Mechanical Bonds and Topological Effects in Radical Dimer Stabilization

While mechanical bonding stabilizes tetrathiafulvalene (TTF) radical dimers, the question arises: what role does topology play in catenanes containing TTF units? Here, we report how topology, together with mechanical bonding, in isomeric [3]- and doubly interlocked [2]catenanes controls the formation of TTF radical dimers within their structural frameworks, including a ring-in-ring complex (formed between an organoplatinum square and a {2+2} macrocyclic polyether containing two 1,5-dioxynaphthalene (DNP) and two TTF units) that is topologically isomeric with the doubly interlocked [2]catenane. The separate TTF units in the two {1+1} macrocycles (each containing also one DNP unit) of the isomeric [3]catenane exhibit slightly different redox properties compared with those in the {2+2} macrocycle present in the [2]catenane, while comparison with its topological isomer reveals substantially different redox behavior. Although the stabilities of the mixed-valence (TTF2)^(•+) dimers are similar in the two catenanes, the radical cationic (TTF^(•+))_2 dimer in the [2]catenane occurs only fleetingly compared with its prominent existence in the [3]catenane, while both dimers are absent altogether in the ring-in-ring complex. The electrochemical behavior of these three radically configurable isomers demonstrates that a fundamental relationship exists between topology and redox properties

Artificial molecular bonding in Si quantum dots tuned by double-layer gates

A quantum-state-controllable artificial molecular device, which plays an important role in such computation directions as quantum/neural computations, is fabricated from a gate-defined silicon (Si) quantum dots in a Si nanowire formed with complementary metal-oxide-semiconductor field-effect-transistor (MOSFET) technologies.The fabricated device demonstrates a state change, through low-temperature transport measurements,from an ionic-bonding state in isolated dots to a covalent-bonding state in coupled dots; transport simulation in qualitatively good agreement with the experimental result is presented for the isolated-dot case, and differential transconductance is provided so that transport for the coupled-dot case can be well understood