Understanding the affinity of bis-exTTF macrocyclic receptors towards fullerene recognition

A new series of fullerene receptors based on exTTF macrocycles with alkyl ether chains of increasing length is reported. The novel macrocyclic receptors are able to favourably interact with fullerene C60 through a synergistic combination of π–π, CH⋯π and n⋯π noncovalent interactions. We identify that the highest affinity towards C60 recognition is achieved for the host with the tightest fit; that is, the smallest receptor with a cavity large enough to host the buckyball inside (log Ka = 5.2 in chlorobenzene at 298 K). However, besides this expected observation, theoretical calculations evidence that the most stable self-assembling configuration corresponds for all the receptors to an outsid…

Determination of association constants towards carbon nanotubes† †Electronic supplementary information (ESI) available: Synthetic details and characterization, thorough description of the method to determine the concentration of the relevant species, full set of TGA data, isotherms not shown in the main text, table with all the association constants, computational details and theoretical calibration of the nanotube length. See DOI: 10.1039/c5sc02916c

We describe a simple procedure for the determination of association constants between soluble molecules and insoluble and heterogeneous carbon nanotube samples.

Controlled Self-Assembly of Electron Donor Nanotubes

We employ a combination of urea-urea hydrogen bonds and pi-pi stacking interactions to obtain soluble self-assembled nanotubes decorated with electron-donor TTF derivatives on the periphery. We have investigated the structure and stability of the nanotubes with a combination of experiments and high-level DFT calculations. We also demonstrate that the association process can be controlled by changes in the hydrogen-bonding ability of the solvent and electrochemically.

Concave Tetrathiafulvalene-Type Donors as Supramolecular Partners for Fullerenes

The cap fits! A new class of concave π-extended tetrathiafulvalene (TTF) derivatives, truxene-TTFs, were prepared and characterized, and their self-assembly with fullerenes was investigated (see picture). Truxene-TTFs represent the first example of TTF-related electron donors that serve, without chemical modification, as monotopic receptors for fullerenes in solution. (Chemical Equation Presented). © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.

Weighting non-covalent forces in the molecular recognition of C60. Relevance of concave–convex complementarity

The relative contributions of several weak intermolecular forces to the overall stability of the complexes formed between structurally related receptors and [60]fullerene are compared, revealing a discernible contribution from concave–convex complementarity. Viruela Martin, Pedro Manuel, Pedro.M.Viruela@uv.es ; Viruela Martin, Rafael, Rafael.Viruela@uv.es ; Orti Guillen, Enrique, Enrique.Orti@uv.es

Titelbild: Electron Transfer in a Supramolecular Associate of a Fullerene Fragment (Angew. Chem. 8/2014)

Bowl-shape electron donors with absorptions in the visible range of the solar spectrum and their supramolecular assemblies with C 60

We describe the synthesis, electronic, optical and photophysical properties of a family of three electron-donor bowl-shaped organic molecules that absorb light in the whole range of the visible spectrum (up to 800 nm in one case), and associate C60 in solution with binding constants in the range of 104–102 M−1 as measured from both UV-vis and fluorescence titrations in several solvents. These molecules are π-extended derivatives of tetrathiafulvalene, based on a truxene core to which two or three units of dithiole are covalently attached. The inclusion of the bulky dithiole groups is responsible for their bowl-shape geometry, which allows them to associate with C60, and their electron-donor…

Cover Picture: Electron Transfer in a Supramolecular Associate of a Fullerene Fragment (Angew. Chem. Int. Ed. 8/2014)

Buckyballs

Buckyballs represent a new and fascinating molecular allotropic form of carbon that has received a lot of attention by the chemical community during the last two decades. The unabating interest on this singular family of highly strained carbon spheres has allowed the establishing of the fundamental chemical reactivity of these carbon cages and, therefore, a huge variety of fullerene derivatives involving [60] and [70]fullerenes, higher fullerenes, and endohedral fullerenes have been prepared. Much less is known, however, of the chemistry of the uncommon non-IPR fullerenes which currently represent a scientific curiosity and which could pave the way to a range of new fullerenes. In this revi…

