Jorge Echeverría

Dihydrogen contacts in alkanes are subtle but not faint

Alkane molecules are held together in the crystal state by purportedly weak homonuclear R–H···H–R dihydrogen interactions. In an apparent contradiction, the high melting points and vaporization enthalpies of polyhedranes in condensed phases require quite strong intermolecular interactions. Two questions arise: ‘How strong can a weak C–H···H–C bond be?’ and ‘How do the size and topology of the carbon skeleton affect these bonding interactions?’ A systematic computational study of intermolecular interactions in dimers of n-alkanes and polyhedranes, such as tetrahedrane, cubane, octahedrane or dodecahedrane, showed that attractive C–H···H–C interactions are stronger than usually thought. We identified factors that account for the strength of these interactions, including the tertiary nature of the carbon atoms and their low pyramidality. An alkane with a bowl shape was designed in the search for stronger dihydrogen intermolecular bonding, and a dissociation energy as high as 12 kJ mol−1 is predicted by our calculations. Intermolecular non-polar H···H interactions between polyhedrane molecules may be as attractive as classical hydrogen bonds. A theoretical study identifies the chemical and structural factors that favour such attractive interactions.

Controlled clockwise and anticlockwise rotational switching of a molecular motor

The design of artificial molecular machines often takes inspiration from macroscopic machines. However, the parallels between the two systems are often only superficial, because most molecular machines are governed by quantum processes. Previously, rotary molecular motors powered by light and chemical energy have been developed. In electrically driven motors, tunnelling electrons from the tip of a scanning tunnelling microscope have been used to drive the rotation of a simple rotor in a single direction and to move a four-wheeled molecule across a surface. Here, we show that a stand-alone molecular motor adsorbed on a gold surface can be made to rotate in a clockwise or anticlockwise direction by selective inelastic electron tunnelling through different subunits of the motor. Our motor is composed of a tripodal stator for vertical positioning, a five-arm rotor for controlled rotations, and a ruthenium atomic ball bearing connecting the static and rotational parts. The directional rotation arises from sawtooth-like rotational potentials, which are solely determined by the internal molecular structure and are independent of the surface adsorption site.

The Trigonal Prism in Coordination Chemistry

Herein we analyze the accessibility of the trigonal-prismatic geometry to metal complexes with different electron configurations, as well as the ability of several hexadentate ligands to favor that coordination polyhedron. Our study combines i) a structural database analysis of the occurrence of the prismatic geometry throughout the transition-metal series, ii) a qualitative molecular orbital analysis of the distortions expected for a trigonal-prismatic geometry, and iii) a computational study of complexes of several transition-metal ions with different hexadentate ligands. Also the tendency of specific electron configurations to present a cis bond-stretch Jahn-Teller distortion is analyzed.

Current-Driven Supramolecular Motor with In Situ Surface Chiral Directionality Switching

Surface-supported molecular motors are nanomechanical devices of particular interest in terms of future nanoscale applications. However, the molecular motors realized so far consist of covalently bonded groups that cannot be reconfigured without undergoing a chemical reaction. Here we demonstrate that a platinum-porphyrin-based supramolecularly assembled dimer supported on a Au(111) surface can be rotated with high directionality using the tunneling current of a scanning tunneling microscope (STM). Rotational direction of this molecular motor is determined solely by the surface chirality of the dimer, and most importantly, the chirality can be inverted in situ through a process involving an intradimer rearrangement. Our result opens the way for the construction of complex molecular machines on a surface to mimic at a smaller scale versatile biological supramolecular motors.

Simultaneous and coordinated rotational switching of all molecular rotors in a network

A range of artificial molecular systems has been created that can exhibit controlled linear and rotational motion. In the further development of such systems, a key step is the addition of communication between molecules in a network. Here, we show that a two-dimensional array of dipolar molecular rotors can undergo simultaneous rotational switching when applying an electric field from the tip of a scanning tunnelling microscope. Several hundred rotors made from porphyrin-based double-decker complexes can be simultaneously rotated when in a hexagonal rotor network on a Cu(111) surface by applying biases above 1 V at 80 K. The phenomenon is observed only in a hexagonal rotor network due to the degeneracy of the ground-state dipole rotational energy barrier of the system. Defects are essential to increase electric torque on the rotor network and to stabilize the switched rotor domains. At low biases and low initial rotator angles, slight reorientations of individual rotors can occur, resulting in the rotator arms pointing in different directions. Analysis reveals that the rotator arm directions are not random, but are coordinated to minimize energy via crosstalk among the rotors through dipolar interactions.

Jahn–Teller distortions of six-coordinate CuII compounds: cis or trans?

Unlike their octahedral analogues, copper(II) compounds with trigonal prismatic stereochemistry undergo an elongation of two bonds in cis positions due to a Jahn-Teller effect, a behavior that can also occur in slightly twisted octahedra.

Application of Symmetry Operation Measures in Structural Inorganic Chemistry

This paper presents an application of the recently proposed symmetry operation measures to the determination of the effective symmetry point group of coordination polyhedra in inorganic solids. Several structure types based on octahedra are found to present distinct distortion patterns each, not strictly attached to the crystallographic site symmetry. These include the (NH4)2[CuCl4], CdI2 (brucite), FeS2 (pyrite), TiO2 (rutile), CaCl2, GdFeO3, PbTiO3,LiNbO3, BiI3, CrCl3, Al2O3, and NiWO4 structures. It is shown that a similar analysis can be applied to the Bailar and tetragonal Jahn-Teller distortions of molecular transition metal complexes, as well as to solids based on tetrahedra, such as the ZnCl2, FeS, BeCl2, SiS2, and KFeS2 structure types.

Supramolecular Rotor and Translator at Work: On-Surface Movement of Single Atoms

A supramolecular nanostructure composed of four 4-acetylbiphenyl molecules and self-assembled on Au (111) was loaded with single Au adatoms and studied by scanning tunneling microscopy at low temperature. By applying voltage pulses to the supramolecular structure, the loaded Au atoms can be rotated and translated in a controlled manner. The manipulation of the gold adatoms is driven neither by mechanical interaction nor by direct electronic excitation. At the electronic resonance and driven by the tunneling current intensity, the supramolecular nanostructure performs a small amount of work of about 8 × 10(-21) J, while transporting the single Au atom from one adsorption site to the next. Using the measured average excitation time necessary to induce the movement, we determine the mechanical motive power of the device, yielding about 3 × 10(-21) W.

Seeding molecular rotators on a passivated silicon surface.

Thermally activated rotation of single molecules adsorbed on a silicon-based surface between 77 and 150 K has been successfully achieved. This remarkable phenomenon relies on a nanoporous supramolecular network, which acts as a template to seed periodic molecule rotors on the surface. Thermal activation of rotation has been demonstrated by STM experiments and confirmed by theoretical calculations.

Concurrent Symmetries: The Interplay Between Local and Global Molecular Symmetries

We analyze in this article the degree to which different groups of atoms retain local symmetries when assembled in a molecule. This study is carried out by applying continuous symmetry measures to several families of mixed sandwiches, a variety of piano-stool molecules, and several organic groups. An analysis of the local symmetry of the electron density shows that, sandwiched between two regions of different symmetry that correspond to the ligand sets, its symmetry is cylindrical at the central metal atom.