"Flexiball" toolkit: a modular approach to self-assembling capsules.
We report the synthesis and characterization of new, self-assembling molecular capsules. The modular strategy makes use of glycoluril building blocks available in multigram amounts combined with aromatic spacer elements. The lengthy syntheses encountered with earlier generations of capsules are avoided, and several capsules of nanometer dimensions are now accessible. Single bond attachments between spacers and glycoluril modules result in monomers as dimeric capsules that are less rigid than their earlier counterparts. The host-guest properties of the homo- and heterodimeric capsules were studied using a combination of NMR and ESI-mass spectrometry. They show a less pronounced selectivity for guests of different sizes, and their increased flexibility prevents self-assembly when no rigidifying elements are present on the central spacer unit. Some of the new capsules bear inwardly directed, secondary amide N-H protons. These can be further functionalized, as shown by their methylation to give tertiary analogues. The structures hold broader implications for the placement of functional groups on concave molecular surfaces.
O'Leary
B M
BM
The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
Szabo
T
T
Svenstrup
N
N
Schalley
C A
CA
Lützen
A
A
Schäfer
M
M
Rebek
J
J
D000480:Alkynes; D000588:Amines / Q000138:chemical synthesis / Q000737:chemistry; D002264:Carboxylic Acids / Q000138:chemical synthesis / Q000737:chemistry; D019281:Dimerization; D007093:Imidazoles / Q000737:chemistry*; D046911:Macromolecular Substances; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008958:Models, Molecular; D008968:Molecular Conformation; D018716:Molecular Mimicry; D021241:Spectrometry, Mass, Electrospray Ionization; D013499:Surface Properties; D006574:Heterocyclic Compounds, 2-Ring; D048289:Imidazolidines
D000480:Alkynes; D000588:Amines; D002264:Carboxylic Acids; D007093:Imidazoles; D046911:Macromolecular Substances; C092018:glycoluril; D006574:Heterocyclic Compounds, 2-Ring; D048289:Imidazolidines