A Metal-Directed Self-Assembled Electroactive Cage with Bis(pyrrolo)tetrathiafulvalene (BPTTF) Side Walls

A straightforward synthesis of a bis­(pyrrolo)­tetrathiafulvalene (BPTTF)-based tetratopic ligand bearing four pyridyl units is described. The first example of a TTF-based self-assembled cage has been produced from this redox-active ligand through metal-directed synthesis with a cis-coordinated square-planar Pt­(II) complex. The resulting cage corresponds to a trigonal-prismatic structure, as shown by X-ray crystallography. A UV–vis titration indicated that the electron-rich cavity can be used to incorporate one molecule of tetrafluorotetracyano-<i>p</i>-quinodimethane (TCNQF₄)

Self-Assembled Containers Based on Extended Tetrathiafulvalene

Two original self-assembled containers constituted each by six electroactive subunits are described. They are synthesized from a concave tetratopic π-extended tetrathiafulvalene ligand bearing four pyridyl units and <i>cis</i>-M­(dppf)­(OTf)₂ (M = Pd or Pt; dppf = 1,1′-bis­(diphenylphosphino)­ferrocene; OTf = trifluoromethane-sulfonate) complexes. Both fully characterized assemblies present an oblate spheroidal cavity that can incorporate one perylene molecule

A Metal-Directed Self-Assembled Electroactive Cage with Bis(pyrrolo)tetrathiafulvalene (BPTTF) Side Walls

A straightforward synthesis of a bis­(pyrrolo)­tetrathiafulvalene (BPTTF)-based tetratopic ligand bearing four pyridyl units is described. The first example of a TTF-based self-assembled cage has been produced from this redox-active ligand through metal-directed synthesis with a cis-coordinated square-planar Pt­(II) complex. The resulting cage corresponds to a trigonal-prismatic structure, as shown by X-ray crystallography. A UV–vis titration indicated that the electron-rich cavity can be used to incorporate one molecule of tetrafluorotetracyano-<i>p</i>-quinodimethane (TCNQF₄)

Self-Assembled Containers Based on Extended Tetrathiafulvalene

Two original self-assembled containers constituted each by six electroactive subunits are described. They are synthesized from a concave tetratopic π-extended tetrathiafulvalene ligand bearing four pyridyl units and <i>cis</i>-M­(dppf)­(OTf)₂ (M = Pd or Pt; dppf = 1,1′-bis­(diphenylphosphino)­ferrocene; OTf = trifluoromethane-sulfonate) complexes. Both fully characterized assemblies present an oblate spheroidal cavity that can incorporate one perylene molecule

Self-Assembled Containers Based on Extended Tetrathiafulvalene

Two original self-assembled containers constituted each by six electroactive subunits are described. They are synthesized from a concave tetratopic π-extended tetrathiafulvalene ligand bearing four pyridyl units and <i>cis</i>-M­(dppf)­(OTf)₂ (M = Pd or Pt; dppf = 1,1′-bis­(diphenylphosphino)­ferrocene; OTf = trifluoromethane-sulfonate) complexes. Both fully characterized assemblies present an oblate spheroidal cavity that can incorporate one perylene molecule

C₆₀ Recognition from Extended Tetrathiafulvalene <i>Bis</i>-acetylide Platinum(II) Complexes

The favorable spatial organization imposed by the square planar 4,4′-di­(<i>tert</i>-butyl)-2,2′-bipyridine (dbbpy) platinum­(II) complex associated with the electronic and shape complementarity of π-extended tetrathiafulvalene derivatives (exTTF) toward fullerenes is usefully exploited to construct molecular tweezers, which display good affinities for C₆₀

Supramolecular Interaction of Single-Walled Carbon Nanotubes with a Functional TTF-Based Mediator Probed by Field-Effect Transistor Devices

The supramolecular interaction between individual single-walled carbon nanotubes and a functional organic material based on tetrathiafulvalene is investigated by means of electric transport measurements in a field-effect transistor configuration as well as by NIR absorption spectroscopy. The results clearly point to a charge-transfer interaction in which the adsorbed molecule serves as an electron acceptor for the nanotubes through its pyrene units. Exposure to iodine vapors enhances this effect. The comparison with pristine carbon nanotube field-effect transistor devices demonstrates the possibility to exploit charge-transfer interactions taking place in supramolecular assemblies in which a mediator unit is used to transduce and enhance an external signal

Electron-Rich Arene–Ruthenium Metalla-architectures Incorporating Tetrapyridyl–Tetrathiafulvene Donor Moieties

A series of arene ruthenium architectures have been prepared from coordination-driven self-assembly using dinuclear <i>p</i>-cymene ruthenium acceptors and π-donating tetratopic tetrapyridyl–tetrathiafulvalene donor ligands. The synthetic strategy, based on a geometric interaction approach, leads to four electroactive metalla-assemblies, <b>1</b>–<b>4</b> (one molecular cube and three metallaplates), that were characterized by NMR, ESI-MS, X-ray diffraction, and cyclic voltammetry. Rationalization of their formation discrepancy was completed by DFT calculations supported by structural features of their constituting TTF and Ru-complex components. Metalla-architectures possessing electron-rich cores (<b>3</b>, <i>cis-</i><b>4</b>, and <i>trans</i>-<b>4</b>) interact strongly with picric acid (PA) to yield cocrystallized products, PA + metalla-assemblies, confirmed by single-crystal X-ray structure analyses