Chiral Honeycomb Lattices of Nonplanar π-Conjugated Supramolecules with Protected Dirac and Flat Bands.

The honeycomb lattice is a fundamental two-dimensional (2D) network that gives rise to surprisingly rich electronic properties. While its expansion to 2D supramolecular assembly is conceptually appealing, its realization is not straightforward because of weak intermolecular coupling and the strong influence of a supporting substrate. Here, we show that the application of a triptycene derivative with phenazine moieties, Trip-Phz, solves this problem due to its strong intermolecular π-π pancake bonding and nonplanar geometry. Our scanning tunneling microscopy (STM) measurements demonstrate that Trip-Phz molecules self-assemble on a Ag(111) surface to form chiral and commensurate honeycomb lattices. Electronically, the network can be viewed as a hybrid of honeycomb and kagome lattices. The Dirac and flat bands predicted by a simple tight-binding model are reproduced by total density functional theory (DFT) calculations, highlighting the protection of the molecular bands from the Ag(111) substrate. The present work offers a rational route for creating chiral 2D supramolecules that can simultaneously accommodate pristine Dirac and flat bands.

Designing 2D stripe winding network through crown-ether intermediate Ullmann coupling on Cu(111) surface.

Chemical synthesis typically yields the most thermodynamically stable ordered arrangement, a principle also governing surface synthesis on an atomically level two-dimensional (2D) surface, fostering the creation of structured 2D formations. The linear connection arising from energetically stable chemical bonding precludes the generation of a 2D random network comprised of one-dimensional (1D) convoluted stripes through on-surface synthesis. Nonetheless, we underscored that on-surface synthesis possesses the capability not solely to fashion a 2D ordered linear network but also to fabricate a winding 2D network employing a precursor with a soft ring and intermediate state bonding within the Ullmann reaction. Here, on-surface synthesis was exhibited on Cu(111) employing a 2D self-assembled monolayer array of 4,4',5,5'-tetrabromodibenzo[18]crown-6 ether (BrCR) precursors. These precursors were purposefully structured, with a crown ether ring at the core and Br atoms positioned at the head and tail ends, facilitating preferential connections along the elongated axis to foster a 1D stripe configuration. We illustrate how adjustments in the quantities of the intermediate state, serving as a primary linkage, can yield a labyrinthine, convoluted winding 2D network of stripes. The progression of growth, underlying mechanisms, and electronic structures were scrutinized using an ultrahigh vacuum low-temperature scanning tunneling microscopy and spectroscopy (STM/STS) setup combined with density functional theory (DFT) calculations. This experimental evidence opens a novel functionality in leveraging on-surface synthesis for the formation of a 2D random network. This discovery holds promise as a pioneering constituent in the construction of a ring host supramolecule, augmenting its capability to ensnare guest atoms, molecules, or ions.

Band-resolved Caroli-de Gennes-Matricon states of multiple-flux-quanta vortices in a multiband superconductor.

Superconductors are of type I or II depending on whether they form an Abrikosov vortex lattice. Although bulk lead (Pb) is classified as a prototypical type-I superconductor, we show that its two-band superconductivity allows for single-flux-quantum and multiple-flux-quanta vortices in the intermediate state at millikelvin temperature. Using scanning tunneling microscopy, the winding number of individual vortices is determined from the real space wave function of its Caroli-de Gennes-Matricon bound states. This generalizes the topological index theorem put forward by Volovik for isotropic electronic states to realistic electronic structures. In addition, the bound states due to the two superconducting bands of Pb can be separately detected and the two gaps close independently inside vortices. This yields strong evidence for a low interband coupling.

Squeezed Abrikosov-Josephson Vortex in Atomic-Layer Pb Superconductors Formed on Vicinal Si(111) Substrates.

Unlike bulk counterparts, two-dimensional (2D) superconductors are sensitive to disorder. Here, we investigated superconductivity of Pb atomic layers formed on vicinal substrates to reveal how surface steps with an interval shorter than the coherence length ξ affect it. Electrical transport showed reduced critical temperature and enhanced critical magnetic field. Scanning tunneling microscopy exhibited vortices elongated along the steps, that is, Abrikosov-Josephson vortices squeezed normal to the steps due to the reduced ξ. These results demonstrate that steps work as disorder and vicinal substrates provide a unique platform to manipulate the degree of disorder on 2D superconductors.

RNA tetraplex as a primordial peptide synthesis scaffold.

Peptide bond formation at the peptidyl transferase center on the ribosome is a crucial phenomenon in life systems. In this study, we conceptually propose possible roles of the RNA tetraplex as a scaffold for two aminoacyl minihelices that enable peptide bond formation. The basic rationale of this model is that "parallel" complementary templates composed of only 10-mer nucleotides can position two amino acids in close proximity, which is conceptually and essentially similar to the situation observed in ribosomes. Using supportive experimental data, we discuss the origin and evolution of peptide bond formation in early biological systems.