2013
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An intrinsically fluorescent glycoligand for direct imaging of ligand trafficking in artificial and living cell systems Article de journal L Garcia; M Lazzaretti; A Diguet; F Mussi; F Bisceglie; J Xie; G Pelosi; A Buschini; D Baigl; C Policar New Journal of Chemistry, 37 (10), p. 3030–3034, 2013. @article{Garcia:2013,
title = {An intrinsically fluorescent glycoligand for direct imaging of ligand trafficking in artificial and living cell systems},
author = {L Garcia and M Lazzaretti and A Diguet and F Mussi and F Bisceglie and J Xie and G Pelosi and A Buschini and D Baigl and C Policar},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84884338239&doi=10.1039%2fc3nj00380a&partnerID=40&md5=227adf277b66a18d63bfec3b8a13ff09},
doi = {10.1039/c3nj00380a},
year = {2013},
date = {2013-01-01},
journal = {New Journal of Chemistry},
volume = {37},
number = {10},
pages = {3030--3034},
abstract = {Glycoligands, sugar-based molecules able to complex metal cations, constitute a new class of molecules with great potential for biological and biochemical applications. To analyze their behaviour in a biological environment, we have synthesized an intrinsically fluorescent glycoligand and analyzed its trafficking in both living (U937 human cancer cells) and artificial (giant unilamellar vesicles) cell systems. We have found that this ligand has moderate cytotoxicity accompanied by specific accumulation in both living and reconstituted membranes, which it can cross to reach inner compartments. © 2013 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Glycoligands, sugar-based molecules able to complex metal cations, constitute a new class of molecules with great potential for biological and biochemical applications. To analyze their behaviour in a biological environment, we have synthesized an intrinsically fluorescent glycoligand and analyzed its trafficking in both living (U937 human cancer cells) and artificial (giant unilamellar vesicles) cell systems. We have found that this ligand has moderate cytotoxicity accompanied by specific accumulation in both living and reconstituted membranes, which it can cross to reach inner compartments. © 2013 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique. |
2012
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Glycosiderophores: Synthesis of tris-hydroxamate siderophores based on a galactose or glycero central scaffold, Fe(III) complexation studies Article de journal C Neff; F Bellot; J -B Waern; F Lambert; J Brandel; G Serratrice; F Gaboriau; C Policar Journal of Inorganic Biochemistry, 112 , p. 59–67, 2012. @article{Neff:2012,
title = {Glycosiderophores: Synthesis of tris-hydroxamate siderophores based on a galactose or glycero central scaffold, Fe(III) complexation studies},
author = {C Neff and F Bellot and J -B Waern and F Lambert and J Brandel and G Serratrice and F Gaboriau and C Policar},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84860271202&doi=10.1016%2fj.jinorgbio.2012.02.030&partnerID=40&md5=67094ead67163b2ab05f9eed02b54bbd},
doi = {10.1016/j.jinorgbio.2012.02.030},
year = {2012},
date = {2012-01-01},
journal = {Journal of Inorganic Biochemistry},
volume = {112},
pages = {59--67},
abstract = {A series of five new hexadentate tris-hydroxamate ligands based on a d-galactose or a glycerol scaffold have been synthesized. Protonation and ferric complex formation constants have been determined from solution studies by potentiometric and spectrophotometric titrations. All ligands form 1:1 Fe:L complexes. The calculated pFe values at pH 7.4 span over the range 19.2-23.0 depending on the scaffold and on the length of the spacers between hydroxamate and central scaffold and on the N-methyl substitution. This new kind of artificial siderophores based on a glycoscaffold is of interest as it opens up an easy way to modulate the pFe. © 2012 Elsevier Inc.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
