Self-Assembled Containers Based on Extended Tetrathiafulvalene

Abstract

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 cis-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 M2L2 Redox-Active Metalla-Macrocycle Based on Electron-Rich 9-(1,3-Dithiol-2-ylidene)Fluorene

“…The resulting 1 H-NMR spectrum exhibits a single set of well resolved signals as anticipated from a symmetrical discrete self-assembly ( Figure 2). H4 and H5 signals are upfield shifted compared to ligand L4Pyr due to through-space interactions between the coligand phenyl units (dppf) and the pyridyl groups, confirming coordination to the metal center [22,24]. A 1 H-NMR DOSY experiment revealed a single set of signals that confirms the formation of a unique discrete species.…”

“…In the course of our research related to the preparation of electron-rich self-assemblies [17,[19][20][21][22][23][24][25][26], we have recently demonstrated that the 9-(1,3-dithiol-2-ylidene)fluorene moiety, which is known to be readily and reversibly oxidized into a cation-radical [27,28], can be used as a building-block for the construction of electro-active self-assembled cages [29]. In line with this work, we describe herein the synthesis of an original electron-rich M 2 L 2 metalla-macrocycle constructed from the cis-blocked Pd(dppf)OTf 2 Pd(dppf)OTf2 (dppf = 1,1′-Bis(diphenylphosphino)ferrocene) acceptor and a 9-(1,3-dithiol-2-ylidene)fluorene ligand (L4Pyr) that incorporates two pyridin-4-yl units in the corresponding 3,6-positions.…”

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

“…In particular, we described self-assembled containers prepared from an electron-rich ligand precursor based on the extended-TTF framework (exTTF) [39]. …”

Synthesis and Characterization of Tetra(pyridyl)cyclo­butadiene Iron Complexes [Cp*Fe(C4py4)]– (py = 3‐pyridyl and 4‐pyridyl, Cp* = C5Me5)

“…[10] The prospect of utilizing 2 and 3 as metalloligands toward transition metal cations will be the subject of future studies.…”