Highly efficient methods for the preparation of shape-persistent macrocyclics

Supramolecular Organization of Foldable Phenylene Ethynylene Oligomers

“…In acetonitrile, almost identical spectra were obtained for 10-13. However, when the chain length reached ten repeat units and above (14)(15)(16)(17)(18), quenching of the fluorescence intensity was observed (Fig. 3).…”

“…To determine if chirality transfer was taking place in column-like aggregates,"sergeant and soldiers" experiments were performed where achiral oligomers were doped with different percentages of chiral oligomers and the resulting CD was observed [67]. The CD maxima of mixtures of chiral (45, n=18) and achiral oligomers (18) were studied in different solvent compositions to determine if chirality was transferred through aggregation. In 100% acetonitrile the CD signal was linear with respect to the percentage of chiral oligomer, indicating that the signals observed in 100% acetonitrile can be attributed to intramolecular effects (Fig.…”

“…However, there are several excellent reviews of pPE synthesis, structure, and function in the recent literature that discuss the intermolecular order of those systems [7][8][9][10][11][12][13][14][15]. Similarly, phenylene ethynylene macrocycles, which form a wide range of supramolecular aggregates with interesting stacking behavior, will not be covered but have been extensively reviewed [16][17][18][19][20][21][22].…”

Poly(aryleneethynylene)s

“…Section 5.10 discusses how alkyne metathesis has been brought to bear on this problem and how it is exquisitely adept at overcoming these shortfalls. However, Pd methods are still used and yields have been improved by using monodisperse precursors (Section 5.6) [47][48][49][50][51][52][53][54]. Macrocycles are of great interest because of their stacking behavior and ability to form porous supramolecular aggregates.…”

Shape‐Persistent Macrocycles Based on Acetylenic Scaffolding

“…The synthesis of acetylenic SPMs has been reviewed on a number of occasions, typically with a focus on a particular structural motif, and those molecules based on an arylene ethynylene framework have received the lions share of the attention [1][2][3][4][5][6][7][8][9][10][11][12][13]. Likewise, the use of acetylenic SPMs in functional systems has also been reviewed, but, again, typically with respect to a particular molecular design [5,[14][15][16].…”