The quest for a molecular capsule assembled via halogen bonds

Aakeröy, Christer B.; Rajbanshi, Arbin; Metrangolo, Pierangelo; Resnati, Giuseppe; Parisi, Melchiorre F.; Desper, John; Pilati, Tullio

doi:10.1039/c2ce26173a

Cited by 64 publications

(61 citation statements)

References 40 publications

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“…13). The 19 F NMR also did not show any real change. This result also highlights the sensitivity of XB to concentration in solution.…”

Section: Iii-a) Nmr Spectroscopymentioning

confidence: 69%

“…These results thus confirm the apparent interference of the bulk CDCl 3 . 19 F NMR experiments in CDCl 3 at 303 K were done to further probe the existence of the halogen bonded assemblies in solution. In the analyses, the fluorine signals of the XB donor 5 were monitored.…”

Section: Resultsmentioning

confidence: 99%

“…Black dots indicate complexation induced shielding of the guest 7.Fig. 3 19. F NMR in CDCl3 at 303 K of: a) 5 (10 mM), b) 1:2 mixture of 1 and 5, c) 1:2:1 mixture of 1, 5 and 6 and d) 1:2:1 mixture of 1, 5 and 7.…”

mentioning

confidence: 97%

“…19 F NMR in CDCl3 at 303 K of: a) 5 (10 mM), b) 1:2 mixture of 2 and 5, c) 1:2:1 mixture of 2, 5 and 6 and d) 1:2:1 mixture of 2, 5 and 7. Stars indicate shifts resulting from the formation of XBs.…”

mentioning

confidence: 99%

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Concerted Halogen-Bonded Networks with N-Alkyl Ammonium Resorcinarene Bromides: From Dimeric Dumbbell to Capsular Architectures

2015

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N-Alkyl ammonium resorcinarene bromides and 1,4-diiodooctafluorobutane via multiple intermolecular halogen bonds (XB) form different exotic supramolecular architectures through subtle changes of the upper rim substituents. Dimeric dumbbell-like assembly with encapsulated guest molecules is generated with N-benzyl substituents. The N-hexyl groups engender an XB-induced polymeric pseudocapsule and an XB-induced dimeric capsule with entrapped 1,4-dioxane guest molecules. The N-propyl and N-cyclohexyl groups generate deep cavity cavitands. The deep cavity cavitands possess cavities for self-inclusion leading to polymeric herringbone arrangement in one direction and that pack into 3D polymeric arrangement resembling egg crate-like supramolecular networks. These assemblies are studied in solution via NMR spectroscopy and in the solid state via X-ray crystallography.

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“…13). The 19 F NMR also did not show any real change. This result also highlights the sensitivity of XB to concentration in solution.…”

Section: Iii-a) Nmr Spectroscopymentioning

confidence: 69%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 97%

mentioning

confidence: 99%

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Concerted Halogen-Bonded Networks with N-Alkyl Ammonium Resorcinarene Bromides: From Dimeric Dumbbell to Capsular Architectures

2015

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“…[20,25] Then ature of the XBs involving organic donors differ from that involving inorganic donors. [26] Halogen bonds with organic donors are usually regarded to be largely electrostatic in nature,w hereas charge-transfer interactions dominates the inorganic XB type.R egardless of the nature of the XBs,the obvious advantages of using I 2 as an XB donor to build dimeric capsules are its small size,linearity,and the bifunctionality of the XB interactions.E ach of these characteristics are useful to stabilize spherical or ellipsoidal assemblies.T he other advantage is that as the XB donor I 2 does not have additional interfering substituents which might sterically block the cavity or render the dimeric capsule formation impossible.…”

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confidence: 99%

A Halogen‐Bonded Dimeric Resorcinarene Capsule

2015

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Iodine (I 2 )a cts as ab ifunctional halogen-bond donor connecting two macrocyclic molecules of the bowlshaped halogen-bond acceptor,N -cyclohexyl ammonium resorcinarene chloride 1,t of orm the dimeric capsule [(1,4-dioxane) 3 @1 2 (I 2 ) 2 ]. The dimeric capsule is constructed solely through halogen bonds and has as ingle cavity (V = 511 3 )l arge enough to encapsulate three 1,4-dioxane guest molecules.Hydrogen bonds (HB) are weak interactions that are extensively used in the design of organic supramolecular assemblies. [1] Their application spans from the preparation of simple compounds to complex materials and those mimicking biological processes. [2] Thehalogen bond (XB) is analogous to HB in strength and directionality,a nd has recently been defined. [3] This noncovalent interaction is based on apolarized halogen atom which interacts with aLewis base,insome cases with coordinative [4] or covalent character,toform aXB. [3] The XB donors exhibit an anisotropic electron distribution leading to an electropositive region on the halogen atom named the s hole. [5] Thes trength of the XB interactions (R À X···A) usually follow the trend X = I > Br @ Cl @ F. Dihalogens (X 2 ) are very interesting XB donors and often display very short XB distances,s ometimes approaching those of the corresponding covalent bonds. [6] Though the polarizability of the halogen in an XB donor is critical, the strength of the X 2 ···A-type XB can be correlated to the ability of Atoaccept ah alogen bond [7] as aL ewis base [8] leading to a" basicity scale" for I 2 ···A halogen bonds.Anions which are Lewis bases are good hydrogen-and halogen-bond acceptors. [7,9] Thea bility of anions to have multiple coordination geometries has led to their utilization in numerous noncovalent interactions. [10] Halides are spherical, symmetrical anions with the negative charge concentrated on as ingle atom making them excellent HB and XB acceptors. [9,10] As ar esult of these properties [11] halides have coordination numbers,t hat is,t he number of hydrogen or halogen bonds,r anging typically from four to eight. If simultaneously present, both HB and XB can therefore be used in tandem to form functional assemblies. [12] Multiple 1D,[*] Dr.

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