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Instruments / Technical Area	Publication Details	Published
	Experimental demonstration of a spectral fingerprint for the saddle and inverted conformations of porphyrins on copper Eleanor S. Frampton , Ailish Gray , Michael Clarke , Matthew Edmondson , Jonathan Bradford , David A. Duncan , Alex Saywell The Journal Of Physical Chemistry Letters DOI: 10.1021/acs.jpclett.5c00498 Open Access Show Abstract ▼ Abstract: Combined density functional theory (DFT) and X-ray standing wave (XSW) studies have previously provided evidence for the preferential adoption of an inverted conformation of 2H-TPP on Cu(111) in contrast to the saddle conformation usually favored by porphyrin molecules adsorbed on metals. We experimentally demonstrate, via X-ray photoelectron spectroscopy (XPS) analysis, that the binding energies of the aminic and iminic nitrogen species provide a spectral fingerprint for both inverted and saddle conformations, as predicted by DFT studies. Our complementary scanning tunneling microscopy (STM) characterization also reveals conversion from the saddle to inverted conformation at an elevated temperature for an analogous porphyrin species (Br2TPP).	May 2025
I09-Surface and Interface Structural Analysis	On-surface synthesis of Ni-porphyrin-doped graphene nanoribbons Matthew Edmondson , Michael Clarke , James N. O’shea , Qiang Chen , Harry L. Anderson , Alex Saywell Acs Nano DOI: 10.1021/acsnano.4c09188 Diamond Proposal Number(s): [33305, 33757] Open Access Show Abstract ▼ Abstract: On-surface synthesis of functional molecular structures provides a route to the fabrication of materials tailored to exhibit bespoke catalytic, (opto)electronic, and magnetic properties. The fabrication of graphene nanoribbons via on-surface synthesis, where reactive precursor molecules are combined to form extended polymeric structures, provides quasi-1D graphitic wires that can be doped by tuning the properties/composition of the precursor molecules. Here, we combine the atomic precision of solution-phase synthetic chemistry with on-surface protocols to enable reaction steps that cannot yet be achieved in solution. Our focus of this work is the inclusion of porphyrin species within graphene nanoribbons to create porphyrin-fused graphene nanoribbons. A combination of scanning tunneling microscopy and photoelectron spectroscopy techniques is used to characterize a porphyrin-fused graphene nanoribbon formed on-surface from a linear polymer consisting of regularly spaced Ni-porphyrin units linked by sections of aryl rings which fuse together during the reaction to form graphitic regions between neighboring Ni-porphyrin units.	Nov 2024
B07-B1-Versatile Soft X-ray beamline: High Throughput ES1 I09-Surface and Interface Structural Analysis	Adsorption structure of iron phthalocyanine and titanyl phthalocyanine on Cu(111) Matthew A. Stoodley , Benedikt P. Klein , Michael Clarke , Leon B. S. Williams , Luke A. Rochford , Pilar Ferrer , David C. Grinter , Alex Saywell , David A. Duncan Inorganica Chimica Acta 21 DOI: 10.1016/j.ica.2023.121679 Diamond Proposal Number(s): [30875, 31165, 29418] Open Access Show Abstract ▼ Abstract: The adsorption structure of iron phthalocyanine (FePc) and titanyl phthalocyanine (TiOPc) was studied by a combination of near edge X-ray absorption fine structure (NEXAFS) spectroscopy and normal incidence X-ray standing waves (NIXSW) technique. The FePc results demonstrate that the molecule adsorbs with the Fe metal centre at an adsorption height of 2.44 ± 0.09 Å, its macrocycle plane mostly parallel with the underlying surface and a single adsorption configuration. However, a small distortion of the isoindole groups, with respect to one another, is required to rationalise the results. The TiOPc results similarly indicate that the macrocycle plane is mostly parallel with the underlying surface up to thick multilayer films, yet, in the monolayer regime, the molecule must adsorb in multiple configurations. These configurations are nominally assigned to a mixture of adsorption configurations with some Ti=O bonds pointing towards the surface, and some pointing away. We determine that, in both configurations, the Ti metal centre sits at a similar adsorption height above the surface of 3.00 ± 0.20 Å.	Jul 2023

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