Journal
ACS NANO
Volume 12, Issue 3, Pages 2677-2684Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsnano.7b08887
Keywords
hexagonal boron nitride; intercalation; tautomerization; porphyrins; STM; nc-AFM; DFT
Categories
Funding
- European Research Council Consolidator Grant NanoSurfs [615233]
- European Research Council [ERC-2015-AdG-694097]
- European Union's Programme [676580, 646259]
- H-MSCA-IF program [658070]
- DFG via a Heisenberg professorship
- Spanish Juan de la Cierva-incorporacion program [IJCI-2014-20147]
- [IT578-13]
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Intercalation of molecules into layered materials is actively researched in materials science, chemistry, and nanotechnology, holding promise for the synthesis of van der Waals heterostructures and encapsulated nanoreactors. However, the intercalation of organic molecules that exhibit physical or chemical functionality remains a key challenge to date. In this work, we present the synthesis of heterostructures consisting of porphines sandwiched between a Cu(111) substrate and an insulating hexagonal boron nitride (h-BN) monolayer. We investigated the energetics of the intercalation, as well as the influence of the capping h-BN layer on the behavior of the intercalated molecules using scanning probe microscopy and density functional theory calculations. While the self-assembly of the molecules is altered upon intercalation, we show that the intrinsic functionalities, such as switching between different porphine tautomers, are preserved. Such insulator/molecule/metal structures provide opportunities to protect organic materials from deleterious effects of atmospheric environment, can be used to control chemical reactions through spatial confinement, and give access to layered materials based on the ample availability of synthesis protocols provided by organic chemistry.
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