Influence of upper rim dibromo-substitution in bis-1,3-diketone calix[4]arenes on spectral properties of ligands and their lanthanide complexes

Podyachev, Sergey N.; Gimazetdinova, Gulnaz Sh.; Sudakova, Svetlana N.; Shamsutdinova, Nataliya; Lapaev, Dmitry V.; Syakaev, Victor V.; Gubaidullin, А. Т.; Nagimov, Rinas N.; Mustafina, Asiya R.

doi:10.1016/j.tet.2017.07.043

Cited by 17 publications

(14 citation statements)

References 36 publications

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“…This is well exemplified [ 23 ] by the series of 1,3-diketones, where substitution of methyl substituents on benzyl or thenoyl moieties modifies the triplet level, which, in turn, enables to sensitize the green or red luminescence of Tb 3+ or Eu 3+ . The similar effect of substituents has been revealed for the differently substituted 1,3-diketone derivatives of calix[4]arenes ( 32a – c [ 55 ] , 41a – c [ 59 ] on Table 1 ). In particular, the lower energy of the triplet level of the benzoylacetone-substituted calix[4]arenes ( 32b, 41b ) versus the acetylacetone-substituted ones ( 32a, 37, 41a,d ) is the reason for the different antenna effects on the Tb 3+ -and Yb 3+ -centered luminescence.…”

Section: Lanthanide-centered Luminescence Sensitized By the Cyclopsupporting

confidence: 67%

“…The synthesis of compounds 33 [ 59 ] and 34 [ 60 ] was carried out by means of protection and deprotection procedures using a benzoyl group, as well as by introduction of bromine atoms at the upper rim of calix[4]arene applying Br 2 . Dibromo-calix[4]arenes 39a,b with alkyl substituents were obtained by the procedures of dialkylation, bromination, and alkylation of the remaining hydroxyl groups.…”

Section: Synthesis Of the 13-diketone Calix[4]arene Derivativesmentioning

confidence: 99%

“…The assumption has been proved by both experimental results and quantum-chemical calculations [ 54 , 55 , 69 ]. The bis-chelation of terbium ions by 1,3-diketonates is more thermodynamically favorable than their coordination with the lower phenolic/phenolate rim of both tetra- ( 27a ) [ 54 ] and bis-acetylacetone-substituted calix[4]arenes 32a , 37 [ 55 , 59 ] as it is illustrated by Figure 3 . Thus, the presence of the lower phenolic rim doesn’t affect the coordination of Tb 3+ ion with 1,3-diketonates embedded at the upper rim of calix[4]arene backbone [ 54 , 55 ].…”

Section: Complex Formation Of 13-diketone Calix[4]arene Derivativmentioning

confidence: 99%

“…As it has been already noted the benzoylacetone moieties embedded onto calix[4]arene platform exhibit the restricted keto-enol transformation [ 59 ]. Thus, the complex formation of the calix[4]arenes bearing benzoylacetone moieties ( 32a – c in Scheme 9 ) with terbium ions is slowed down and comes to the equilibrium conditions within one day, while the complex formation extent is still insignificant within one day for the diphenyl substituted 1,3-diketone derivatives Figure 5 [ 55 ].…”

Section: Complex Formation Of 13-diketone Calix[4]arene Derivativmentioning

confidence: 99%

“…The fluorination or bromination of methyl or phenyl moieties is the well-known prerequisite for rigidifying of the inner-sphere environment of lanthanide ions [ 23 , 35 , 75 ]. The upper-rim bromination of 1,3-diketone derivatives of calix[4]arene ( 37 , 41a – f ) decreases the radiationless decay, which exemplifies the so-called heavy atom effect [ 59 ] ( Figure 7 a).…”

Section: Lanthanide-centered Luminescence Sensitized By the Cyclopmentioning

confidence: 99%

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1,3-Diketone Calix[4]arene Derivatives—A New Type of Versatile Ligands for Metal Complexes and Nanoparticles

