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van der Waals-induced chromatic shifts in hydrogen-bonded two-dimensional porphyrin arrays on boron nitride

Korolkov, Vladimir V.; Svatek, Simon A.; Summerfield, Alex; Kerfoot, James; Yang, Lixu; Taniguchi, Takashi; Watanabe, Kenji; Champness, Neil R.; Besley, Nicholas A.; Beton, Peter H.


Vladimir V. Korolkov

Simon A. Svatek

Alex Summerfield

James Kerfoot

Lixu Yang

Takashi Taniguchi

Kenji Watanabe

Neil R. Champness

Nicholas A. Besley


The fluorescence of a two-dimensional supramolecular network of 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin (TCPP) adsorbed on hexagonal boron nitride (hBN) is red shifted due to, primarily, adsorbate–substrate van der Waals interactions. TCPP is deposited from solution on hBN and forms faceted islands with typical dimensions of 100 nm and either square or hexagonal symmetry. The molecular arrangement is stabilized by in-plane hydrogen bonding as determined by a combination of molecular resolution atomic force microscopy performed under ambient conditions and density functional theory; a similar structure is observed on MoS2 and graphite. The fluorescence spectra of submonolayers of TCPP on hBN are red-shifted by ∼30 nm due to the distortion of the molecule arising from van der Waals interactions, in agreement with time-dependent density functional theory calculations. Fluorescence intensity variations are observed due to coherent partial reflections at the hBN interface, implying that such hybrid structures have potential in photonic applications.


Korolkov, V. V., Svatek, S. A., Summerfield, A., Kerfoot, J., Yang, L., Taniguchi, T., …Beton, P. H. (2015). van der Waals-induced chromatic shifts in hydrogen-bonded two-dimensional porphyrin arrays on boron nitride. ACS Nano, 9(10),

Journal Article Type Article
Publication Date Sep 8, 2015
Deposit Date Feb 15, 2016
Publicly Available Date Feb 15, 2016
Journal ACS Nano
Print ISSN 1936-0851
Electronic ISSN 1936-086X
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 9
Issue 10
Keywords boron nitride, fluorescence, molybdenum disulfide, atomic force microscopy, porphyrin
Public URL
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