orientation control
  • porous coordination polymers
  • self-assembled monolayers
  • thin films

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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