Van der Waals forces are among the weakest, yet most decisive interactions governing condensation and aggregation processes and the phase behaviour of atomic and molecular matter. Understanding the resulting structural motifs and patterns has become increasingly important in studies of the nanoscale regime. Here we measure the paradigmatic van der Waals interactions represented by the noble gas atom pairs Ar–Xe, Kr–Xe and Xe–Xe with a Xe-functionalized tip of an atomic force microscope at low temperature. Individual rare gas atoms were fixed at node sites of a surface-confined two-dimensional metal–organic framework. We found that the magnitude of the measured force increased with the atomic radius, yet detailed simulation by density functional theory revealed that the adsorption induced charge redistribution strengthened the van der Waals forces by a factor of up to two, thus demonstrating the limits of a purely atomic description of the interaction in these representative systems.
Realization of long-range magnetic order in surface-supported two-dimensional systems has been challenging, mainly due to the competition between fundamental magnetic interactions as the short-range Kondo effect and spin-stabilizing magnetic exchange interactions. Spin-bearing molecules on conducting substrates represent a rich platform to investigate the interplay of these fundamental magnetic interactions. Here we demonstrate the direct observation of long-range ferrimagnetic order emerging in a two-dimensional supramolecular Kondo lattice. The lattice consists of paramagnetic hexadeca-fluorinated iron phthalocyanine (FeFPc) and manganese phthalocyanine (MnPc) molecules co-assembled into a checkerboard pattern on single-crystalline Au(111) substrates. Remarkably, the remanent magnetic moments are oriented in the out-of-plane direction with significant contribution from orbital moments. First-principles calculations reveal that the FeFPc-MnPc antiferromagnetic nearest-neighbour coupling is mediated by the Ruderman–Kittel–Kasuya–Yosida exchange interaction via the Au substrate electronic states. Our findings suggest the use of molecular frameworks to engineer novel low-dimensional magnetically ordered materials and their application in molecular quantum devices.
The blends based on poly(lactic acid), (PLA) and polyacrylates (1:1 weight ratio) have been prepared by photopolymerization of three different multifunctional acrylate monomers (pentaerythritol triacrylate, pentaerythritol tetraacrylate and dipentaerythritol pentaacrylate) in matrix of linear PLA. The structure of these systems has been studied by Atomic Force Microscopy (AFM), Differential Scanning Calorimetry (DSC) and X-ray Diffraction (XRD). It was found that the blends are highly crosslinked, rough, heterogeneous and some of them – semicrystalline. The effect of UV-irradiation on surface morphology of obtained mixtures was studied. The viscometry has been applied for measurements of changes of PLA molecular weight resulting of photodegradation. It was shown that blends are much more photostable than pure PLA.
24 June 2014 in Journal of the American Chemical Society
The Shockley surface state on Cu(111) reacts sensitively to the perturbation by molecular adsorbates on the surface. In the porous structure of a metal-coordinated molecular network on Cu(111), the surface state is confined to a series of discrete states. Energy and momentum of eigenstates in the pores are related to both the energy dispersion of the free surface state and the geometric and energetic details of the confining barrier formed by the molecular network. The penetration of the confined state into the barrier is found to be sensitive to the constituting architectural elements.