Calixarene-Based Copper(I) Complexes as Models for Monocopper Sites in Enzymes

Blanchard, Sébastien; Clainche, Loïc Le; Rager, Marie‐Noëlle; Chansou, Benoît; Tuchagues, Jean‐Pierre; Duprat, Arthur F.; Mest, Yves Le; Reinaud, Olivia

doi:10.1002/(sici)1521-3773(19981016)37:19<2732::aid-anie2732>3.0.co;2-7

Cited by 116 publications

(71 citation statements)

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“…Like the [Cu(L)X] system, the ligand constrains the Cu I centre in a tetrahedral environment and provides a hydrophobic cavity around the axial coordination site, therefore providing a means of stabilising the Cu I state. 27 Where X = NO 2 − the resulting complex shows nitrite in a nitro coordination mode. This complex exhibits a quasi-reversible Cu I/II redox couple like that seen in 2 at 0.41 V vs. Ag/AgCl (DE = 100 mV).…”

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confidence: 99%

Syntheses of copper(i)cis-1,3,5-tri-iminocyclohexane complexes

et al. 2006

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Copper(I) complexes of the ligand cis-1, 3,5-tris(cinnamylideneamino)cyclohexane (L) have been prepared from a versatile precursor complex, [Cu I (L)NCMe]BF 4 , which incorporates a labile acetonitrile ligand that can be exchanged to give a range of new Cu(L)X complexes (where X = Cl, Br, NO 2 , SPh). 1 H NMR spectra and X-ray structures of the Cl, Br and NO 2 complexes show L coordinated in a symmetric fashion about the copper centre. The complexes have been further characterised using UV/Visible spectroscopy and cyclic voltammetry. CuLCl shows an electrochemically reversible Cu I/II redox couple at 0.51 V (vs. Ag/AgCl) while the CuLNO 2 complex shows an analogous quasi-reversible wave at 0.41 V (vs. Ag/AgCl).

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Section: Resultsmentioning

confidence: 99%

Syntheses of copper(i)cis-1,3,5-tri-iminocyclohexane complexes

et al. 2006

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“…Inspired by Nature (7,8), we have developed a calixarene-based system that mimics some aspects of mononuclear metalloenzyme active sites. The model compounds offer a hydrophobic cone-shaped cavity to a guest molecule and present an additional binding site at the narrow end in the form of a fixed metal ion (9). The host-guest metal coordination and other noncovalent interactions within the cone drive the selective recognition events (10).…”

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confidence: 99%

Multipoint molecular recognition within a calix[6]arene funnel complex

Coquière

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Martí

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

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A multipoint recognition system based on a calix[6]arene is described. The calixarene core is decorated on alternating aromatic subunits by 3 imidazole arms at the small rim and 3 aniline groups at the large rim. This substitution pattern projects the aniline nitrogens toward each other when Zn(II) binds at the Tris-imidazole site or when a proton binds at an aniline. The XRD structure of the monoprotonated complex having an acetonitrile molecule bound to Zn(II) in the cavity revealed a constrained geometry at the metal center reminiscent of an entatic state. Computer modeling suggests that the aniline groups behave as a tritopic monobasic site in which only 1 aniline unit is protonated and interacts with the other 2 through strong hydrogen bonding. The metal complex selectively binds a monoprotonated diamine vs. a monoamine through multipoint recognition: coordination to the metal ion at the small rim, hydrogen bonding to the calix-oxygen core, CH/ interaction within the cavity's aromatic walls, and H-bonding to the anilines at the large rim.amines ͉ biomimetic receptor ͉ host-guest interactions ͉ Zn complex M olecular recognition is a fundamental process in biology arising from weak, noncovalent interactions such as electrostatics, hydrogen-bonding CH/ and cation/ interactions as well as hydrophobic effects. Synthetic receptors (1-6) offer models for understanding the driving forces that govern the recognition event and provide applications for developing technologies such as sensor devices. Inspired by Nature (7, 8), we have developed a calixarene-based system that mimics some aspects of mononuclear metalloenzyme active sites. The model compounds offer a hydrophobic cone-shaped cavity to a guest molecule and present an additional binding site at the narrow end in the form of a fixed metal ion (9). The host-guest metal coordination and other noncovalent interactions within the cone drive the selective recognition events (10). The flexible calix core allows adjustment of its properties (11) for the recognition of a range of guests (12, 13). Among the 3 generations (14-16) of these so-called funnel complexes, the most flexible one features coordination of the metal ion to 3 appended imidazole arms at the small rim (Fig. 1). This fixes 3 aromatic walls in a well-defined cone-shaped cavity required of a host structure.The prototype of this family of biomimetic receptors is ligand 1 tBu , a calix[6]arene functionalized in alternate positions at the small rim by methyl and 2-methyl-N-methylimidazole groups (17). Recent developments related to the large rim functionalization of this system have expanded its versatility, allowing tuning its properties such as water solubility (13,18). It also opened a route to ditopic receptors (19)(20). Specifically ligand 1 NH2 presents 3 amino functions at the large rim on aromatic units that alternate with those bearing the imidazole arms. Besides a significant increase of the hydrophilicity, replacing 3 tBu groups for NH 2 at the large rim was shown to (i) widen the door for gues...

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“…The crystal structures of the out/out and in/out isomer of amide based furano-catenanes, [2] amide based catenanes and catenanes, where an amide group is substituted by a sulfonamide group, [3] are presented and compared. For the first time X-ray crystal structures of amide based [1]rotaxanes and the [2]rotaxane from which they were derived are shown.…”

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confidence: 99%

“…For the first time X-ray crystal structures of amide based [1]rotaxanes and the [2]rotaxane from which they were derived are shown.…”

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confidence: 99%