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.

Abstract

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.

Citation

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), https://doi.org/10.1021/acsnano.5b04443

• 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
• DOI: https://doi.org/10.1021/acsnano.5b04443
• Keywords: boron nitride, fluorescence, molybdenum disulfide, atomic force microscopy, porphyrin
• Public URL: https://nottingham-repository.worktribe.com/output/761772
• Publisher URL: http://pubs.acs.org/doi/10.1021/acsnano.5b04443