Isolated single chains of the coordination polymer [Cd(6‐MCP)2 · 2H2O]n (6‐MCP = 6‐mercaptopurinate) (see Figure and inside cover) have been prepared by ultrasonic dispersion, ultracentrifugation, and deposition on a treated mica surface, and their mechanical and electrical properties studied. The observed insulating behaviour of the chains has been confirmed using density functional theory calculations.

The direct reaction between 6-mercaptopurine (6-MP) and Cd(II) under different conditions yields either [Cd2(6-MP)4(NO3)2](NO3)2 (1) or [Cd(6-MP-)2.2H2O]n (4). Compound 1 behaves as the building block of the polymer [Cd(6-MP2-)2]n[Ca(H2O)6]n (3), by deprotonation of 6-MP ligand. In the reaction of 1 to give 3, the dinuclear compound [Cd2(6-MP)4(H2O)2](NO3)4.2H2O (2) can be isolated as an intermediate. Polymers 3 and 4 convert into each other in water via deprotonation-protonation reactions. The structures of compounds 1-3 have been determined by X-ray diffraction. Given the small differences in the arrangement shown in the crystal structures of the polymer 4 and the polyanion of 3, the stabilities and energetics of the two arrangements have been examined by DFT calculations to determine the possibility of identifying new conformations of both polymers. In addition, the two polymers have been characterized on surfaces by means of AFM. The direct reaction between 6-MP and Cd(II) and the deprotonation of the polymer 4 have proven to be useful routes for the isolation of one-dimensional systems on surfaces. The development of new strategies to characterize these types of polymers on surfaces opens the possibility to perform nanoscale studies on their properties and their potential use as nanomaterials.

Crystals of [Pt2(n‐pentylCS2)4I] show a transition from semiconductor to metallic with the increase of the temperature (conductivity is 0.3–1.4 S · cm−1 at room temperature) and a second metallic–metallic transition at 330 K, inferred by electrical conductivity measurements. X‐ray diffraction studies carried out at different temperatures (100, 298, and 350 K) confirm the presence of three different phases. The valence‐ordering of these phases is analyzed using structural, magnetic, and electrical data. Density functional theory calculations allow a further analysis of the band structure derived for each phase. Nanostructures adsorbed on an insulating surface show electrical conductivity. These results suggest that MMX‐polymer‐based nanowires could be suitable for device applications.

Coordination polymers, also known as metal-organic frameworks (MOFs), are currently in the spotlight of an intense research activity. The rich library of available metal-organic compounds allows access to a large set of molecular architectures, each designed to have specific chemical-physical properties. [1] The fact that well-organized coordination architectures can be prepared on technologically attractive surfaces, as well as the host-guest interactions typical of these systems, provides an incentive for implementing MOFs 1D and 2D nanodevices. [2][3][4] The practical applications of these new materials require controlling the spatial order of the constituent blocks at nanoscale. In many cases, the periodicity of the nanostructures derived from their spatial order can be tailored by controlling the self-assembly process via the design of the building blocks. Knowledge of the dynamic processes occurring during the self-assembly of the nanostructures and the understanding of the multiple competing interactions taking place (namely hydrogen bonds, coordination bonds, and van der Waals forces) are topics of great importance in supramolecular coordination chemistry in nanoscience.[4] 1D nanostructures (such as fibers, wires, rods, and tubes) have shown many promising and exciting properties suitable for a wide range of applications. [5,6] These nanostructures are based on coordination polymers, and present advantages over the classic metal-, oxide-or carbon-based 1D nanostructures, such as easier synthesis, higher reactivity, or the fact that their magnetic, electronic, and optical properties can be deeply modified by careful selection of the building blocks. [7][8][9] Herein, we report the development of a new method to organize coordination polymers on solid surfaces at the nanometer scale. Different preparation methods of coordination polymers have been used so far: i) deposition from solution, [2,10,11] ii) self-assembled monolayer formation, [12,13] iii) deposition by coevaporation of organic ligands [14] and metal atoms, and iv) evaporation of organic ligands and reaction with metal atoms of the surface.[15] While the first method gives rise to unclean surfaces and fibers with defects, preparation by the second method provides clean and well-ordered MOFs at the atomic level. We define fiber as a bundle of individual polymer chains. However, the coevaporation-based methods are limited by the difficulties in promoting coordination reactions on surfaces. We propose a novel and straightforward method for the preparation of lowdimensional MOFs on solid surfaces. The approach overcomes the above drawbacks and involves the deposition from vapor phase on a substrate of oligomeric species obtained by direct sublimation of a bulk MOF in vacuum. The simple idea behind this is that the different binding energies between coordination and covalent bonds will result in the smart fragmentation of the bulk polymer. Using the same hypothesis, we expect self-organization of the polymer on the host surface. The reliability o...