2014
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Conjugation of a new series of dithiocarbazate schiff base copper(II) complexes with vectors selected to enhance antibacterial activity Article de journal M L Low; L Maigre; P Dorlet; R Guillot; J -M Pagès; K A Crouse; C Policar; N Delsuc Bioconjugate Chemistry, 25 (12), p. 2269–2284, 2014. @article{Low:2014,
title = {Conjugation of a new series of dithiocarbazate schiff base copper(II) complexes with vectors selected to enhance antibacterial activity},
author = {M L Low and L Maigre and P Dorlet and R Guillot and J -M Pag\`{e}s and K A Crouse and C Policar and N Delsuc},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84918505283&doi=10.1021%2fbc5004907&partnerID=40&md5=d51ad81235fa7fd9aec14b7acd2c908a},
doi = {10.1021/bc5004907},
year = {2014},
date = {2014-01-01},
journal = {Bioconjugate Chemistry},
volume = {25},
number = {12},
pages = {2269--2284},
abstract = {A new series of six Schiff bases derived from S-methyldithiocarbazate (SMDTC) and S-benzyldithiocarbazate (SBDTC) with methyl levulinate (SMML, SBML), levulinic acid (SMLA, SBLA), and 4-carboxybenzaldehyde (SM4CB, SB4CB) were reacted with copper(II), producing complexes of general formula MLtextlessinftextgreater2textless/inftextgreater (M = Cu(II)},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
A new series of six Schiff bases derived from S-methyldithiocarbazate (SMDTC) and S-benzyldithiocarbazate (SBDTC) with methyl levulinate (SMML, SBML), levulinic acid (SMLA, SBLA), and 4-carboxybenzaldehyde (SM4CB, SB4CB) were reacted with copper(II), producing complexes of general formula MLtextlessinftextgreater2textless/inftextgreater (M = Cu(II) |
Electrochemical formation and reactivity of a manganese peroxo complex: Acid driven Ħ2O2 generation vs. O-O bond cleavage Article de journal H Y V Ching; E Anxolabéhère-Mallart; H E Colmer; C Costentin; P Dorlet; T A Jackson; C Policar; M Robert Chemical Science, 5 (6), p. 2304–2310, 2014. @article{Ching:2014,
title = {Electrochemical formation and reactivity of a manganese peroxo complex: Acid driven {H}2O2 generation vs. O-O bond cleavage},
author = {H Y V Ching and E Anxolab\'{e}h\`{e}re-Mallart and H E Colmer and C Costentin and P Dorlet and T A Jackson and C Policar and M Robert},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84900329910&doi=10.1039%2fc3sc53469c&partnerID=40&md5=8b4ecc598d6455d82b1681e608484bc1},
doi = {10.1039/c3sc53469c},
year = {2014},
date = {2014-01-01},
journal = {Chemical Science},
volume = {5},
number = {6},
pages = {2304--2310},
abstract = {The formation of a side-on peroxo [MnIIIL(O2)] complex (L = phenolato-containing pentadentate ligand), resulting from the reaction of electrochemically reduced O2 and [MnIIL] +, is monitored in DMF using cyclic voltammetry, low temperature electronic absorption spectroscopy and electron paramagnetic resonance spectroscopy. Mechanistic studies based on cyclic voltammetry reveal that upon addition of a strong acid the Mn-O bond is broken, resulting in the release of H2O2, whereas in the presence of a weak acid the O-O bond is cleaved via a concerted dissociative electron transfer. This dichotomy of M-O versus O-O bond cleavage is unprecedented for peroxomanganese(iii) complexes and the latter offers a route for electrochemical O2 activation by a manganese(ii) complex. This journal is © the Partner Organisations 2014.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The formation of a side-on peroxo [MnIIIL(O2)] complex (L = phenolato-containing pentadentate ligand), resulting from the reaction of electrochemically reduced O2 and [MnIIL] +, is monitored in DMF using cyclic voltammetry, low temperature electronic absorption spectroscopy and electron paramagnetic resonance spectroscopy. Mechanistic studies based on cyclic voltammetry reveal that upon addition of a strong acid the Mn-O bond is broken, resulting in the release of H2O2, whereas in the presence of a weak acid the O-O bond is cleaved via a concerted dissociative electron transfer. This dichotomy of M-O versus O-O bond cleavage is unprecedented for peroxomanganese(iii) complexes and the latter offers a route for electrochemical O2 activation by a manganese(ii) complex. This journal is © the Partner Organisations 2014. |
Influence of the side-chain length on the cellular uptake and the cytotoxicity of rhenium triscarbonyl derivatives: A bimodal infrared and luminescence quantitative study Article de journal S Clède; F Lambert; R Saint-Fort; M -A Plamont; H Bertrand; A Vessières; C Policar Chemistry - A European Journal, 20 (28), p. 8714–8722, 2014. @article{Clede:2014,
