RESUMEN
Integration of molecular switching units into complex electronic circuits is considered to be the next step toward the realization of novel logic and memory devices. This paper reports on an ordered 2D network of neighboring ternary switching units represented by triazatruxene (TAT) molecules organized in a honeycomb lattice on a Ag(111) surface. Using low-temperature scanning tunneling microscopy, the bonding configurations of individual TAT molecules can be controlled, realizing up to 12 distinct states per molecule. The switching between those states shows a strong bias dependence ranging from tens of millivolts to volts. The low-bias switching behavior is explored in active units consisting of two and more interacting TAT molecules that are purposefully defined (programmed) by high-bias switching within the honeycomb lattice. Within such a unit the low-bias switching can be triggered and accessed by single-point measurements on a single TAT molecule, demonstrating up to 9 and 19 distinguishable states in a dyad and a tetrad of coupled molecules, respectively. High experimental control over the desired state, owing to bias-dependent hierarchical switching and pronounced switching directionality, as well as full reversibility, make this system particularly appealing, paving the way to design complex molecule-based memory systems.
RESUMEN
We report on seven new ferrocenyl-(1, 3)- and ferrocenylethynyl-modified N,N',Nâ³-triethyltriazatruxenes (EtTATs) 4-7 as well as the dodecyl counterpart 2 of compound 1 and their use as molecular switching units when deposited on a Ag(111) surface. Such functional units may constitute a new approach to molecule-based high-density information storage and processing. Besides the five compounds 1-3, 6, and 7, where the 3-fold rotational symmetry of the triazatruxene (TAT) template is preserved, we also included 2-ethynylferrocenyl-TAT 4 and 2,2'-di(ethynylferrocenyl)-TAT 5, whose mono- and disubstitution patterns break the 3-fold symmetry of the TAT core. Voltammetric studies indicate that the ferrocenyl residues of compounds 1-7 oxidize prior to the oxidation of the TAT core. We have noted strong electrostatic effects on TAT oxidation in the 2,2',2â³-triferrocenyl-TAT derivatives 1 and 2 and the 3,3',3â³-isomer 3. The oxidized complexes feature multiple electronic excitations in the near-infrared and the visible spectra, which are assigned to dδ/δ* transitions of the ferrocenium (Fc+) moieties, as well as TAT â Fc+ charge-transfer transitions. The latter are augmented by intervalence charge-transfer contributions Fc â Fc+ in mixed-valent states, where only a part of the available ferrocenyl residues is oxidized. EtTAT was previously identified as a directional three-level switching unit when deposited on Ag(111) and constitutes a trinary-digit unit for on-surface information storage. The symmetrically trisubstituted compound 6 retains this property, albeit at somewhat reduced switching rates due to the additional interaction between the ferrocenyl residues and the Ag surface. In particular, the high directionality at low bias and the inversion of the preferred sense of the on-surface rocking motion with either a clockwise or counterclockwise switching sense, depending on the identity of the surface enantiomer, are preserved. Unsymmetrical substitution in mono- and diferrocenylated 4 and 5 alters the underlying ratchet potential in a manner such that a two-state switching between the two degenerate surface conformations of 4 or a pronounced suppression of switching (5) is observed.
RESUMEN
Careful optimization of the reaction conditions provided access to the particularly small tetraruthenium macrocycle 2Ru2Ph-Croc, which is composed out of two redox-active divinylphenylene-bridged diruthenium entities {Ru}-1,4-CH=CH-C6H4-CH=CH-{Ru} (Ru2Ph; {Ru} = Ru(CO)Cl(PiPr3)2) and two likewise redox-active and potentially non-innocent croconate linkers. According to single X-ray diffraction analysis, the central cavity of 2Ru2Ph-Croc is shielded by the bulky PiPr3 ligands, which come into close contact. Cyclic voltammetry revealed two pairs of split anodic waves in the weakly ion pairing CH2Cl2/NBu4BArF24 (BArF24 = [B{C6H3(CF3)2-3,5}4]- electrolyte, while the third and fourth waves fall together in CH2Cl2/NBu4PF6. The various oxidized forms were electrogenerated and scrutinized by IR and UV/Vis/NIR spectroscopy. This allowed us to assign the individual oxidations to the metal-organic Ru2Ph entities within 2Ru2Ph-Croc, while the croconate ligands remain largely uninvolved. The lack of specific NIR bands that could be assigned to intervalence charge transfer (IVCT) in the mono- and trications indicates that these mixed-valent species are strictly charge-localized. 2Ru2Ph-Croc is hence an exemplary case, where stepwise IR band shifts and quite sizable redox splittings between consecutive one-electron oxidations would, on first sight, point to electronic coupling, but are exclusively due to electrostatic and inductive effects. This makes 2Ru2Ph-Croc a true "pretender".
