Macrocyclization and Molecular Interlocking via Mitsunobu Alkylation:  Highlighting the Role of C−H···O Interactions in Templating

Abstract

[reaction: see text] A series of diimide-based macrocycles have been prepared using Mitsunobu-mediated alkylation as the macrocyclization step. These macrocycles could not be incorporated into [2]catenanes using previously established building blocks and coupling methodology. However, when one of the macrocycle syntheses was conducted in the presence of a dinaphtho crown ether, catenane formation was achieved. This result is discussed in terms of the ability of the components to establish intermolecular C-H...O hydrogen-bonding contacts.

Perylene as an electron-rich moiety in healable, complementary π–π stacked, supramolecular polymer systems

“…S2) of the interaction between 3 and a simplified chain-folding bis-diimide motif predicted formation of a 1:1 pep-stacked complex with an average distance of 3.5 Å between the carbon atoms of the complexing p-systems, close to the optimum van der Waals contact distance and consistent with values previously reported for pep stacking interactions [41,49,50].…”

Molecular Links and Knots from Naphthalenediimide: A Balance of Weak Interactions

“…[34] The formation of am ixed NDI-PMI[ 2]catenane (C4)t hrough aM itsunobu alkylationr eaction, in which both the p-donor andt he p-acceptor possessed acidic CH 2 protons for hydrogen bonds,i sa lso consistent with this conclusion ( Figure 6). [35] In 2003, Gunter and Farquhar also reported the synthesis of as eries of [2]catenanesf rom the coppermediated oxidative coupling reactiono fabis-acetyleneN DI in the presence of ac rown ether that containedb oth aD Nm olecule and aporphyrin unit. [36] In 1998, Harding, Sanders, and co-workers described af ivecomponent assembly of metallo-[2]catenane C5,w hich featured reversible Zn 2+ + Àbipyridine coordination (Figure 7).…”

Templated Synthesis of Interlocked Molecules

“…The neutral p-stacking motifs that involve p-electron-deficient diimides, such as pyromellitimide 23 (Scheme 3) and p-electron-rich aromatic ethers, such as the previously mentioned DNP derivative 12, self-assemble to give charge-transfer complexes with intense colors [98]. By employing this type of neutral recognition motif (Scheme 3a) when a [101]. In the synthetic studies of other similar neutral [2]catenanes, the authors [97] conclude that the acidic methylene protons adjacent to the diimide unit facilitate the formation of the [2]catenanes from the macrocycle 20 by additional [N-C-H … O] hydrogen bonding.…”