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

scanbot

Jules has put in the hard yards implementing nanonisTCP as a python module, and leveraged that to create scanbot, a tool for automating the tasks of preparing a good imaging & spectroscopy probe, as well as a suite of functions for performing nuanced, drift-corrected measurements over very long timescales.

See the below example of systematically grid scanning 100x100nm images to concatenate a comprehensive view of the surface. Right is the upper left red corner, where self-assembled molecular islands are visible.

Ceddia et al., (2024). Scanbot: An STM Automation Bot. Journal of Open Source Software, 9(99), 6028, https://doi.org/10.21105/joss.06028

Mott transition in kagome MOF

Ben & Bernard’s work on the two-dimensional kagome metal-organic framework is out this week (26 April 2024) in Nature Comms.

It was fantastic to see interesting electronic properties emerge at relatively big energy scales for this sort of work, when we were finally able to get the 2d kagome MOF composed of Cu adatoms & DCA molecules, to self-assemble on insulating hexagonal boron nitride (hBN) supported by a Cu111 metallic substrate.

We teamed up with Ben Powell’s group at UQ for the many-body expertise required to understand the tunnel junction and substrate work function dependent modulations of the electronic gap in the language of Mott physics.

Lowe, B., Field, B., Hellerstedt, J. et al. Local gate control of Mott metal-insulator transition in a 2D metal-organic framework. Nat Commun 15, 3559 (2024). https://doi.org/10.1038/s41467-024-47766-8

Striped Phase

While pursuing metal-organic frameworks, we stumbled on something unexpected but experimentally robust back in June of 2019. DCA molecules and Au adatoms on Ag111 form DCA-Au-DCA units, and the cyano groups aren’t involved as you’d intuitively expect.

It took some heroic effort and creative thinking from Adam & the team in Prague to “just run this one through the computer real quick”, but nonetheless we’re pleased to have this explanation of the selective C-H scisson necessary to justify the observed end products.

Lowe, B., et. al. (2022). Selective Activation of Aromatic C–H Bonds Catalyzed by Single Gold Atoms at Room Temperature. J. Am. Chem. Soc. https://doi.org/10.1021/jacs.2c10154

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

Counting Molecules

9-azidophenanthrene produces a rich manifold of products when deposited on Ag(111).

The images we took for this study inspired this work to develop a lightweight script to count the molecules we observed, and categorize them.

Our personal journey of computer vision rediscovery led us to Zernike moments, a rotationally invariant basis set that solves the problem of identifying the same molecules with relative rotations, in an image.

We put some effort into making this module user-friendly, the example scripts offer a reasonable template to apply to any old SXM file you might want to histogram.

Hellerstedt, J., et. al. (2022). Counting Molecules: Python based scheme for automated enumeration and categorization of molecules in scanning tunneling microscopy images. Software Impacts https://doi.org/10.1016/j.simpa.2022.100301

github repo

2021 AIP summer meeting

The AIP summer meeting was a hybrid event this year 6-9 Dec. ’21 with the border restrictions still in place preventing us from travelling to Brisbane.

Iolanda kindly invited me to talk about Marina’s MgPc hybridization work as well as new results of orbital tomography performed at the Australian Synchrotron (in preparation).

Ben Lowe contributed a talk to the scanning probe microscopy focus session, with an update on how we’re closing in on understanding the mechanism of formation for some unusual metal-organic products identified with ncAFM measurements.

Thanks also to Peggy Schönherr, Peggy Zhang, Peter Jacobson, and Iolanda DiBernardo for contributing talks to the SPM focus session.

Bernard Field talked about how he’s pushing forward how we can rationalise our observations of self-assembled MOF structures, stemming from our recently published experimental results that Agustin talked about in the MOF focus session.

Kagome metal-organic framework

Dhaneesh Kumar has extensively studied the on-surface properties of the DCA molecule for his PhD. After getting a good handle on just the DCA on Ag111, we started sprinkling some Cu atoms into the mix.

We observed the same honeycomb kagome structure that forms on Cu111– as seen in an ncAFM force volume shown in the right image. It has also been synthesized on graphene.

The key difference we observed on Ag111 was the Kondo effect, an STS peak at Fermi we tracked up to 150 K!

The consistent spatial distribution of this feature across the MOF was another key observation.

ncAFM force volume of DCA (structure superimposed upper right) self-assembly on Cu111 surface. dZ denotes lift of sensor away from surface for each frame.

Bernard put in the hard yards with DFT/ +U calculations in conjunction with mean-field Hubbard modelling to rationalise our experimental observations as strong Coulomb interactions between electrons within the kagome MOF.

STS maps
dI/dV STS mapping at biases indicated upper left
DCA Cu Kagome schematic
Schematic of Kondo screened spin moments within the MOF. Blender by Dhaneesh

We’re excited by the possibilities for solid-state architectures to offer further access & control of these intriguing quantum states.

Kumar, D., et. al. (2021). Manifestation of Strongly Correlated Electrons in a 2D Kagome Metal–Organic Framework. Advanced Functional Materials, 2106474. https://doi.org/10.1002/adfm.202106474

ArXiv link
FLEET blog

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

March Meeting 2021

I’m presenting Marina’s work on MgPc hybridization in Focus Session B56 on Monday 15/3 at 1318 (CDT).

Link to my presentation slides.

Other talks from our group:
Dhaneesh Kumar, “Kondo Effect in a 2D Kagome Metal-organic Framework on a Metal” (15/3 1218 CDT)

Bernard Field, “Electronic and Magnetic Structure of Metal-Organic Lattices on Substrates” (15/3 1242 CDT)

Ben Lowe, “Atomic-Scale Evidence of Surface-Catalyzed Gold-Carbon Covalent Bonding” (18/3 1206 CDT)