Solvent Triggering between Conformational States in Amphiphilic Shape-Persistent Macrocycles

Abstract

The amphiphilic shape-persistent macrocycle 1 containing four phenol-OH groups as polar side groups and four hexyloxy groups as nonpolar side groups in an adaptable arrangement was recrystallized from solvents of different polarity. X-ray crystallography reveals that the conformation of the macrocycle is solvent dependent such that in the pyridine solvate only two of the nonpolar side groups point outward while in the THF solvate all four of them point outward. Moreover, in the latter case the three-dimensional packing leads to the formation of a supramolecular channel structure with a large pore size.

Shape-Persistent, Nano-Sized Macrocycles

“…Depending on the polarity of the solvate (THF and pyridine), 14f crystallizes in two different forms, one in which the channels are packed with side chains and one where they are filled with solvent molecules. [40] …”

“…B 2 MS, 1 H NMR 9a [33] 14% 209 mg B 2 GPC, MS, 1H NMR, EA 9b [33] 5% 79 mg B 4 GPC, MS, 1H NMR, EA 10a [34] 54% 220 mg B [c] 2 MS, NMR, UV, EA 10b [34] 32% 90mg D 2 UV, (EA), charact. as complex 11a [35] 28% 383 mg B 2 GPC, MS, NMR, EA, X-ray 11b [35] 25% 250 mg B 2 GPC, MS, NMR, X-ray 11c* [36] 14% 160 mg B 2 GPC, MS, NMR, X-ray 11d [37] 18% 83 mg B 2 GPC, MS, NMR 11e [37] 21% 340 mg B 2 GPC, MS, NMR 12a [38] 21% 25mg B 2 MS, NMR, X-ray 12b [38] 14% 42mg B 2 MS, NMR, STM, X-ray 12c [38] 25% 114 mg B 2 MS, NMR, X-ray 12d* [38] 18% 135 mg B 2 MS, NMR 12e [38] 18% 216 mg B 2 MS, NMR 13a [38] 27% 40 mg B 2 MS, 1H NMR 13b [38] 8% 28 mg D 2 MS, 1H NMR 13c [38] 18% 39 mg B 2 MS 13d* [38] 19% 46 mg B 2 MS 13e [38] 11% 45 mg B 2 MS, NMR 14a [39] 48% 860 mg D 2 m.p., MS, NMR 14b [39] R m.p., MS, NMR 14c [39] R m.p., MS, NMR 14d [39] R m.p., MS, NMR, STM 14e [39] R MALDI, NMR, m.p., STM 14f [40] R X-ray 14g [41] n.s. n.s.…”

Donor–Acceptor‐Substituted Phenylacetylene Macrocycles with Threefold Symmetry

“…[16][17][18] In addition, the capability of the acetylene linkage to transmit electronic perturbation within a conjugated system makes them useful components in the construction of molecular wires, [19,20] conjugated dendrimers [21,22] and optical systems. [23][24][25] Interest in such macrocycles published in recent years has predominantly been focused on self-association behaviour based on weak interactions [26][27][28][29] involving liquid crystals [30] and monolayer surfaces. [7] The large cavities of these phenylacetylene macrocycles (PAMs) should allow the incorporation of metal salts.…”

Shape‐Persistent Macrocycles: From Molecules to Materials

“…[16] Recrystallization of 3 a from pyridine leads to half of the nonpolar alkyl groups point to the outside and half of them to the inside, whereas recrystallization from the less polar solvent THF leads to the macrocycle adopting a conformation in which all nonpolar alkyl groups point to the outside. The different conformations lead also to a different supramolecular organization of the rings in the crystal lattice: 3 a¥¥¥12 THF forms a supramolecular tube consisting of channels with pore sizes (ca.…”