2,4-Substituted bispidines as rigid hosts for versatile applications: from κ-opioid receptor to metal coordination

Nonat, Aline; Roux, Amandine Le; Sy, Maryame; Charbonnière, Loı̈c J.

doi:10.1039/c9dt03480c

Cited by 33 publications

(36 citation statements)

References 51 publications

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“…The rigidity of the bispidine platform [50–52] and the versatility in terms of denticity and donor types as well as the synthetic availability of a large number of ligands, makes this type of chelator a favorable platform for a variety of applications, including Ln III based luminescence probes [53–56] . Moreover, with negatively charged donors ( e. g .…”

Section: Introductionmentioning

confidence: 99%

“…The rigidity of the bispidine platform [50][51][52] and the versatility in terms of denticity and donor types as well as the synthetic availability of a large number of ligands, makes this type of chelator a favorable platform for a variety of applications, including Ln III based luminescence probes. [53][54][55][56] Moreover, with negatively charged donors (e. g. carboxylates) or non-coordinating substituents, the overall charge of the complexes may be affected, allowing to tune the cell permeability for in-cell imaging. Also, a number of bispidine derivatives have been reported that allow their attachment to biological vectors; of particular interest is the substitution at C9, i. e. remote from the coordination site.…”

Section: Introductionmentioning

confidence: 99%

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Excited State Properties of Lanthanide(III) Complexes with a Nonadentate Bispidine Ligand

Abad-Galán

Cieslik

Comba

et al. 2021

Chemistry A European J

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Eu III , Tb III , Gd III and Yb III complexes of the nonadentate bispidine derivative L 2 (bispidine = 3,7-diazabicyclo [3.3.1]nonane) were successfully synthesized and their emission properties studied. The X-ray crystallography reveals full encapsulation by the nonadentate ligand L 2 that enforces to all Ln III cations a common highly symmetrical capped square antiprismatic (CSAPR) coordination geometry (pseudo C 4v symmetry). The well-resolved identical emission spectra in solid state and in solution confirm equal structures in both media. As therefore expected, this results in long-lived excited states and high emission quantum yields ([Eu III L 2 ] + , H 2 O, 298 K, τ = 1.51 ms, ϕ = 0.35; [Tb III L 2 ] + , H 2 O, 298 K, τ = 1.95 ms, ϕ = 0.68). Together with the very high kinetic and thermodynamic stabilities, these complexes are a possible basis for interesting biological probes.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Excited State Properties of Lanthanide(III) Complexes with a Nonadentate Bispidine Ligand

Abad-Galán

Cieslik

Comba

et al. 2021

Chemistry A European J

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“…A fused bicyclic skeleton of two piperidine molecules named 3,7-diazabicyclo[3.3.1]nonane, was synthesized for the first time by Mannich [1] in 1930 and was later impregnated by transition metals by Stetter [2] and Haller [3] in 1957 and 1969 respectively. Since then, this molecular scaffold named bispidine, has been subjected to various kinds of studies involving coordination chemistry, [4][5][6][7] diverse organic synthesis, [8][9][10][11] radiopharmaceutical chemistry, [12] and also medicinal chemistry. [13][14][15][16] There could be three structural conformers of bispidine, as shown in Figure 1.…”

Section: Introductionmentioning

confidence: 99%

Eccentricities in Spectroscopy and Reactivity of Non‐Heme Metal Intermediates Contained in Bispidine Scaffolds

Mukherjee

Sastri

2020

Israel Journal of Chemistry

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Ligand framework in a metal complex has a pivotal role to play in orchestrating the spectroscopic and reactivity parameters. High-valent non-heme metal intermediates are known to be crucial species in the catalytic cycles of several metalloenzymes. Among the plethora of a variety of ligand frameworks employed in bioinorganic chemistry, the bispidine molecular scaffold is unique and privileged. In this review, we intend to discuss the overwhelming effects of the bispidine ligand scaffold in tuning the spectroscopic signatures and reactivity parameters of non-heme metal intermediates. The basic skeleton constituting a fused and rigid bicyclic diamine framework with its tentacles tethered to C2, C4, N3 and N7 provides tuneable features to both the primary and secondary coordination spheres. Therefore, the bispidine framework offers a handle to optimize the balance of rigidity and flexibility in a coordination molecule which is thereby important in understanding the rich but surprising results in the reactivity of metal intermediates contained in these scaffolds. Herein, we summarize the significant developments in different types of oxidation reactions of reactive metal intermediates stabilized in bispidine ligands and noted their mechanistic details.

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“…Bispidines (chelators based on a3 ,7-diazabicyclo[3.3.1]nonane core) are widely used chelators with ah ighly preorga-nised coordinatings ite ( Figure 1). [25,26] They have been used to complexarange of metals, including radiometals such as 64 Cu, complexes of which were found to be remarkably inert. [27,28] Their applicationt oG a III complexation, and particularly 68 Ga complexation, remains relativelyu nexplored.…”

Section: Introductionmentioning

confidence: 99%

Evaluation of a Bispidine‐Based Chelator for Gallium‐68 and of the Porphyrin Conjugate as PET/PDT Theranostic Agent

Price

Yap

Gillet

et al. 2020

Chemistry A European J

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In this study a bispidine ligand has been applied to the complexation of gallium(III) and radiolabelled with gallium‐68 for the first time. Despite its 5‐coordinate nature, the resulting complex is stable in serum for over two hours, demonstrating a ligand system well matched to the imaging window of gallium‐68 positron emission tomography (PET). To show the versatility of the bispidine ligand and its potential use in PET, the bifunctional chelator was conjugated to a porphyrin, producing a PET/PDT‐theranostic, which showed the same level of stability to serum as the non‐conjugated gallium‐68 complex. The PET/PDT complex killed >90 % of HT‐29 cells upon light irradiation at 50 μm. This study shows bispidines have the versatility to be used as a ligand system for gallium‐68 in PET.

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2,4-Substituted bispidines as rigid hosts for versatile applications: from κ-opioid receptor to metal coordination

Abstract: Bispidines and their applications in medicine, catalysis, magnetism and medical imaging: what do we know about the influence of substituents?

Cited by 33 publications

References 51 publications

Excited State Properties of Lanthanide(III) Complexes with a Nonadentate Bispidine Ligand

Excited State Properties of Lanthanide(III) Complexes with a Nonadentate Bispidine Ligand

Eccentricities in Spectroscopy and Reactivity of Non‐Heme Metal Intermediates Contained in Bispidine Scaffolds

Evaluation of a Bispidine‐Based Chelator for Gallium‐68 and of the Porphyrin Conjugate as PET/PDT Theranostic Agent

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