A series of five new hexadentate tris-hydroxamate ligands based on a d-galactose or a glycerol scaffold have been synthesized. Protonation and ferric complex formation constants have been determined from solution studies by potentiometric and spectrophotometric titrations. All ligands form 1:1 Fe:L complexes. The calculated pFe values at pH 7.4 span over the range 19.2-23.0 depending on the scaffold and on the length of the spacers between hydroxamate and central scaffold and on the N-methyl substitution. This new kind of artificial siderophores based on a glycoscaffold is of interest as it opens up an easy way to modulate the pFe. © 2012 Elsevier Inc. |
A rhenium tris-carbonyl derivative as a single core multimodal probe for imaging (SCoMPI) combining infrared and luminescent properties Article de journal S Clède; F Lambert; C Sandt; Z Gueroui; M Réfrégiers; M -A Plamont; P Dumas; A Vessières; C Policar Chemical Communications, 48 (62), p. 7729–7731, 2012. @article{Clede:2012,
title = {A rhenium tris-carbonyl derivative as a single core multimodal probe for imaging (SCoMPI) combining infrared and luminescent properties},
author = {S Cl\`{e}de and F Lambert and C Sandt and Z Gueroui and M R\'{e}fr\'{e}giers and M -A Plamont and P Dumas and A Vessi\`{e}res and C Policar},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84863947366&doi=10.1039%2fc2cc32163g&partnerID=40&md5=289388c6720aee80e800fb8ad80cdb27},
doi = {10.1039/c2cc32163g},
year = {2012},
date = {2012-01-01},
journal = {Chemical Communications},
volume = {48},
number = {62},
pages = {7729--7731},
abstract = {A rhenium tris-carbonyl derivative has been designed to couple infrared and luminescent detection in cells. Both spectroscopies are consistent with one another; they point out the reliability of the present SCoMPI (for Single Core Multimodal Probe for Imaging) for bimodal imaging and unambiguously indicate a localization at the Golgi apparatus in MDA-MB-231 breast cancer cells. © 2012 The Royal Society of Chemistry.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
A rhenium tris-carbonyl derivative has been designed to couple infrared and luminescent detection in cells. Both spectroscopies are consistent with one another; they point out the reliability of the present SCoMPI (for Single Core Multimodal Probe for Imaging) for bimodal imaging and unambiguously indicate a localization at the Golgi apparatus in MDA-MB-231 breast cancer cells. © 2012 The Royal Society of Chemistry. |
Metal complexation of a Đ -ribose-based ligand decoded by experimental and theoretical studies Article de journal F Cisnetti; J -D Maréchal; M Nicaise; R Guillot; M Desmadril; F Lambert; C Policar European Journal of Inorganic Chemistry, (20), p. 3308–3319, 2012. @article{Cisnetti:2012,
title = {Metal complexation of a {D} -ribose-based ligand decoded by experimental and theoretical studies},
author = {F Cisnetti and J -D Mar\'{e}chal and M Nicaise and R Guillot and M Desmadril and F Lambert and C Policar},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84863687434&doi=10.1002%2fejic.201200322&partnerID=40&md5=0682fc752866de140dd4439a4be02cdd},
doi = {10.1002/ejic.201200322},
year = {2012},
date = {2012-01-01},
journal = {European Journal of Inorganic Chemistry},
number = {20},
pages = {3308--3319},
abstract = {A combination of experimental and theoretical methods have been used to elucidate the complexation properties of a new sugar-derived hexadentate ligand, namely methyl 2,3,4-tri-O-(2-picolyl)-β-D-ribopyranoside (L). The coordination bond lengths in the complexes with Mn II, Co II, Ni II, and Zn II show substantial deviations from ideal octahedra with deformation towards trigonal-prismatic geometries, which is indicative of a conformationally constrained ligand. The metal-cation-ligand interactions were studied for L and the acyclic analogue L' [1,2,3-tri-O-(2-picolyl)-1,2,3-propanetriol] by spectroscopic methods and isothermal calorimetric titrations for the series Mn II, Co II, Ni II, Zn II, and Cu II. The results indicate a stabilization of the complexes obtained with L compared with L', depending on the nature of the metal. Molecular modeling studies showed that the presence of the sugar moiety strongly favors conformations compatible with metal binding, which suggests an entropic origin of the stabilization of L complexes with regards to L' complexes. Moreover, the differences in the metal chelation profiles of L and L' are related to the constraints in the sugar group in the metal-bound structures. This study shows that foreseeing the degree of preorganization of flexible ligands may drive the design of a new generation of chelating compounds. A new sugar-derived ligand, with its coordination site embedded in a pyranoside cycle in the chair conformation, has been designed. Its transition-metal complexes were characterized by experimental and complexation methods and revealed a dramatic impact of the preorganization and complementarity of the carbohydrate scaffold on the metal binding. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