title = {Influence of the side-chain length on the cellular uptake and the cytotoxicity of rhenium triscarbonyl derivatives: A bimodal infrared and luminescence quantitative study},
author = {S Cl\`{e}de and F Lambert and R Saint-Fort and M -A Plamont and H Bertrand and A Vessi\`{e}res and C Policar},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84903724808&doi=10.1002%2fchem.201402471&partnerID=40&md5=7334edd420d748a4418df936173a79b9},
doi = {10.1002/chem.201402471},
year = {2014},
date = {2014-01-01},
journal = {Chemistry - A European Journal},
volume = {20},
number = {28},
pages = {8714--8722},
abstract = {Rhenium triscarbonyl complexes fac-[Re(CO)3(NtextasciicircumN)] with appropriate ancillary NtextasciicircumN ligands are relevant for fluorescent bio-imaging. Recently, we have shown that [Re(CO)3] cores can also be efficiently mapped inside cells using their IR signature and that they can thus be used in a bimodal approach. To describe them we have coined the term SCoMPIs for single-core multimodal probes for imaging. In the context of the use of these SCoMPIs in bio-imaging, the questions of their cellular uptake and cytotoxicity are critical. We report here a series of compounds derived from the [Re(CO) 3Cl(pyta)] core (pyta=4-(2-pyridyl)-1,2,3-triazole). The pyta ligand is of interest because it can be easily functionalized. Aliphatic side chains (C4, C8, and C12) were appended to this core. A correlative study involving IR and luminescence was performed to monitor and quantify their cellular internalization. We studied the relationship between lipophilicity (log P(o/w)), cytotoxicity (IC50), and cellular uptake, and we showed that both uptake and cytotoxicity increase with the length of the side chain, with a higher uptake for the C12 derivative. This study stresses the distinction that has to be made between apparent toxicity, determined as an incubation concentration IC50, and intrinsic toxicity. Indeed, the intrinsic toxicity of a compound can remain hidden if it is not cell permeable. Therefore it must be kept in mind that IC50 values are composite values, reflecting both cellular uptake and intrinsic toxicity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Rhenium triscarbonyl complexes fac-[Re(CO)3(NtextasciicircumN)] with appropriate ancillary NtextasciicircumN ligands are relevant for fluorescent bio-imaging. Recently, we have shown that [Re(CO)3] cores can also be efficiently mapped inside cells using their IR signature and that they can thus be used in a bimodal approach. To describe them we have coined the term SCoMPIs for single-core multimodal probes for imaging. In the context of the use of these SCoMPIs in bio-imaging, the questions of their cellular uptake and cytotoxicity are critical. We report here a series of compounds derived from the [Re(CO) 3Cl(pyta)] core (pyta=4-(2-pyridyl)-1,2,3-triazole). The pyta ligand is of interest because it can be easily functionalized. Aliphatic side chains (C4, C8, and C12) were appended to this core. A correlative study involving IR and luminescence was performed to monitor and quantify their cellular internalization. We studied the relationship between lipophilicity (log P(o/w)), cytotoxicity (IC50), and cellular uptake, and we showed that both uptake and cytotoxicity increase with the length of the side chain, with a higher uptake for the C12 derivative. This study stresses the distinction that has to be made between apparent toxicity, determined as an incubation concentration IC50, and intrinsic toxicity. Indeed, the intrinsic toxicity of a compound can remain hidden if it is not cell permeable. Therefore it must be kept in mind that IC50 values are composite values, reflecting both cellular uptake and intrinsic toxicity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
2013
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Toward optimal spatial and spectral quality in widefield infrared spectromicroscopy of IR labelled single cells Article de journal E C Mattson; M Unger; S Clède; F Lambert; C Policar; A Imtiaz; R D'Souza; C J Hirschmugl Analyst, 138 (19), p. 5610–5618, 2013. @article{Mattson:2013,
title = {Toward optimal spatial and spectral quality in widefield infrared spectromicroscopy of IR labelled single cells},
author = {E C Mattson and M Unger and S Cl\`{e}de and F Lambert and C Policar and A Imtiaz and R D'Souza and C J Hirschmugl},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84883213711&doi=10.1039%2fc3an00383c&partnerID=40&md5=77ab18447e02b2a40b9a4b70fb8f05b0},
doi = {10.1039/c3an00383c},
year = {2013},
date = {2013-01-01},
journal = {Analyst},
volume = {138},
number = {19},
pages = {5610--5618},
