Lanthanide ion complexes of the calixarenes. Part 4. Double inclusion by p-t-butylcalix[4]arene (H4L). Crystal structures of [Eu2(HL)2(dmf)4].7dmf (dmf = dimethylformamide) and H4L.dmso (dmso = dimethyl sulphoxide)

Furphy, Brenda M.; Harrowfield, J. M.; Ogden, Mark I.; Skelton, Brian W.; White, Allan H.; Wilner, Faye R.

doi:10.1039/dt9890002217

Cited by 49 publications

(28 citation statements)

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“…Synthesis of p-tert-Butylcalix [4]arenedithiol. p-tertButylcalix [4]arene substituted with thiol groups was synthesized from p-tert-butylcalix [4]arene by using the method by Gutsche and co-workers.…”

Section: Methodsmentioning

confidence: 99%

Formation of Well-Definedp-tert-Butylcalix[4]arenedithiolate Monolayers on a Au(100)−(1 × 1) Surface Studied by In Situ Scanning Tunneling Microscopy

et al. 2003

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p-tert- Butylcalix[4]arene-1,3-dithiol (BCAD) was synthesized to prepare a functionalized surface for host-guest molecular recognition by immobilizing it on the Au(100)-(1 × 1) surface in 0.05 M HClO4. In situ scanning tunneling microscopy (STM) was employed to investigate the structure of the adlayer of BCAD formed on the Au(100)-(1 × 1) surface. Highly ordered adlayers of BCAD with two different packing arrangements were found to form on the Au(100)-(1 × 1) surface. High-resolution STM images revealed the packing arrangement and even the internal molecular structure of BCAD.

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Section: Methodsmentioning

confidence: 99%

Formation of Well-Definedp-tert-Butylcalix[4]arenedithiolate Monolayers on a Au(100)−(1 × 1) Surface Studied by In Situ Scanning Tunneling Microscopy

et al. 2003

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“…12 In the case of p-tert-butylcalix [4]arene 2 : 2 dimeric complexes were obtained, in which the two metal atoms are separated by only 3.91 Å. 13 In our laboratory we have mainly studied the photophysical properties of bimetallic complexes with p-tert-butylcalix [8]arene [14][15][16] and demonstrated the influence of the low-lying ligand-to-metal charge-transfer state (LMCT) on the Eu III -containing assemblies, which enhances the f-f absorption probabilities through mixing with the 4f orbitals and quenches the 5 D 0 (Eu) excited level. Moreover, the sensitisation of Eu III and/or Tb III can be conveniently tuned by changing the nature of the para substituent.…”

mentioning

confidence: 99%

Complexes of p-tert-butylcalix[5]arene with lanthanides: synthesis, structure and photophysical properties †

