Crystal‐Packing Trends for a Series of 6,9,12,15,18‐Pentaaryl‐1‐hydro[60]fullerenes

Abstract

The relationship between the size of the substituents of aryl groups in a series of fifteen 6,9,12,15,18-pentaaryl-1-hydro[60]fullerenes and the solid-state structures and packing motifs of these compounds has been analyzed. Pentaarylfullerenes have a characteristic "badminton shuttlecock" shape that causes several derivatives to crystallize into columnar stacks. However, many pentaarylfullerenes form non-stacked structures with, for example, dimeric, layered, diamondoid, or feather-in-cavity relationships between molecules. Computational modeling gave a qualitative estimate of the best shape match between the ball and socket surfaces of each pentaarylfullerene. The best match was for pentaarylfullerenes with large, spherically shaped para-substituents on the aryl groups. The series of pentaarylfullerenes was characterized by single-crystal X-ray diffraction. A total of 34 crystal structures were obtained as various solvates and were categorized by their packing motifs.

New Penta(tetrathiafulvalenyl)[60]fullerenes for Supramolecular Materials

“…The host cavity created around the fullerene together with the π–π and electronic interactions make possible their self‐assembly through supramolecular nesting organization. We have designed monomers 3 a / 3 b taking advantage of the singular and unique properties of penta(organo)[60]fullerenes, which possess a complementary conical cavity in size and shape to the fullerene surface . To this cage, we have attached five electroactive recognition units (TTFs), through an efficient single‐step reaction, to drive the self‐assembly process.…”

“…We have designed monomers 3a/3b taking advantageo ft he singular and unique properties of penta(organo)[60]fullerenes, which possess acomplementary conical cavity in size and shapet ot he fullerene surface. [14] To this cage, we have attached five electroactiverecognition units (TTFs), [15] through an efficients ingle-step reaction, to drive the self-assembly process.…”

Panoramic View of Electrochemical Pseudocapacitor and Organic Solar Cell Research in Molecularly Engineered Energy Materials (MEEM)

“…92 For example, the use of t-butyl phenyl alkyl groups (1a) leads to SCs that strongly prefer to assemble into 1D stacks, as evidenced by the crystal structure shown in Figure 11a. 92,94 In contrast, the use of methyl alkyl groups (either in the para (1d) or meta (1e) positions) produces SCs that have no preference to stack ball-in-cup, as shown by the crystal structure of 1d in Figure 11b. Ethyl (1c) and isopropyl (1b) substituents lead to intermediate behavior in the preference to stack.…”

“…Ethyl (1c) and isopropyl (1b) substituents lead to intermediate behavior in the preference to stack. 94 To understand how tuning the ability to form self-assembled stacks affects the properties of OPV devices based on these materials, we blended all of the SC molecules whose structures are shown in Figure 10 with poly(3-hexylthiophene 2,5 diyl) (P3HT). We found that the SCs that preferred to stack (1a,1b) produced solar cells with much higher power conversion efficiencies than those based on the SCs that do not stack (1c−1e), as shown in Figure 12a.…”

A Three‐Dimensional Dynamic Supramolecular “Sticky Fingers” Organic Framework

“…Upon purification, the resulting hexaadduct was characterized by the usual analytical and spectroscopic techniques (see the Supporting Information for further details). Theu nit cell is composed of eight symmetryequivalent hexaadducts placed in four unequal layers.Importantly,i nc ontrast to the major packing driving force of pristine [60]fullerene, [37] in 3 there is no evidence of any supramolecular p-p contacts between neighboring fullerene buckyballs (Figure 1g;S upporting Information, Table S2). This method afforded large,r egular,o range crystals that were suitable for X-ray diffraction analysis ( Figure 1b;for full synthetic details see the Supporting Information).…”