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

Abstract

SummaryThe synthesis of a new Pd coordination-driven self-assembled ring M6L3 constructed from a concave tetrapyridyl π-extended tetrathiafulvalene ligand (exTTF) is described. The same ligand is also able to self-assemble in a M4L2 mode as previously described. Herein, we demonstrate that the bulkiness of the ancillary groups in the Pd complex allows for modulating the size and the shape of the resulting discrete self-assembly, which therefore incorporate two (M4L2) or three (M6L3) electroactive exTTF sidewalls.

Selective C70 encapsulation by a robust octameric nanospheroid held together by 48 cooperative hydrogen bonds

“…An established pathway to spherical structures involves the careful design and synthesis (often multi-stage) of an organic ligand with precisely spaced functional groups. Nanocapsules can be produced via reversible covalent bonds such as disulfide1314, boronic esters1516 and imines171819202122 or supramolecular interactions such as coordinative bonds23242526 and hydrogen bonding2728293031, the last being exemplified in the present work.…”

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.…”

Cages vs. Prisms: Controlling the Formation of Metallosupramolecular Architectures with Ligand Side‐Chains

“…Prismatic structures are not the only possible outcome for reactions of tetratopic N‐donor ligands with cis ‐blocked Pd II or Pt II complexes. If the ligand can adopt a concave geometry, it is possible to form M 4 L 2 ‐type structures . These complexes do not qualify as prisms, even though they can show a barrel‐like geometry.…”