2021

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The present review is aimed at highlighting outlooks for cyclophanic 1,3-diketones as a new type of versatile ligands and building blocks of the nanomaterial for sensing and bioimaging. Thus, the main synthetic routes for achieving the structural diversity of cyclophanic 1,3-diketones are discussed. The structural diversity is demonstrated by variation of both cyclophanic backbones (calix[4]arene, calix[4]resorcinarene and thiacalix[4]arene) and embedding of different substituents onto lower or upper macrocyclic rims. The structural features of the cyclophanic 1,3-diketones are correlated with their ability to form lanthanide complexes exhibiting both lanthanide-centered luminescence and magnetic relaxivity parameters convenient for contrast effect in magnetic resonance imaging (MRI). The revealed structure–property relationships and the applicability of facile one-pot transformation of the complexes to hydrophilic nanoparticles demonstrates the advantages of 1,3-diketone calix[4]arene ligands and their complexes in developing of nanomaterials for sensing and bioimaging.

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Section: Lanthanide-centered Luminescence Sensitized By the Cyclopsupporting

confidence: 67%

Section: Synthesis Of the 13-diketone Calix[4]arene Derivativesmentioning

confidence: 99%

Section: Complex Formation Of 13-diketone Calix[4]arene Derivativmentioning

confidence: 99%

Section: Complex Formation Of 13-diketone Calix[4]arene Derivativmentioning

confidence: 99%

Section: Lanthanide-centered Luminescence Sensitized By the Cyclopmentioning

confidence: 99%

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1,3-Diketone Calix[4]arene Derivatives—A New Type of Versatile Ligands for Metal Complexes and Nanoparticles

2021

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Polystyrenesulfonate-coated nanoparticles with low cytotoxicity for determination of copper(II) via the luminescence of Tb(III) complexes with new calix[4]arene derivatives

et al. 2018

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The authors describe new ligands with two 1,3-diketone groups and two heteroaromatic (pyridyl or quinolyl) moieties embedded to the upper and lower rims of dibromo-substituted calix[4]arene scaffold. The ligands bind Tb(III) ions in alkaline DMF solutions to form 1:1 complexes. The strong Tb(III)-centered luminescence (with excitation/emission peaks at 330/545 nm) of the complexes results from efficient ligand-to-metal energy transfer. The complexes were incorporated into polystyrenesulfonate (PSS) colloids by diluting a DMF solution of the complex with aqueous solution of PSS. The luminescence of the colloids is quenched by copper(II), and this was used to develop a method for its fluorometric determination in nanomolar concentrations. The lower limit of detection is 0.88 nM. Quenching is a result of (a) ion exchange which converts the terbium complexes into their copper counterparts, and (b) energy transfer from Tb(III) to Cu(II) complexes. The low cytotoxicity of the colloidal nanoprobe conceivably makes it a promising tool for use in cellular imaging. Graphical abstract New calix[4]arene derivative provide efficient binding sites for Tb(III) and Cu(II) ions. The Tb(III) complexes were embedded to core-shell nanoparticles by solvent-mediated aggregation followed by polystryrenesulfonate deposition. The nanoparticles exhibit luminescence response on copper ions in nanomolar concentration range.

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Substrate-induced luminescence response of terbium-containing polymeric vesicles doped with the tetra- and bis-1,3-diketone derivatives of calix[4]arenes bearing nonyl substituents at the lower rims

et al. 2019

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Influence of upper rim dibromo-substitution in bis-1,3-diketone calix[4]arenes on spectral properties of ligands and their lanthanide complexes

Cited by 17 publications

References 36 publications

1,3-Diketone Calix[4]arene Derivatives—A New Type of Versatile Ligands for Metal Complexes and Nanoparticles

1,3-Diketone Calix[4]arene Derivatives—A New Type of Versatile Ligands for Metal Complexes and Nanoparticles

Polystyrenesulfonate-coated nanoparticles with low cytotoxicity for determination of copper(II) via the luminescence of Tb(III) complexes with new calix[4]arene derivatives

Substrate-induced luminescence response of terbium-containing polymeric vesicles doped with the tetra- and bis-1,3-diketone derivatives of calix[4]arenes bearing nonyl substituents at the lower rims

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