0000000001309074
AUTHOR
Ulrike Warzok
Surprising solvent-induced structural rearrangements in large [N⋯I+⋯N] halogen-bonded supramolecular capsules
Coordinative halogen bonds have recently gained interest for the assembly of supramolecular capsules. Ion mobility-mass spectrometry and theoretical calculations now reveal the well-defined gas-phase structures of dimeric and hexameric [N...I+...N] halogen-bonded capsules with counterions located inside their cavities as guests. The solution reactivity of the large hexameric capsule shows the intriguing solvent-dependent equilibrium between the hexamer and an unprecedented pentameric [N...I+...N] halogen-bonded capsule, when the solvent is changed from chloroform to dichloromethane. The intrinsic flexibility of the cavitands enables this novel structure to adopt a pseudo-trigonal bipyramida…
Nano-sized I12L6 Molecular Capsules Based on the [N⋅⋅⋅I+⋅⋅⋅N] Halogen Bond
Summary Self-assembly of pre-organized subunits with a concave overall shape is an effective strategy for the synthesis of supramolecular capsules. We report the synthesis of a cavitand-based hexameric capsule held together solely by 12 robust [N⋅⋅⋅I + ⋅⋅⋅N] halogen bonds and its characterization in solution and in the gas phase via 1 H NMR spectroscopy, diffusion-ordered nuclear magnetic resonance spectroscopy (DOSY), and electrospray ionization mass spectrometry. The [N⋅⋅⋅I + ⋅⋅⋅N] halogen-bonded hexameric capsule was efficiently synthesized from the isolobal metallosupramolecular Ag + capsule by application of the [N⋅⋅⋅Ag + ⋅⋅⋅N] → [N⋅⋅⋅I + ⋅⋅⋅N] cation-exchange reaction.
[N⋅⋅⋅I+⋅⋅⋅N] Halogen-Bonded Dimeric Capsules from Tetrakis(3-pyridyl)ethylene Cavitands
Two [N⋅⋅⋅I+⋅⋅⋅N] halogen-bonded dimeric capsules using tetrakis(3-pyridyl)ethylene cavitands with different lower rim alkyl chains are synthesized and analyzed in solution and the gas phase. These first examples of symmetrical dimeric capsules making use of the iodonium ion (I+) as the main connecting module are characterized by 1H NMR spectroscopy, diffusion ordered NMR spectroscopy (DOSY), electrospray ionization mass spectrometry (ESI-MS), and ion mobility-mass spectrometry (TW-IMS) experiments. The synthesis and effective halogen-bonded dimerization proceeds through analogous dimeric capsules with [N⋅⋅⋅Ag+⋅⋅⋅N] binding motifs as the intermediates as evidenced by the X-ray structures of …
CCDC 1498390: Experimental Crystal Structure Determination
Related Article: Lotta Turunen, Ulrike Warzok, Rakesh Puttreddy, Ngong Kodiah Beyeh, Christoph A. Schalley, Kari Rissanen|2016|Angew.Chem.,Int.Ed.|55|14033|doi:10.1002/anie.201607789