A combination of experimental and theoretical methods have been used to elucidate the complexation properties of a new sugar-derived hexadentate ligand, namely methyl 2,3,4-tri-O-(2-picolyl)-β-D-ribopyranoside (L). The coordination bond lengths in the complexes with Mn II, Co II, Ni II, and Zn II show substantial deviations from ideal octahedra with deformation towards trigonal-prismatic geometries, which is indicative of a conformationally constrained ligand. The metal-cation-ligand interactions were studied for L and the acyclic analogue L' [1,2,3-tri-O-(2-picolyl)-1,2,3-propanetriol] by spectroscopic methods and isothermal calorimetric titrations for the series Mn II, Co II, Ni II, Zn II, and Cu II. The results indicate a stabilization of the complexes obtained with L compared with L', depending on the nature of the metal. Molecular modeling studies showed that the presence of the sugar moiety strongly favors conformations compatible with metal binding, which suggests an entropic origin of the stabilization of L complexes with regards to L' complexes. Moreover, the differences in the metal chelation profiles of L and L' are related to the constraints in the sugar group in the metal-bound structures. This study shows that foreseeing the degree of preorganization of flexible ligands may drive the design of a new generation of chelating compounds. A new sugar-derived ligand, with its coordination site embedded in a pyranoside cycle in the chair conformation, has been designed. Its transition-metal complexes were characterized by experimental and complexation methods and revealed a dramatic impact of the preorganization and complementarity of the carbohydrate scaffold on the metal binding. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. |
Evaluation of the anti-oxidant properties of a SOD-mimic Mn-complex in activated macrophages Article de journal Anne-Sophie Bernard; Claire Giroud; Vincent H Y Ching; Anne Meunier; Vinita Ambike; Christian Amatore; Manon Guille-Collignon; Frederic Lemaitre; Clotilde Policar Dalton Transactions, 41 (21), p. 6399-6403, 2012, (Times Cited: 23). @article{,
title = {Evaluation of the anti-oxidant properties of a SOD-mimic Mn-complex in activated macrophages},
author = {Anne-Sophie Bernard and Claire Giroud and Vincent H Y Ching and Anne Meunier and Vinita Ambike and Christian Amatore and Manon Guille-Collignon and Frederic Lemaitre and Clotilde Policar},
year = {2012},
date = {2012-01-01},
journal = {Dalton Transactions},
volume = {41},
number = {21},
pages = {6399-6403},
note = {Times Cited: 23},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
Recent analytical applications of molecular spectroscopy in bioorganometallic chemistrypart I: Metal carbonyls Article de journal I S Butler; R P Kengne-Momo; G Jaouen; C Policar; A Vessières Applied Spectroscopy Reviews, 47 (7), p. 531–549, 2012. @article{Butler:2012,
title = {Recent analytical applications of molecular spectroscopy in bioorganometallic chemistrypart I: Metal carbonyls},
author = {I S Butler and R P Kengne-Momo and G Jaouen and C Policar and A Vessi\`{e}res},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84865204418&doi=10.1080%2f05704928.2012.673189&partnerID=40&md5=520598e533375e3ff67b73f9e50d4386},
doi = {10.1080/05704928.2012.673189},
year = {2012},
date = {2012-01-01},
journal = {Applied Spectroscopy Reviews},
volume = {47},
number = {7},
pages = {531--549},
abstract = {This is the first part of a two-part review on the analytical applications of molecular spectroscopy in bioorganometallic chemistry since 2005. In this case, radiopharmaceutical studies are included and the review is focused particularly on biological molecules labeled with metal carbonyl fragments. Copyright © Taylor & Francis Group, LLC.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This is the first part of a two-part review on the analytical applications of molecular spectroscopy in bioorganometallic chemistry since 2005. In this case, radiopharmaceutical studies are included and the review is focused particularly on biological molecules labeled with metal carbonyl fragments. Copyright © Taylor & Francis Group, LLC. |
