Concave Tetrathiafulvalene‐Type Donors as Supramolecular Partners for Fullerenes

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

“…These two dispositions resemble the arrangement found in the crystal packing for the homodimers of truxTTF and the related C 30 H 12 , implying a mixture of p-p and CH-p interactions. [30,32] All the optimized heterodimeric structures (1)(2)(3)(4) show close intermolecular contacts in the 2.5-3.7 range ( Figure S1 in the Supporting Information), indicative of stabilizing noncovalent interactions between both bowls.…”

“…To provide a more realistic description reflecting the strength of complexation at room temperature and in solution, we made theoretical estimations of the free energy of the dimerization process for all the possible conformers of truxTTF·C 32 H 12 and truxTTF·C 38 H 14 , and compared them with that computed for truxTTF·C 30 H 12 (see Supporting Information for full computational details). The free energies in the gas phase show that entropic effects are similar for both bowl-inbowl and staggered dimers (Table S1, Supporting Information).…”

“…For the three buckybowls, the staggered dimers in which the dithiole ring is placed inside the bowl These are not the final page numbers! ÞÞ Full Paper 1 1 2 2 3 3 4 4 5 5 6 6 7 7 8 8 9 9 10 10 11 11 12 12 13 13 14 14 15 15 16 16 17 17 18 18 19 19 20 20 21 21 22 22 23 23 24 24 25 25 26 26 27 27 28 28 29 29 30 30 31 31 32 32 33 33 34 34 35 35 36 36 37 37 38 38 39 39 40 40 41 41 42 42 43 43 44 44 45 45 46 46 47 47 48 48 49 49 50 50 51 51 52 52 53 53 54 54 55 55 56 56 57 30 H 12 (log K a,theor = 3.7) with respect to the experimental value (log K a , exp = 3.6 AE 0.3) reported previously. [27] Calculations using chlorobenzene led to both qualitatively and quantitatively similar results (Table S1, Supporting ...…”

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

“…[1][2][3][4][5][6][7][8][9][10][11] To achieve these objectives, the formation of stable associates with fullerenes is a prerequisite. In this regard, the group of Kawase has recently coined the term ''concave-convex interactions'' [5][6][7][8] to denote the increase in non-covalent interactions between curved aromatic hosts and guests, and suggested these might play a distinct role in the stabilization of the complexes.…”

“…9,10 Receptor 1 features 2-[9-(1,3-dithiol-2-ylidene)anthracen-10(9H)-ylidene]-1,3-dithiole (exTTF) as the recognizing element (Chart 1). 9 Despite the lack of preorganization in its design, 1 forms stable associates with C 60 (see Table 1).…”