Understanding Noncovalent Interactions of Small Molecules with Carbon Nanotubes

We combine experimental methods, density functional theory (DFT) calculations, and molecular dynamics (MD) simulations in the quantitative analysis of noncovalent interactions between (6,5)-enriched single-walled carbon nanotubes (SWNTs), as hosts, and a set of pyrene derivatives with different electronic properties and surface areas, as guests. The experiments and calculations were carried out in two solvents with markedly different polarities, namely 1,1',2,2'-tetrachloroethane (TCE) and N,N-dimethylformamide (DMF). Our results show that dispersion forces govern the supramolecular association of small molecules with (6,5)-SWNTs, with negligible contributions from ground-state charge-trans…

Biomimetic oxidation of pyrene and related aromatic hydrocarbons. Unexpected electron accepting abilities of pyrenequinones

We present a mild catalytic method to oxidize PAHs and, in particular, pyrene. The pyrenediones are much better electron acceptors than benzoquinone in the gas phase and present similar accepting abilities in solution.

Complexation and Electronic Communication between Corannulene-Based Buckybowls and a Curved Truxene-TTF Donor

Abstract: The association behavior of an electron-donating, bowl-shaped, truxene-based tetrathiafulvalene (truxTTF) with two corannulene-based fullerene fragments, C32H12 and C38H14, is investigated in several solvents. Formation of 1:1 complexes is followed by absorption titrations and complemented by density functional theory (DFT) calculations. The binding constants are in the range logKa=2.9–3.5. DFT calculations reveal that the most stable arrangement is the conformation in which the 1,3-dithiole ring of truxTTF is placed inside the concave cavity of the corannulene derivative. This arrangement is confirmed experimentally by NMR measurements, and implies that a combination of p–p and C…

Diskrete supramolekulare Donor-Akzeptor-Komplexe

A bis-exTTF macrocyclic receptor that associates C60 with micromolar affinity

An exTTF-based macrocyclic receptor that associates C(60) with a binding constant10(6) M(-1) in chlorobenzene at room temperature is described. This represents an improvement of 3 orders of magnitude with respect to the previous examples of exTTF-based receptors and one of the highest binding constants toward C(60) reported to date.

Exploiting multivalent nanoparticles for the supramolecular functionalization of graphene with a nonplanar recognition motif.

The supramolecular modification of planar graphene with the geometri- cally mismatched, curved 9,10-di(1,3-dithiole-2-ylidene)-9,10-dihydroanthracene (exTTF) molecule is demonstrated. The exTTF-graphene interaction is governed by p-p and CH-p interactions, with a negligible contribution from charge transfer. We amplified these weak forces through multivalent gold nanoparticles. Our re- sults show that planarity is not a prerequisite for recognition motifs for graphene.

Electron transfer in a supramolecular associate of a fullerene fragment

Herein, we investigate the association of a fullerene fragment, hemifullerene C30H12, with an electron-donating bowl-shaped tetrathiafulvalene derivative (truxTTF). UV/Vis titrations and DFT calculations support formation of the supramolecular complex, for which an association constant of log Ka = 3.6±0.3 in CHCl3 at room temperature is calculated. Remarkably, electron transfer from truxTTF to C30H12 to form the fully charge-separated species takes place upon irradiation of the associate with light, constituting the first example in which a fullerene fragment mimics the electron-accepting behavior of fullerenes within a supramolecular complex.

Determination of association constants towards carbon nanotubes

Single-walled carbon nanotubes (SWNTs) are one of the most promising nanomaterials and their supramolecular chemistry has attracted a lot of attention. However, despite well over a decade of research, there is no standard method for the quantification of their noncovalent chemistry in solution/suspension. Here, we describe a simple procedure for the determination of association constants (Ka) between soluble molecules and insoluble and heterogeneous carbon nanotube samples. To test the scope of the method, we report binding constants between five different hosts and two types of SWNTs in four solvents. We have determined numeric values of Ka in the range of 1–104 M−1. Solvent effects as wel…

Discrete supramolecular donor-acceptor complexes

The renewed interest in noncovalently associating electroactive molecules arises in part from the quest for new organic materials that convert solar energy into electrical/ chemical equivalents. In this context, the formation of charge-separated states is a key prerequisite. Charge-transfer events triggered by light have been studied in supramolecular donor–acceptor systems based on hydrogen bonds and coordinative metal bonds. Although many of the most widely utilized electroactive fragments feature large pconjugated surfaces, to date the use of p–p aromatic interactions has mainly been limited to the construction of semi-infinite ensembles of chromophores either to achieve charge transport…