Recent applications of molecular spectroscopy in bioorganometallic chemistry-Part 2: Ferrocenes and other organometallic complexes Article de journal I S Butler; R P Kengne-Momo; A Vessières; G Jaouen; C Policar Applied Spectroscopy Reviews, 47 (8), p. 620–632, 2012. @article{Butler:2012a,
title = {Recent applications of molecular spectroscopy in bioorganometallic chemistry-Part 2: Ferrocenes and other organometallic complexes},
author = {I S Butler and R P Kengne-Momo and A Vessi\`{e}res and G Jaouen and C Policar},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84867002904&doi=10.1080%2f05704928.2012.697088&partnerID=40&md5=9a894613d259bfe47cd1f47469a86497},
doi = {10.1080/05704928.2012.697088},
year = {2012},
date = {2012-01-01},
journal = {Applied Spectroscopy Reviews},
volume = {47},
number = {8},
pages = {620--632},
abstract = {This is the second part of an overview of the applications of the various molecular spectroscopic methods that have been employed in bioorganometallic chemistry research since 2005 focusing on ferrocenes and other non-metal carbonyl organometallic complexes. These spectroscopic methods encompass infrared (IR), nuclear magnetic resonance (NMR), mass, Raman, ultraviolet-visible (UV-Vis), and several other less common spectroscopic techniques. © 2012 Taylor & Francis Group, LLC.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
This is the second part of an overview of the applications of the various molecular spectroscopic methods that have been employed in bioorganometallic chemistry research since 2005 focusing on ferrocenes and other non-metal carbonyl organometallic complexes. These spectroscopic methods encompass infrared (IR), nuclear magnetic resonance (NMR), mass, Raman, ultraviolet-visible (UV-Vis), and several other less common spectroscopic techniques. © 2012 Taylor & Francis Group, LLC. |
2011
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Intrinsically fluorescent glycoligands to study metal selectivity Article de journal L Garcia; S Maisonneuve; J Oudinet-Sin Marcu; R Guillot; F Lambert; J Xie; C Policar Inorganic Chemistry, 50 (22), p. 11353–11362, 2011. @article{Garcia:2011,
title = {Intrinsically fluorescent glycoligands to study metal selectivity},
author = {L Garcia and S Maisonneuve and J Oudinet-Sin Marcu and R Guillot and F Lambert and J Xie and C Policar},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-81255195281&doi=10.1021%2fic200897v&partnerID=40&md5=2d82616942d473b2774c71363fb8ff6a},
doi = {10.1021/ic200897v},
year = {2011},
date = {2011-01-01},
journal = {Inorganic Chemistry},
volume = {50},
number = {22},
pages = {11353--11362},
abstract = {Glycoligands are a versatile family of ligands centered on a sugar platform and functionalized by Lewis bases. In this article, pentofuranoses were appended with the fluoroionophores 4-(pyridin-2′-yl)-1,2,3-triazol-1-yl and 4-(2′,1′,3′-benzothiadiazol-4′-yl)-1,2,3-triazol-1- yl using the "click-like" cycloaddition [2 + 3] of Huisgen catalyzed by copper(I). Their fluorescence properties were used to study metal cation complexation. A possible selective functionalization of furanoscaffolds allows the synthesis of "mixed" glycoligands with the successive insertion of these different fluoroionophores. The metal selectivity and the chelating behavior of these six resulting intrinsically fluorescent glycoligands were investigated. The change in the configuration at the carbon C3 of furanose did not influence either the metal selectivity or the binding constants. However, different selectivities and binding constants were found to depend on the nature of the fluoroionophore moieties. Overall, the triazolylbenzothiadiazolyl chelating group was shown to be less efficient than the triazolylpyridyl claw for complexation. Interestingly enough, the triazolylbenzothiadiazolyl claw, which fluoresces in the visible range, did not interfere in the binding and selectivity of the more efficient triazolylpyridyl claw. This study suggests that the triazolylbenzothiadiazolyl moiety could be used as an adequate fluorescent reporter to qualitatively monitor complexation of other moieties. © 2011 American Chemical Society.