Synthesis and Configurational Analysis of a Novel Class of Cavitands Containing Four Dioxaphosphocin Moieties

Lippmann, Tino; Wilde, H.; Dalcanale, Enrico; Mavilla, Luigi; Mann, G.; Heyer, Ute; Spera, Silvia

doi:10.1021/jo00106a039

Cited by 49 publications

(24 citation statements)

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“…The iiii stereoisomer of tetra-phosphonate resorcin [4]arene cavitands and other phosphonate derivatives with at least one PO group inwardly directed are known to interact with primary alkylammonium cations by establishing simultaneously NH···O hydrogen bonds and cation−dipole interactions. 25,32 We became interested in assessing the effect provided by one inwardly oriented PO group on the complexation of a primary ammonium salt, that is, octylammonium chloride (OAMCl, 10, Figure 6), by the tetra-phosphonate calix [4]pyrrole 7iooo cavitand. We learned from previous studies with the series of bis-phosphonate calix [4]pyrrole cavitands 2 that octylammonium chloride 10 formed a 1:1 complex with the 2io isomer that was approximately 2-fold thermodynamically more stable than the analogous complex with the 2oo isomer.…”

Section: ■ Introductionmentioning

confidence: 99%

Tetra-phosphonate Calix[4]pyrrole Cavitands as Multitopic Receptors for the Recognition of Ion Pairs

2015

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ABSTRACT:The synthesis, structural characterization and binding properties of two unprecedented multitopic receptors for ion-pair recognition are described. We isolated two of the six possible diastereomeric deep cavitand receptors resulting from the installation of four phosphonate groups at the upper rim of a calix[4]pyrrole-resorcin[4]arene hybrid scaffold. The isolated tetra-phosphonate receptors display either three (iooo) or four (oooo) of their P=O groups oriented away from the deep and functionalized aromatic cavity. In contrast to analogous tetra-phosphonate resorcin[4]arene cavitands, the fourteen-membered macrocyclic rings that contain the P=O groups in the tetraphosphonate calix[4]pyrrole cavitands are conformationally flexible, always adopting a conformation locating the phenyl substituents in equatorial position. The tetra-phosphonate calix[4]pyrroles exhibited larger affinity constants than the previously reported bis-phosphonate calix[4]pyrrole counterparts in the complexation of both tetramethylphosphonium and octylammonium chloride salts in non-polar solvents. We demonstrated that the iooo diastereoisomer was able to function as a multitopic receptor for organic chloride salts by switching the geometry of the 1:1 ion-paired complex from receptor-separated to close-contact depending on the quaternary or primary nature of the cobound organic cation. The ion-paired 1:1 complexes formed between the diastereomeric receptors and organic chloride salts were studied and thermodynamically characterized in solution. The determined stability constant values were compared with those obtained for the bis-phosphonate counterparts. The structure of the TMPCl7iooo complex was determined by X-ray structure and its formation was also evidenced in the gas phase.

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Section: ■ Introductionmentioning

confidence: 99%

Tetra-phosphonate Calix[4]pyrrole Cavitands as Multitopic Receptors for the Recognition of Ion Pairs

2015

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“…Synthesis of the cavitand ligand 6, and self-assembly of nanosize coordination cages 7 a and 7 b. pointing outwards from the cavity (Scheme 2). [13] The stereochemical control of the reaction is assured by the bulkiness of the bridging units, which can be accommodated only in the outward orientation.…”

Section: Introductionmentioning

confidence: 99%

Surface‐Confined Single Molecules: Assembly and Disassembly of Nanosize Coordination Cages on Gold (111)

Menozzi

Pinalli

Speets

et al. 2004

Chemistry A European J

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A cavitand functionalized with four alkylthioether groups at the lower rim, and four tolylpyridine groups on the upper rim is able to bind to a gold surface by its thioether groups, and forms a coordination cage with [Pd(dppp)(CF(3)SO(3))(2)] by its pyridine groups. The cavitand or the cage complex can be inserted from solution into a self-assembled monolayer (SAM) of 11-mercaptoundecanol on gold. The inserted molecules can be individually detected as they protrude from the SAM by atomic force microscopy (AFM). The cages can be reversibly assembled and disassembled on the gold surface. AFM can distinguish between single cavitand and cage molecules of 2.5 nm and 5.8 nm height, respectively.

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“…Cavitands are particularly attractive as hosts because of the wide choice of suitable bridging groups, which shape the cavity and affect the properties of the cavitand. The most common bridging groups are alkylenedioxy [4], dialkylsilicon [5,6], heterophenylene [7,8], and phosphoryl [9,10].…”

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ESI-FTICR mass spectrometric study of alcohol complexation properties of mono- and diphosphonate-bridged cavitands

Ventola

Vainiotalo

Suman

et al. 2006

J. Am. Soc. Mass Spectrom.

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Alcohol complexation properties of eight mono-and diphenyl phosphonate-bridged cavitands (Scheme 1). were studied by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR) and theoretical calculations. The cavitands varied in number and position of phenyl phosphonate bridges and their orientation with respect to the cavity, length of the lower rim alkyl chains, and substituents at apical positions of the resorcarene skeleton. The specificities of the different cavitands toward primary, secondary, and tertiary alcohols varying long of the alkyl chain were investigated, together with the stabilities of the formed complexes. The number, position, and orientation of the P ϭ O moieties affected the complex formation of the cavitands and stability of the complexes dramatically. Methyl groups at apical positions of the resorcarene skeleton also affected the complexation properties. Although length and branching of the alkyl chain of the alcohol influenced the complex formation, the effect on stability of the complexes was negligible. (J Am Soc Mass Spectrom 2006, 17, 213-221)

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Synthesis and Configurational Analysis of a Novel Class of Cavitands Containing Four Dioxaphosphocin Moieties

Cited by 49 publications

References 0 publications

Tetra-phosphonate Calix[4]pyrrole Cavitands as Multitopic Receptors for the Recognition of Ion Pairs

Tetra-phosphonate Calix[4]pyrrole Cavitands as Multitopic Receptors for the Recognition of Ion Pairs

Surface‐Confined Single Molecules: Assembly and Disassembly of Nanosize Coordination Cages on Gold (111)

ESI-FTICR mass spectrometric study of alcohol complexation properties of mono- and diphosphonate-bridged cavitands

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