The Fe(II) spin crossover complex [Fe{H B(pz) } (bipy)] (pz = pyrazol-1-yl, bipy = 2,2'-bipyridine) can be locked in a largely low-spin-state configuration over a temperature range that includes temperatures well above the thermal spin crossover temperature of 160 K. This locking of the spin state is achieved for nanometer thin films of this complex in two distinct ways: through substrate interactions with dielectric substrates such as SiO and Al O , or in powder samples by mixing with the strongly dipolar zwitterionic p-benzoquinonemonoimine C H (-⋯ NH ) (-⋯ O) . Remarkably, it is found in both cases that incident X-ray fluences then restore the [Fe{H B(pz) } (bipy)] moiety to an electronic state characteristic of the high spin state at temperatures of 200 K to above room temperature; that is, well above the spin crossover transition temperature for the pristine powder, and well above the temperatures characteristic of light- or X-ray-induced excited-spin-state trapping. Heating slightly above room temperature allows the initial locked state to be restored. These findings, supported by theory, show how the spin crossover transition can be manipulated reversibly around room temperature by appropriate design of the electrostatic and chemical environment.

A strategy to synthesize a 2D graphenic but ternary monolayer containing atoms of carbon, nitrogen, and boron, h-BCN, is presented. The synthesis utilizes bis-BN cyclohexane, B 2 N 2 C 2 H 12 , as a precursor molecule and relies on thermally induced dehydrogenation of the precursor molecules and the formation of an epitaxial monolayer on Ir(111) through covalent bond formation. The lattice mismatch between the film and substrate causes a strain-driven periodic buckling of the film. The structure of the film and its corrugated morphology is discussed based on comprehensive data from molecular-resolved scanning tunneling microscopy imaging, X-ray photoelectron spectroscopy, low-energy electron diffraction, and density functional theory. First-principles calculations further predict a direct electronic band gap that is intermediate between gapless graphene and insulating h-BN.

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Atomically precise graphene nanoribbons (GNRs) of two types, chevron GNRs and N = 7 straight armchair GNRs (7-AGNRs), have been synthesized through a direct contact transfer (DCT) of molecular precursors on Au(111) and gradual annealing. This method provides an alternative to the conventional approach for the deposition of molecules on surfaces by sublimation and simplifies preparation of dense monolayer films of GNRs. The DCT method allows deposition of molecules on a surface in their original state and then studying their gradual transformation to polymers to GNRs by scanning tunneling microscopy (STM) upon annealing. We performed STM characterization of the precursors of chevron GNRs and 7-AGNRs, and demonstrate that the assemblies of the intermediates of the GNR synthesis are stabilized by π-π interactions. This conclusion was supported by the density functional theory calculations. The resulting monolayer films of GNRs have sufficient coverage and density of nanoribbons for ex situ characterization by spectroscopic methods, such as Raman spectroscopy, and may prove useful for the future GNR device studies.