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Glycoligands are a versatile family of ligands centered on a sugar platform and functionalized by Lewis bases. In this article, pentofuranoses were appended with the fluoroionophores 4-(pyridin-2′-yl)-1,2,3-triazol-1-yl and 4-(2′,1′,3′-benzothiadiazol-4′-yl)-1,2,3-triazol-1- yl using the "click-like" cycloaddition [2 + 3] of Huisgen catalyzed by copper(I). Their fluorescence properties were used to study metal cation complexation. A possible selective functionalization of furanoscaffolds allows the synthesis of "mixed" glycoligands with the successive insertion of these different fluoroionophores. The metal selectivity and the chelating behavior of these six resulting intrinsically fluorescent glycoligands were investigated. The change in the configuration at the carbon C3 of furanose did not influence either the metal selectivity or the binding constants. However, different selectivities and binding constants were found to depend on the nature of the fluoroionophore moieties. Overall, the triazolylbenzothiadiazolyl chelating group was shown to be less efficient than the triazolylpyridyl claw for complexation. Interestingly enough, the triazolylbenzothiadiazolyl claw, which fluoresces in the visible range, did not interfere in the binding and selectivity of the more efficient triazolylpyridyl claw. This study suggests that the triazolylbenzothiadiazolyl moiety could be used as an adequate fluorescent reporter to qualitatively monitor complexation of other moieties. © 2011 American Chemical Society. |
Proton-coupled electron transfers in biomimetic water bound metal complexes. the electrochemical approach Article de journal E Anxolabéhère-Mallart; C Costentin; C Policar; M Robert; J -M Savéant; A -L Teillout Faraday Discussions, 148 , p. 83–95, 2011. @article{Anxolabehere-Mallart:2011,
title = {Proton-coupled electron transfers in biomimetic water bound metal complexes. the electrochemical approach},
author = {E Anxolab\'{e}h\`{e}re-Mallart and C Costentin and C Policar and M Robert and J -M Sav\'{e}ant and A -L Teillout},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-79952268478&doi=10.1039%2fc004276e&partnerID=40&md5=24036168d6b9ca482d1b9f949b3a5995},
doi = {10.1039/c004276e},
year = {2011},
date = {2011-01-01},
journal = {Faraday Discussions},
volume = {148},
pages = {83--95},
abstract = {Water-bound metal (M) complexes play a central role in the catalytic centers of natural systems such as Photosystem II (PSII), superoxide dismutase, cytochrome c oxidase and others. In these systems, electron transfer reactions involving the metal center are coupled to proton transfers. Besides its fundamental interest, comprehension of these reactions and of possible bio-inspired catalytic devices is an additional motivation for studying the coupling between proton and electron transfer (proton-coupled electron transfers, PCET), starting with an aqua-MII/hydroxo-MIII couple, and going to higher oxidation degrees as in the case of PSII (hydroxo-MIII/oxo-MIV couple). Factors that determine the occurrence of the stepwise and concerted pathways are recalled from the illustrating example of a recently described mononuclear osmium complex, thus opening perspectives for further studies of the biomimicking complex. PCET in a mononuclear aqua/hydroxo manganese couple was then studied using the electrochemical approach. © 2011 The Royal Society of Chemistry.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Water-bound metal (M) complexes play a central role in the catalytic centers of natural systems such as Photosystem II (PSII), superoxide dismutase, cytochrome c oxidase and others. In these systems, electron transfer reactions involving the metal center are coupled to proton transfers. Besides its fundamental interest, comprehension of these reactions and of possible bio-inspired catalytic devices is an additional motivation for studying the coupling between proton and electron transfer (proton-coupled electron transfers, PCET), starting with an aqua-MII/hydroxo-MIII couple, and going to higher oxidation degrees as in the case of PSII (hydroxo-MIII/oxo-MIV couple). Factors that determine the occurrence of the stepwise and concerted pathways are recalled from the illustrating example of a recently described mononuclear osmium complex, thus opening perspectives for further studies of the biomimicking complex. PCET in a mononuclear aqua/hydroxo manganese couple was then studied using the electrochemical approach. © 2011 The Royal Society of Chemistry. |
