Molecular Chessboard Assemblies Sorted by Site-Specific Interactions of Out-of-Plane d‑Orbitals with a Semimetal Template

We show that highly ordered two-dimensional (2D) chessboard arrays consisting of a periodic arrangement of two different molecules can be obtained by self-assembly of unsubstituted metal–phthalocyanines (metal-Pcs) on a suitable substrate serving as the template. Specifically, CuPc + MnPc and CuPc + CoPc mixtures sort into highly ordered Cu/Mn and Cu/Co chessboard arrays on the square p(10 × 10) reconstruction of bismuth on Cu(100). Such created bimolecular chessboard assemblies emerge from the site-specific interactions between the central transition-metal ions and the periodically reconstructed substrate. This work provides a conceptually new approach to induce 2D chessboard patterns in that no functionalization of the molecules is needed

Improvement of internet portal sites for Mountain villages by the comparison of the sites for rural tourism villages nationwide and overseas [Korean]

This study aims to compare internet portal sites for rural tourism, and to suggest the improved contents for homepage information on mountain villages under the Korea Forest Service. Design, interface, information source, and communication as estimation indicators were used to understand the characteristics of portal sites, and sub-items under indicators to analyse the portal sites were established. Nationwide portal sites were compared for rural tourism information. Also, German and Italian portal sites were compared as overseas cases. As a result, an internet portal site for information on mountain villages under the Korea Forest Service has to be improved as compared with other portal sites related to rural tourism. Firstly, it is necessary to modify and improve the category explaining mountain villages. Secondly, homepage for developing mountain villages has to be established and linked to potential visitors. Thirdly, portal sites for developing mountain villages subsequently have to be constructed under the site of the Korea Forest Service

The Different Faces of 4′-Pyrimidinyl-Functionalized 4,2′:6′,4′′-Terpyridines: Metal–Organic Assemblies from Solution and on Au(111) and Cu(111) Surface Platforms

A comparative investigation of crystal growth from solution and on-surface assembly <i>in vacuo</i> between copper and three 4′-(2-R-pyrimidin-5-yl)-4,2′:6′,4′′-terpyridines, with R = H (<b>1</b>), Me (<b>2</b>), or Et (<b>3</b>), is presented. In solution, ligand <b>3</b> combines with copper­(II) acetate or copper­(I) triflate in MeOH solution to give [Cu₂(OAc)₄(<b>3</b>)]_<i>n</i> or {[Cu­(<b>3</b>)­(OMe)­(MeOH)]­[CF₃SO₃]·MeOH}_<i>n</i>. In [Cu₂(OAc)₄(<b>3</b>)]_<i>n</i>, paddle-wheel {Cu₂(μ-OAc)₄} nodes direct the assembly of one-dimensional (1D) zigzag chains which pack into two-dimensional (2D) sheets. In {[Cu­(<b>3</b>)­(OMe)­(MeOH)]­[CF₃SO₃]·MeOH}_<i>n</i>, the solvent is a ligand and also generates {Cu₂(μ-OMe)₂} units which function as planar 4-connecting nodes to generate a 2D (4,4) net with ligand <b>3</b>. On Au(111) or Cu(111) surfaces <i>in vacuo</i>, no additional solvent or anions are involved in the assembly. The different substituents in <b>1</b>, <b>2</b>, or <b>3</b> allow precise molecular resolution imaging in scanning tunneling microscopy. On Au(111), <b>1</b> and <b>2</b> assemble into close-packed assemblies, while <b>3</b> forms a regular porous network. The deposition of Cu adatoms results in reorganization leading to ladder-shaped surface metal–organic motifs. These on-surface coordination assemblies are independent of the 4′-substituent in the 4,2′:6′,4′′-tpy and are reproduced on Cu(111) where Cu adatoms are available during the deposition and relaxation process at room temperature. Upon annealing at elevated temperatures, the original surface assemblies of <b>1</b> and <b>3</b> are modified and a transition from ladders into rhomboid structures is observed; for <b>2</b>, a further quasi-hexagonal nanoporous network is observed

Controlling the Dimensionality of On-Surface Coordination Polymers via Endo- or Exoligation

The formation of on-surface coordination polymers is controlled by the interplay of chemical reactivity and structure of the building blocks, as well as by the orientating role of the substrate registry. Beyond the predetermined patterns of structural assembly, the chemical reactivity of the reactants involved may provide alternative pathways in their aggregation. Organic molecules, which are transformed in a surface reaction, may be subsequently trapped via coordination of homo- or hetero­metal adatoms, which may also play a role in the molecular transformation. The amino-functionalized perylene derivative, 4,9-diamino­perylene quinone-3,10-diimine (DPDI), undergoes specific levels of dehydrogenation (−1 H₂ or −3 H₂) depending on the nature of the present adatoms (Fe, Co, Ni or Cu). In this way, the molecule is converted to an endo- or an exoligand, possessing a concave or convex arrangement of ligating atoms, which is decisive for the formation of either 1D or 2D coordination polymers

Adsorbate-Induced Modification of the Confining Barriers in a Quantum Box Array

Quantum devices depend on addressable elements, which can be modified separately and in their mutual interaction. Self-assembly at surfaces, for example, formation of a porous (metal-) organic network, provides an ideal way to manufacture arrays of identical quantum boxes, arising in this case from the confinement of the electronic (Shockley) surface state within the pores. We show that the electronic quantum box state as well as the interbox coupling can be modified locally to a varying extent by a selective choice of adsorbates, here C₆₀, interacting with the barrier. In view of the wealth of differently acting adsorbates, this approach allows for engineering quantum states in on-surface network architectures

Adsorbate-Induced Modification of the Confining Barriers in a Quantum Box Array

Quantum devices depend on addressable elements, which can be modified separately and in their mutual interaction. Self-assembly at surfaces, for example, formation of a porous (metal-) organic network, provides an ideal way to manufacture arrays of identical quantum boxes, arising in this case from the confinement of the electronic (Shockley) surface state within the pores. We show that the electronic quantum box state as well as the interbox coupling can be modified locally to a varying extent by a selective choice of adsorbates, here C₆₀, interacting with the barrier. In view of the wealth of differently acting adsorbates, this approach allows for engineering quantum states in on-surface network architectures