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

Abstract

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-p-quinodimethane (TCNQF(4)).

A Self-Assembled Electro-Active M8L4 Cage Based on Tetrathiafulvalene Ligands

“…It has to be noted that the electro-activity can also be located on the metal complex [28–38] or on pendant units [39–43] instead of being centered on the side-walls. In the course of our studies related to the preparation of electron-rich functional metallosupramolecular discrete architectures, we recently described the first metalla-cycles [44,45] and metalla-cages [46,47] constructed from derivatives of the π-donating tetrathiafulvelene unit [ i.e. , bispyrrolo(tetrathiafulvalene) (BPTTF) or the so-called extended-tetrathiafulvalene ( ex TTF)].…”

Assembly and Stepwise Oxidation of Interpenetrated Coordination Cages Based on Phenothiazine

“…[2] In this sense, coordination cages have found application in fields such as selective anion recognition, [3] sequestering of hazardous substances, [4] drug delivery, [5] stabilization of reactive reagents and intermediates, [6] catalysis, [7] material science, and photophysical devices. [8] For the area of non-silicon photovoltaics [9] as well as for the related topic of molecular electronics, [10] discrete redoxactive (in)organic compounds show potential for technological application [11] because of their tuneable optical and electronic properties, monodispersity, and bottom-up integration into complex aggregates of defined morphology. [12] The pharmaceutically important heterocycle phenothiazine (1) [13] serves as a promising candidate for the preparation of such materials because of its beneficial redox behavior of readily undergoing a reversible one-electron oxidation to its radical cation (E 0 =+ 0.73 V in acetonitrile versus SCE) [14] with the possibility of further oxidation or disproportionation processes.…”

Tuning the size of a redox-active tetrathiafulvalene-based self-assembled ring

“…We recently depicted the preparation and properties of redox-active rings [29,35] and cages [36–40] integrating the tetrathiafulvalene (TTF) skeleton. In particular, we described self-assembled containers prepared from an electron-rich ligand precursor based on the extended-TTF framework (exTTF) [39].…”