Subcellular IR imaging of a metal-carbonyl moiety using photothermally induced resonance Article de journal C Policar; J B Waern; M -A Plamont; S Clède; C Mayet; R Prazeres; J -M Ortega; A Vessières; A Dazzi Angewandte Chemie - International Edition, 50 (4), p. 860–864, 2011. @article{Policar:2011,
title = {Subcellular IR imaging of a metal-carbonyl moiety using photothermally induced resonance},
author = {C Policar and J B Waern and M -A Plamont and S Cl\`{e}de and C Mayet and R Prazeres and J -M Ortega and A Vessi\`{e}res and A Dazzi},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-78650905440&doi=10.1002%2fanie.201003161&partnerID=40&md5=68f3379717f4b84ab8336cdb50461a5f},
doi = {10.1002/anie.201003161},
year = {2011},
date = {2011-01-01},
journal = {Angewandte Chemie - International Edition},
volume = {50},
number = {4},
pages = {860--864},
abstract = {Some like it hot! The photothermally induced resonance technique, in which an AFM microscope is coupled to a tunable pulsed IR laser, allows IR mapping and gives access to local IR spectra at the subcellular level. A metal-carbonyl compound was internalized in cells and detected in the cell nucleus thanks to its IR signature. The local IR spectrum at the nucleus showed the characteristic IR bands of the Re(CO)3 unit. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Some like it hot! The photothermally induced resonance technique, in which an AFM microscope is coupled to a tunable pulsed IR laser, allows IR mapping and gives access to local IR spectra at the subcellular level. A metal-carbonyl compound was internalized in cells and detected in the cell nucleus thanks to its IR signature. The local IR spectrum at the nucleus showed the characteristic IR bands of the Re(CO)3 unit. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
2010
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Sugars to control ligand shape in metal complexes: Conformationally constrained glycoligands with a predetermination of stereochemistry and a structural control Article de journal L Garcia; S Maisonneuve; J Xie; R Guillot; P Dorlet; E Rivière; M Desmadril; F Lambert; C Policar Inorganic Chemistry, 49 (16), p. 7282–7288, 2010. @article{Garcia:2010,
title = {Sugars to control ligand shape in metal complexes: Conformationally constrained glycoligands with a predetermination of stereochemistry and a structural control},
author = {L Garcia and S Maisonneuve and J Xie and R Guillot and P Dorlet and E Rivi\`{e}re and M Desmadril and F Lambert and C Policar},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-77955475481&doi=10.1021%2fic1002379&partnerID=40&md5=d7e719000261dc5be94c8bbf72ce40ca},
doi = {10.1021/ic1002379},
year = {2010},
date = {2010-01-01},
journal = {Inorganic Chemistry},
volume = {49},
number = {16},
pages = {7282--7288},
abstract = {In coordination chemistry, ligand shape can be used to tune properties, such as metal selectivity, coordination number, electronic structure, redox potential, and metal center stereochemistry including coordination helicates formation, and also to generate cavities for encapsulation. The results presented in this article indicate that two epimeric glycoligands (3 and 4) based on the conformationally restrained xylo-and ribo-1,2-O- isopropylidenefurano scaffolds are preorganized in water through π-π stacking due to hydrophobic interactions, as evidenced from excimer observation. The structure obtained in the solid state for one of the Cu(II) complexes (5) is chiral, with an original helical chirality arising from the coiling of the two ligands around the Cu-Cu axis. It shows an unusual double-deck type structure, with π-π interaction between two triazoyl-pyridyl rings and with a small cavity between the two Cu(II) ions able to host a bridging water molecule, as suggested by electron paramagnetic resonance. The Cu(II) complex from the epimeric ligand (6) shows similar properties with a mirror-image CD spectrum in the d-d region of the Cu(II). There is a predetermination of chirality at the metal center by the glycoligand induced by the C3 configuration, 6 and 5 being pseudoenantiomers. Interestingly, the stereochemistry at the metal center is here controlled by the combination of π-stacking and chiral backbone. © 2010 American Chemical Society.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