Charbonnière¹,

Balsiger²,

Schenk³

et al. 1998

J. Chem. Soc., Dalton Trans.

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Spectrophotometric pK a determination for p-tert-butylcalix [5]arene (H 5 L) in acetonitrile (pK a1 = 11.5 ± 0.7, pK a2 = 15.4 ± 1.0 at 298 K) evidenced both intra-and inter-molecular stabilisation of the deprotonated forms. Dimeric complexes [Ln 2 (H 2 L) 2 (dmso) 4 ] (Ln = Eu III , GdIII , or Tb III; dmso = dimethyl sulfoxide) were isolated from tetrahydrofuran (thf) in the presence of NaH as base. A single-crystal analysis of [Eu 2 (H 2 L) 2 (dmso) 4 ]ؒ 10thf showed the deformation of the cone conformation of the calixarene upon complexation and co-ordination of dmso molecules by inclusion through the hydrophobic cavity of the ligand. A photophysical investigation revealed a total quenching of the metal luminescence by a ligand-to-metal charge-transfer state in the case of Eu III while luminescence of Tb III is sensitised (quantum yield in thf: 5.1%). The temperature-dependent lifetime of Tb III is analysed in terms of a potential metal-to-ligand back-transfer process.The cyclic framework of calixarenes, 1 associated with the presence of phenol oxygen donor atoms, affords an interesting platform for the complexation of metal atoms, 2 while the hydrophobic cavity allows the inclusion of charged 3 and neutral 4 organic guests. The relative facility with which calixarenes can be partially or totally functionalised at the upper or lower rims, coupled with their easy large-scale synthesis, at least for the even members of the series (n = 4, 6 or 8), has opened further perspectives for their use in supramolecular chemistry. 5In particular, the hard acid character of the lower rim makes calixarenes interesting potential ligands for the complexation of trivalent lanthanide ions, either for extraction purposes 6 or for the design of efficient lanthanide-based luminescent devices.7-9 Antenna effects 10 can be generated directly by the phenol units or by lower or upper rim substitution.Previous work on the complexation of lanthanides with calix[n]arenes has mainly focused on the four-, six-and eightmembered systems. While p-tert-butylcalix [8] 19 who isolated water-soluble inclusion complexes between p-sulfonatocalix [5]arene with La, Gd, Eu, Tb and Yb and showed by X-ray crystallography that the interaction is either outer sphere or occurs exclusively via one sulfonato functionality, the metal centre acting often as a bridging brick. In this paper we present the isolation and the structural and photophysical properties of lanthanoid() (Ln = Eu, Gd or Tb) phenolate-bonded inner-sphere complexes with p-tert-butylcalix [5]arene (H 5 L). The reported data add valuable information on the interaction between lanthanoid() ions and p-tert-butylcalix [n]arenes and demonstrate that multiple bonds between the ligand and the metal ions can be generated only in the presence of a strong base. In addition, the spectrophotometric determination of the first two pK a values of the ligand is reported. Results and Discussion Acid-base behaviour of H 5 L in acetonitrileThe compound H 5 L was titrated at 298 K by Et 3 N in acetonitril...

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“…These phenolato groups bridge to neighbouring ions within a cluster (for example see Figure 1B) and impart a degree of directionality in the assembly process; this can also be considered as structural capping behaviour (vide infra). C [4]-supported clusters can also be synthesised under solvothermal (13,14) or air-sensitive conditions (15)(16)(17), but discussion of this expansive chemistry is far beyond the scope of this contribution; in these cases the resulting structures differ markedly from those reported herein. Thia-, sulfonyl-and sulfinyl-bridged C [4]s have also been used in cluster-forming chemistry, but lower-rim coordination chemistry is drastically different to that of the methylene-bridged analogues, leading to vastly different structure types and physical properties.…”

Section: Introductionmentioning

confidence: 90%

Exploratory studies into 3d/4f cluster formation with fully bridge-substituted calix[4]arenes

Fong

McCormick

Teat

et al. 2018

Supramolecular Chemistry

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Supporting information (additional figures to support discussion and crystallographic information files, CIFs) can can be accessed at https://doi.org/……. Exploratory studies into 3d/4f cluster formation with fully bridgesubstituted calix[4]arenes Calix[4]arenes are extremely versatile ligands that are capable of supporting the formation of a wide variety of polymetallic clusters of paramagnetic metal ions. One can exert influence over cluster formation through alteration of the calix[4]arene framework and subsequent 'expansion' of the lower-rim polyphenolic binding site. The present contribution investigates cluster formation with calix[4]arenes substituted at all four methylene bridge positions with furan moieties. Two known cluster types have been isolated with this ligand, the structures of which lend insight into factors that may ultimately preclude the formation of mixed-metal species.

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Lanthanide ion complexes of the calixarenes. Part 4. Double inclusion by p-t-butylcalix[4]arene (H4L). Crystal structures of [Eu2(HL)2(dmf)4].7dmf (dmf = dimethylformamide) and H4L.dmso (dmso = dimethyl sulphoxide)

Cited by 49 publications

References 1 publication

Formation of Well-Definedp-tert-Butylcalix[4]arenedithiolate Monolayers on a Au(100)−(1 × 1) Surface Studied by In Situ Scanning Tunneling Microscopy

Formation of Well-Definedp-tert-Butylcalix[4]arenedithiolate Monolayers on a Au(100)−(1 × 1) Surface Studied by In Situ Scanning Tunneling Microscopy

Complexes of p-tert-butylcalix[5]arene with lanthanides: synthesis, structure and photophysical properties †

Exploratory studies into 3d/4f cluster formation with fully bridge-substituted calix[4]arenes

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