Hydrogen Bonding Interfaces in Fullerene•TTF Ensembles

Abstract

Novel thermodynamically stable supramolecular donor-acceptor dyads have been synthesized. In particular, we assembled successfully C(60), as an electron acceptor, with the strong electron donor TTF through a complementary guanidinium-carboxylate ion pair. Two strong and well-oriented hydrogen bonds, in combination with ionic interactions, ensure the formation of stable donor-acceptor dyads. The molecular architecture has been fine-tuned by using chemical spacers of different lengths (i.e., phenyl versus biphenyl) and functional groups (i.e., ester versus amide), thus providing meaningful incentives to differentiate between through-bond and through-space electron-transfer scenarios. In electrochemical studies, both the donor and acceptor character of the TTF and C(60) units, respectively, have been clearly identified. Steady-state and time-resolved emission studies, however, show a solvent-dependent fluorescence quenching in C(60)*TTF dyads as well as the formation of the C(60)(*)(-)*TTF(*)(+) radical ion pairs, for which we determined lifetimes that are in the range of hundred of nanoseconds to microseconds. The complex network that connects C(60) with TTF in the dyads and the flexible nature of the spacer result in through-space electron-transfer processes. This first example of electron transfer in C(60)-based dyads, connected by strong hydrogen bonds, demonstrates that this approach can add outstanding benefits to the construction of artificial photosynthetic systems that bear a closer resemblance to the natural one.

Concave Tetrathiafulvalene‐Type Donors as Supramolecular Partners for Fullerenes

“…[8] Among these, p-extended TTF derivatives [9] in which the dithioles are connected to a p-conjugated corehave been shown to exhibit improved photophysical properties. [10] Furthermore, the concave aromatic surface of 2-[9-(1,3-dithiol-2-ylidene)anthracen-10(9H)-ylidene]-1,3-dithiole (exTTF) has been successfully exploited in the molecular recognition of C 60 .…”

Exciting Supramolecular Architectures: Light‐Induced Processes and Synthetic Transformations in Noncovalent Assemblies

“…[64] Compared to their covalent counterparts, these assemblies could present advantages such as increased modularity and ease of synthesis. [65] However, as in most other all-organic devices, issues of low durability and efficiency remain difficult to solve.…”

Wasserstoffbrückenmotive in der Fullerenchemie

“…[30] Die Kombination des Polymers 15 (Schema 4) mit OPVs, die mit UP-Gruppen funktionalisiert sind, liefert vierfach wasserstoffverbrückte Heterodimere. Diese Strategie führte Kürzlich beschrieben wir in Zusammenarbeit mit Mendozas Gruppe die wasserstoffverbrückten C 60 -TTF-Ensembles 27 a-d (TTF = Tetrathiafulvalen, TBDPS = tert-Butyldiphenylsilyl), [32] in denen die Tetrathiafulvalen-Einheiten als Elektronendonoren wirken. [33] In diesen Verbindungen werden die photoaktiven Einheiten nicht nur über komplementäre Wasserstoffbrücken, sondern zusätzlich durch starke elektrostatische Wechselwirkungen von Guanidinium-Carboxylat-Ionenpaaren zusammengehalten.…”