Electronic band structure of 1D π–d hybridized narrow-gap metal–organic polymers

Abstract

One-dimensional (1D) metal-organic (MO) nanowires are captivating from fundamental and technological perspectives due to their distinctive magnetic and electronic properties. The solvent-free synthesis of such nanomaterials on catalytic surfaces provides...

Light-Controlled Multiconfigurational Conductance Switching in a Single 1D Metal–Organic Wire

“…The model consists of a linear chain of sites with energy ϵ d , representing selected d-orbital residing on the Co atom (as will be rationalized later), coupled by an effective hopping with the nearest neighbor sites t π –d or two electrodes for edge sites Γ as shown in Figure E (details in the Supporting Information). t π– d stands for an electronic coupling between the Co-localized d-orbitals through the ligand π-orbitals, forming delocalized π–d bands observed in previous ARPES measurements . With a proper choice of model parameters ϵ d = 1.1 eV, t π –d = 0.5 eV, we recover the experimental value of the characteristic decay length λ = 1.08 nm –1 .…”

“…t π−d stands for an electronic coupling between the Co-localized d-orbitals through the ligand π-orbitals, forming delocalized π−d bands observed in previous ARPES measurements. 26 With a proper choice of model parameters ϵ d = 1.1 eV, t π−d = 0.5 eV, we recover the experimental value of the characteristic decay length λ = 1.08 nm −1 . These values ensure that the top edge of the chain band is located −0.1 eV below the Fermi energy (E F = 0).…”

“…These values ensure that the top edge of the chain band is located −0.1 eV below the Fermi energy (E F = 0). As a consequence, the proximity of the dispersive π−d valence to the Fermi level 26 leads to the high conductivity of the suspended chain. Light-Induced Conductance Switching.…”

“…We synthesize isostructural Co-QDI chains on a Au(111) surface by co-deposition of single Co atoms and 2,5-diamino-1,4-benzoquinonediimine (QDI) precursors under ultra-high-vacuum (UHV) conditions following the procedure introduced in our previous works. − This results in the formation of flexible and planar π–d coordination polymers consisting of 4-fold-coordinated Co atoms to QDI ligands (Figure A and Figure S1). The chains weakly interact with the underlying metallic Au(111) surface and can be vertically manipulated , at cryogenic temperatures (5 K) by a scanning probe, as shown in Figure A (detailed in the Supporting Information).…”

Emergence of Band Structure in a Two-Dimensional Metal–Organic Framework upon Hierarchical Self-Assembly

“…In this context, a thorough understanding of the interaction between the TM’s 3d states with the π states of the ligand is critical, defining the electronic delocalization effects within the materials and, thus, their functionality. , Specifically, π-conjugated MOFs offer exciting properties from high electrical conductivity and superconductivity to ferromagnetism . Recently, not only have the band structures of on-surface stabilized MOFs been studied, ,,− but ferromagnetic order and Mott metal–insulator transitions have also been reported . Understanding how the band structure emerges in 2D-MOFs upon coupling of the building blocks is crucial for advancing materials’ design, enabling targeted manipulation of electronic properties for tailored applications in electronics and photonics. , …”