In coordination chemistry, ligand shape can be used to tune properties, such as metal selectivity, coordination number, electronic structure, redox potential, and metal center stereochemistry including coordination helicates formation, and also to generate cavities for encapsulation. The results presented in this article indicate that two epimeric glycoligands (3 and 4) based on the conformationally restrained xylo-and ribo-1,2-O- isopropylidenefurano scaffolds are preorganized in water through π-π stacking due to hydrophobic interactions, as evidenced from excimer observation. The structure obtained in the solid state for one of the Cu(II) complexes (5) is chiral, with an original helical chirality arising from the coiling of the two ligands around the Cu-Cu axis. It shows an unusual double-deck type structure, with π-π interaction between two triazoyl-pyridyl rings and with a small cavity between the two Cu(II) ions able to host a bridging water molecule, as suggested by electron paramagnetic resonance. The Cu(II) complex from the epimeric ligand (6) shows similar properties with a mirror-image CD spectrum in the d-d region of the Cu(II). There is a predetermination of chirality at the metal center by the glycoligand induced by the C3 configuration, 6 and 5 being pseudoenantiomers. Interestingly, the stereochemistry at the metal center is here controlled by the combination of π-stacking and chiral backbone. © 2010 American Chemical Society. |
2009
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Design, self-assembly, and molecular structures of 3D copper(II) capsules templated by BF4 - guest anions Article de journal C Desmarets; C Policar; L -M Chamoreau; H Amouri European Journal of Inorganic Chemistry, (29-30), p. 4396–4400, 2009. @article{Desmarets:2009,
title = {Design, self-assembly, and molecular structures of 3D copper(II) capsules templated by BF4 - guest anions},
author = {C Desmarets and C Policar and L -M Chamoreau and H Amouri},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-70350150888&doi=10.1002%2fejic.200900606&partnerID=40&md5=a0e5525563850dda7c2083f3b040390c},
doi = {10.1002/ejic.200900606},
year = {2009},
date = {2009-01-01},
journal = {European Journal of Inorganic Chemistry},
number = {29-30},
pages = {4396--4400},
abstract = {The synthesis of two 3D M2L4 copper(II) capsules, [BF4C(CH3CN)2Cu2(L 1)4][BF4]3 (1) and ([BF 4C(BF4J2Cu2(L1) 4][BF4]) (2), by using l,3-(benzimidazol-l-ylmethyl)-2, 5dimethoxy-4,6-dimethylbenzene (L1) as a semirigid exobidentate ligand and [Cu(CH3CN)4][BF4]2 as a metallobrick is reported. Single-crystal X-ray diffraction studies show the encapsulation of a BF4 - anion in 1 and 2. Moreover, 2 dis-played three coordinated BF4 - anions, which is rare in supramolecular coordination host-guest chemistry. Remarkably, in both metallocages the weakly coordinated BF4 - anion acts as a template and interacts with the metal center through a weak Cu⋯F contact. © Wiley-VCH Verlag GmbH & Co. KGaA.},
keywords = {},
pubstate = {published},
tppubtype = {article}
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The synthesis of two 3D M2L4 copper(II) capsules, [BF4C(CH3CN)2Cu2(L 1)4][BF4]3 (1) and ([BF 4C(BF4J2Cu2(L1) 4][BF4]) (2), by using l,3-(benzimidazol-l-ylmethyl)-2, 5dimethoxy-4,6-dimethylbenzene (L1) as a semirigid exobidentate ligand and [Cu(CH3CN)4][BF4]2 as a metallobrick is reported. Single-crystal X-ray diffraction studies show the encapsulation of a BF4 - anion in 1 and 2. Moreover, 2 dis-played three coordinated BF4 - anions, which is rare in supramolecular coordination host-guest chemistry. Remarkably, in both metallocages the weakly coordinated BF4 - anion acts as a template and interacts with the metal center through a weak Cu⋯F contact. © Wiley-VCH Verlag GmbH & Co. KGaA. |
