Chirality in 2D Metal-Organic Framework

Another installment in the annals of the bullying of the Shockley surface state, this time the trick isn’t exotic adatoms or massive molecular weight, just a 120° tilt of hexaazatriphenylene (HAT) ligands that converts an achiral lattice into a pair of enantiomeric 2-D metal–organic frameworks. The result: chirality-imposed scattering potentials that lift degeneracies and open ΔE ≈ 80 meV gaps in the Ag(111) two-dimensional electron gas while leaving the global periodicity intact.

Key take-aways

  • Structural chirality prints straight onto k-space
    nc-AFM resolves two co-existing enantiomers, pinwheel (PW) and “Y” phases, built from Cu–N coordination and an approximately 6° molecular cant relative to the substrate plane. STS maps acquired at 5K reveal the surface-state band dispersion reconstructed by these potentials: back-folded bands, avoided crossings and a pronounced energy gap at the new Brillouin-zone boundary.
  • No new chemistry, only symmetry
    The gaps appear without changing the molecular building blocks; tilting the HAT plane breaks mirror symmetry and generates the required chiral scattering.
  • Two tools, one story
    Electronic plane-wave expansion (EPWE) calculations feed the experimental topographies into a scattering potential and reproduce the experimental dI/dV linecuts almost quantitatively. DFT overlays the intrinsic MOF bands, showing that substrate hybridisation broadens the pyrazine and shallow-pore states but leaves the chirality-imposed gap untouched.

Why it matters

Tuning interface electronic properties usually means adding heavy metals, strain or strong correlations. Here the knob is symmetry engineering at the level of a single torsion angle, giving a gap that survives room-temperature disorder and is addressable by STM patterning. For anyone chasing chiral superconductivity, topological Bloch modes or valley-splitting without magnetic fields, that’s a tantalising new dial to turn, keeping in mind that the circumstances of its rotation are a bit rarefied, and the organics that underpin it aren’t typically associated the materials systems that carry those clusters of keywords.

Acknowledgments

The project has long roots: Sebastian synthesised the first and final HAT batch in-house back in 2019, but that’s a lot of molecules when you image them by the hundred. The low-temperature data were collected during Julian’s PhD tenure, during the LHe heyday when the coarse motor piezos had been beated back into shape (thanks Ben). Bernard, now a postdoc at LBNL, nevertheless kept pushing the modelling forward to get this across the finish line.

Tuning Interface Electronic Properties via Chiral Two-Dimensional Metal-Organic Frameworks (2025). Small Structures. https://doi.org/10.1002/sstr.202500422

MgPc ARPES

We had the opportunity to use the new toroidal analyzer at the Australian synchrotron to do ARPES of self-assembled monolayers of MgPc on Ag100.

Careful simultaneous fitting of different high-symmetry EDC measurements, in concert with the structural understanding gleaned from ncAFM & LEED characterization, allowed us to tease out a feature with bandwidth 20 meV, which was surprising to us given that we did the ARPES at room temperature.

Bruce Cowie & Anton Tadich made it possible to break into this kind of measurement with just a week of time; Anton has been instrumental in supporting the analysis that was required to get this one across the finish line.

Hellerstedt, J., et. al. (2022). Direct observation of narrow electronic energy band formation in 2D molecular self-assembly. Nanoscale Advances https://doi.org/10.1039/D2NA00385F

Concerted Proton Transfer

We stumbled on a very curious observation in the summer of 2018 with DABQDI molecules provided by Olivier Siri‘s team.

ncAFM image of 26 molecule chain. Unfiltered data.
STM chain manipulation
Repeated manipulations with STM tip are capable of dragging a DABQDI chain around the Au111 surface.

While evaluating its experimental suitability for 1d coordination with metals, which has already proven to be fruitful, we noticed the molecules forming chain-like structures even before we introduced metal adatoms.

The low temperature SPM results are sublime: unusual mechanical stability, distinctive intermolecular bonding, and near-Fermi electronic states lighting up at the ends of the chains.

It took an extraordinary cast of theorists hailing from Pavel’s core group, FZU, Charles, Reykjavik, & Madrid Universities to unravel this puzzle and explain these observations as concerted proton tunneling causing a delocalization of electrons.

“Significance of Nuclear Quantum Effects in Hydrogen Bonded Molecular Chains”, ACS Nano, 2021. 10.1021/acsnano.1c02572

ArXiv link

MgPc-MgPc Hybridization

ncAFM atomic registration of MgPc molecule on Ag100
nc-AFM atomic registration of single MgPc molecule on Ag100 (surface atoms top and bottom stripes)

Marina Castelli studied the phthalocyanine containing magnesium (MgPc) via 5K scanned probe microscopies extensively during her PhD.

‘Routine’ STM characterisation showed that the molecules were interacting with one another on the Ag100 surface.

ncAFM showed identical contrast for all molecules, pointing to an electronic origin to the observed changes in appearance.

Our key observation was to track the shape of the occupied LUMO for different pairwise distances, an electronic feature that otherwise remained isoenergetic.

With multipass dI/dV mapping we were able to quantitatively track from four- to two-fold rotational symmetry, over distances out to ~3 nm. We found the spatial extent of this attractive hybridization quite surprising.

“Long-Range Surface-Assisted Molecule-Molecule Hybridization”, Small (2021). 10.1002/smll.202005974

FLEET PR
ArXiv link

STM image of MgPc molecules on Ag100 surface
STM image showing the neighbor-induced symmetry reduction