First Insights into the Electronic Properties of a Cu(II) Center Embedded in the PN<sub>3</sub> Cap of a Calix[6]arene-Based Ligand

Izzet, Guillaume; Zeng, Xianshun; Over, Diana; Douziech, Bénédicte; Zeitouny, Joceline; Giorgi, Michel; Jabin, Ivan; Mest, Yves Le; Reinaud, Olivia

doi:10.1021/ic0620384

Cited by 26 publications

(20 citation statements)

References 11 publications

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“…[Ti(Cp){ t BuC6(H) 3 }] 3 and [Mo=NR{HC6(H) 2 }] 25 are the only monometallic calix [6]arene complexes containing the metal center coordinated directly to the calixarene lower rim. Some other mononuclear complexes with metals such as Cu(I), 26 Cu(II), 27 Zn(II), 28 Pd(II), and Pt(II) 29 were obtained with the aid of nitrogen or phosphorus lower rim substituted calix [6]arene ligands.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

Synthesis of bismuth and antimony complexes of the “larger” calix[n]arenes (n = 6–8); from mononuclear to tetranuclear complexes

2009

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A series of calix[n]arene (n=6-8) bismuth and antimony complexes were synthesized and fully characterized by NMR, X-ray, IR, UV-Vis and elemental analysis. The monobismuth calix[6]arene complex [Bi{tBuC6(H)3}]2 1 was prepared by the reaction of para-tert-butylcalix[6]arene (tBuC6(H)6) with one equivalent of Bi[N(SiMe3)2]3. Complex 1 featured a Bi2(micro-O)2 central core similar to other bismuth calixarene complexes prepared by our group. Reaction of calix[6]arene (HC6(H)6) with two equivalents of Bi(OtBu)3 yielded different outcomes depending on the reaction solvent. If THF was used, complex [Bi{HC6(H)3}] 2 was obtained in 72% yield; however, when toluene was used, complexes 2 and [Bi2{HC6}] 3 were isolated in 23 and 57% yields, respectively. Mononuclear complexes 1 and 2 displayed dimeric structures in the solid state with cone-like conformations for the calixarene ligands. The 1H NMR spectrum of complex 2 displays patterns for an asymmetric structure with two signals in a 2:1 ratio for the unreacted OH groups. Treatment of calix[6]arenes RC6(H)6 (R=H, tBu) with two equivalents of SbR3 (R=OtBu, NMe2) produced dinuclear complexes [Sb2{HC6}] 4, and [Sb2{tBuC6}] 5, respectively. The 1H NMR spectra for the dinuclear complexes 3, 4, and 5 showed the characteristic calixarene pattern for a 1,2,3-alternate conformer. In the process of recrystallization of complex 4 an unexpected trimetallic complex with composition [Sb3O2{HC6(H)}] 4a was obtained in low yield. Treatment of para-tert-butylcalix[7]arene (tBuC7(H)7) with two equivalents of Bi(OtBu)3 produced the bimetallic complex [Bi2O{tBuC7(H)3}]2 6. Complex 6 contains an overall Bi4O2(OAr)8 core system with a structural resemblance to other bimetallic bismuth calixarene complexes reported by our group. The larger para-benzylcalix[8]arene (BnC8(H)8) and calix[8]arene (HC8(H)8) reacted with excess Bi(OtBu)3 to produce the tetranuclear complexes [Bi4O2{HC8}] 7 and [Bi4O2{BnC8}] 8, respectively. The solid state structure of complex 8 featured a dimeric unit with the calixarene ligands in pinched-cone conformation and displaying an overall Bi8O4(OAr)16.H2O core. No metal pi-arene interactions were observed.

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Section: Synthesis and Characterizationmentioning

confidence: 99%

Synthesis of bismuth and antimony complexes of the “larger” calix[n]arenes (n = 6–8); from mononuclear to tetranuclear complexes

2009

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“…As part of our continuous interest in the synthesis and study of calix[6]arene-based receptors for neutral or charged species, we wanted to exploit the cavity-based selectivity of these receptors for the design of highly selective fluorescent systems. In this regard, we were interested in the elaboration of fluorescent derivatives of calix[6]tris(urea) compounds 1a and 1b (Figure ).…”

Section: Introductionmentioning

confidence: 99%

“…11 Moreover, to our knowledge, there are no examples of fluorescent receptors that can bind organic contact ion pairs, 12 as most of the systems are devoted to the recognition of cations, 13 anions, 14 or neutral guests. 15 As part of our continuous interest in the synthesis and study of calix [6]arene-based receptors for neutral 16 or charged 17 species, we wanted to exploit the cavity-based selectivity of these receptors for the design of highly selective fluorescent systems. In this regard, we were interested in the elaboration of fluorescent derivatives of calix [6]tris(urea) compounds 1a and 1b (Figure 1).…”

