Van der Waals-induced chromatic shifts in hydrogen-bonded two-dimensional porphyrin arrays on boron nitride
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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 redshifted due to, primarily, adsorbate-substrate van der Waals interactions. TCPP is deposited from solution on hBN and forms facetted islands with typical dimensions of 100 nm and either square or hexagonal symmetry. The molecular arrangement is stabilised 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 sub-monolayers of TCPP on hBN are redshifted 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.
- Boron nitride
- Molybdenum disulfide
- Van der Waals forces
- Atomic force microscopy
- Red shift
- boron nitride; fluorescence; molybdenum disulphide; atomic force microscopy; porphyrin, graphite; chromatic shifts.
- JACS Subjects::Physical sciences::Physics::Chemical physics, Solid-state physics
- JACS Subjects::Physical sciences::Chemistry::Physical chemistry
- Library of Congress Subject Areas::Q Science::QC Physics::QC350 Optics. Light, including spectroscopy
- Library of Congress Subject Areas::Q Science::QD Chemistry::QD450 Physical and theoretical chemistry
- Faculties, Schools and Departments::University of Nottingham, UK Campus::Faculty of Science::School of Physics and Astronomy
Data typeAtomic force microscopy images, fluorescence spectra
- Korolkov, Vladimir V.
- Svatek, Simon A.
- Summerfield, Alex
- Kerfoot, James
- Yang, Lixu
- Champness, Neil R.
- Besley, Nicholas A.
- Funders::Engineering & Physical Sciences Research Council
- The Royal Society
- The University of Nottingham
Data collection methodAtomic force micrscopes: Asylum Cypher and Asylum MFP3D. Fluorescence spectra: Horiba LABRAM confocal microscope
- University of Nottingham