Section: ■ Introductionmentioning

confidence: 99%

Fluorescent Chemosensors for Anions and Contact Ion Pairs with a Cavity-Based Selectivity

et al. 2014

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The association of a concave macrocyclic compound to one or multiple fluorophores is an appealing strategy for the design of chemosensors. Indeed, as with biological systems, a cavity-based selectivity can be expected with such fluorescent receptors. Examples of calix[6]arene-based systems using this strategy are rare in the literature, and to our knowledge, no examples of fluorescent receptors that can bind organic contact ion pairs have been reported. This report describes the straightforward synthesis of fluorescent calix[6]arene-based receptors 4a and 4b bearing three pyrenyl subunits and the study of their binding properties toward anions and ammonium salts using different spectroscopies. It was found that receptor 4a exhibits a remarkable selectivity for the sulfate anion in DMSO, enabling its selective sensing by fluorescence spectroscopy. In CDCl3, the receptor is able to bind ammonium ions efficiently only in association with the sulfate anion. Interestingly, this cooperative binding of ammonium sulfate salts was also evidenced in a protic environment. Finally, a cavity-based selectivity in terms of size and shape of the guest was observed with both receptors 4a and 4b, opening interesting perspectives on the elaboration of fluorescent cavity-based systems for the selective sensing of biologically relevant ammonium salts such as neurotransmitters.

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“…This motivates us to consider the selection of a required host for the desired construction of 1D Ga nanocrystals. Structurally, calix[6]arene (CA-6) has a high degree of conformational flexibility, [19][20][21][22] which may be an ideal host molecule for the design of 1D Ga nanoarchitecture. Therefore, four Ga materials doped by calix [4]arene (CA-4), 23,24 g-CD 25 and 18-crown-6 (18C-6) 26 were prepared and marked as Ga-a to Ga-d, respectively.…”

Section: Introductionmentioning

confidence: 99%

Distinctive electronic structure, unusual magnetic properties and large enhancement in SERS of 1D gallium nanoribbons achieved by doping calix[6]arene

et al. 2012

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The present work provides a novel route for forming one-dimensional (1D) gallium (Ga) nanoribbon materials with a host molecule calix[6]arene (CA-6) as a template by a facile, one-step and low temperature chemical bath method. Field-emission scanning electron microscopy and transmission electron microscopy showed that the uniform 1D Ga nanoribbon material (Ga-a) can be constructed only in the presence of CA-6, and the formation of ribbon structures is highly dependent on doping ratios and deposition times. Our data indicate that the unusual effect of CA-6 is due to a combination of two factors: a high density of OH groups in the outer surface of its cavity and an appropriate cavity diameter. Especially, the uniform 1D Ga nanoribbon material exhibits a distinct electronic structure and very rare magnetic behaviour when compared to those 3D Ga materials obtained by means of other host molecules: calix[4]arene, g-cyclodextrin and 18-crown-6. For example, of all the Ga materials, the uniform 1D nanoribbon material has the lowest electron density of Ga core levels in light of X-ray photoelectron spectroscopy analysis. This result suggests that there is a stronger molecule-atom interaction between Ga atoms and CA-6 molecules compared with those in other host-guest systems. More importantly, the uniform 1D Ga nanoribbon material exhibits a magnetic transformation from a diamagnetic to a paramagnetic state under the influence of an applied field, which is completely different from those of all the 3D Ga materials and all the irregular Ga nanoribbon materials. Such a transformation is novel in metals and particularly useful in the chemistry of materials since it allows dramatic modifications of magnetic properties of metal nanocrystals. Finally, a strong surfaceenhanced Raman scattering of the uniform 1D Ga nanoribbon material has been observed for organic molecules adsorbed on their surface. Taken together, we believe this work opens a new channel for development of 1D metal-based nanomaterials.

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First Insights into the Electronic Properties of a Cu(II) Center Embedded in the PN₃ Cap of a Calix[6]arene-Based Ligand

Cited by 26 publications

References 11 publications

Synthesis of bismuth and antimony complexes of the “larger” calix[n]arenes (n = 6–8); from mononuclear to tetranuclear complexes

Synthesis of bismuth and antimony complexes of the “larger” calix[n]arenes (n = 6–8); from mononuclear to tetranuclear complexes

Fluorescent Chemosensors for Anions and Contact Ion Pairs with a Cavity-Based Selectivity

Distinctive electronic structure, unusual magnetic properties and large enhancement in SERS of 1D gallium nanoribbons achieved by doping calix[6]arene

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First Insights into the Electronic Properties of a Cu(II) Center Embedded in the PN3 Cap of a Calix[6]arene-Based Ligand

Cited by 26 publications

References 11 publications

Synthesis of bismuth and antimony complexes of the “larger” calix[n]arenes (n = 6–8); from mononuclear to tetranuclear complexes

Synthesis of bismuth and antimony complexes of the “larger” calix[n]arenes (n = 6–8); from mononuclear to tetranuclear complexes

Fluorescent Chemosensors for Anions and Contact Ion Pairs with a Cavity-Based Selectivity

Distinctive electronic structure, unusual magnetic properties and large enhancement in SERS of 1D gallium nanoribbons achieved by doping calix[6]arene

Contact Info

Product

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First Insights into the Electronic Properties of a Cu(II) Center Embedded in the PN₃ Cap of a Calix[6]arene-Based Ligand