abstract = {Advancements in widefield infrared spectromicroscopy have recently been demonstrated following the commissioning of IRENI (InfraRed ENvironmental Imaging), a Fourier Transform infrared (FTIR) chemical imaging beamline at the Synchrotron Radiation Center. The present study demonstrates the effects of magnification, spatial oversampling, spectral pre-processing and deconvolution, focusing on the intracellular detection and distribution of an exogenous metal tris-carbonyl derivative 1 in a single MDA-MB-231 breast cancer cell. We demonstrate here that spatial oversampling for synchrotron-based infrared imaging is critical to obtain accurate diffraction-limited images at all wavelengths simultaneously. Resolution criteria and results from raw and deconvoluted images for two Schwarzschild objectives (36×, NA 0.5 and 74×, NA 0.65) are compared to each other and to prior reports for raster-scanned, confocal microscopes. The resolution of the imaging data can be improved by deconvolving the instrumental broadening that is determined with the measured PSFs, which is implemented with GPU programming architecture for fast hyperspectral processing. High definition, rapidly acquired, FTIR chemical images of respective spectral signatures of the cell and 1 shows that 1 is localized next to the phosphate- and Amide-rich regions, in agreement with previous infrared and luminescence studies. The infrared image contrast, localization and definition are improved after applying proven spectral pre-processing (principal component analysis based noise reduction and RMie scattering correction algorithms) to individual pixel spectra in the hyperspectral cube. © The Royal Society of Chemistry.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Advancements in widefield infrared spectromicroscopy have recently been demonstrated following the commissioning of IRENI (InfraRed ENvironmental Imaging), a Fourier Transform infrared (FTIR) chemical imaging beamline at the Synchrotron Radiation Center. The present study demonstrates the effects of magnification, spatial oversampling, spectral pre-processing and deconvolution, focusing on the intracellular detection and distribution of an exogenous metal tris-carbonyl derivative 1 in a single MDA-MB-231 breast cancer cell. We demonstrate here that spatial oversampling for synchrotron-based infrared imaging is critical to obtain accurate diffraction-limited images at all wavelengths simultaneously. Resolution criteria and results from raw and deconvoluted images for two Schwarzschild objectives (36×, NA 0.5 and 74×, NA 0.65) are compared to each other and to prior reports for raster-scanned, confocal microscopes. The resolution of the imaging data can be improved by deconvolving the instrumental broadening that is determined with the measured PSFs, which is implemented with GPU programming architecture for fast hyperspectral processing. High definition, rapidly acquired, FTIR chemical images of respective spectral signatures of the cell and 1 shows that 1 is localized next to the phosphate- and Amide-rich regions, in agreement with previous infrared and luminescence studies. The infrared image contrast, localization and definition are improved after applying proven spectral pre-processing (principal component analysis based noise reduction and RMie scattering correction algorithms) to individual pixel spectra in the hyperspectral cube. © The Royal Society of Chemistry. |
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. |
Detection of an estrogen derivative in two breast cancer cell lines using a single core multimodal probe for imaging (SCoMPI) imaged by a panel of luminescent and vibrational techniques Article de journal S Clède; F Lambert; C Sandt; S Kascakova; M Unger; E Harté; M -A Plamont; R Saint-Fort; A Deniset-Besseau; Z Gueroui; C Hirschmugl; S Lecomte; A Dazzi; A Vessières; C Policar Analyst, 138 (19), p. 5627–5638, 2013. @article{Clede:2013a,
title = {Detection of an estrogen derivative in two breast cancer cell lines using a single core multimodal probe for imaging (SCoMPI) imaged by a panel of luminescent and vibrational techniques},
author = {S Cl\`{e}de and F Lambert and C Sandt and S Kascakova and M Unger and E Hart\'{e} and M -A Plamont and R Saint-Fort and A Deniset-Besseau and Z Gueroui and C Hirschmugl and S Lecomte and A Dazzi and A Vessi\`{e}res and C Policar},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84883254315&doi=10.1039%2fc3an00807j&partnerID=40&md5=02420b772ef22a07206b5ae31c42dd2e},
doi = {10.1039/c3an00807j},
year = {2013},
date = {2013-01-01},
journal = {Analyst},
volume = {138},
number = {19},
pages = {5627--5638},
abstract = {3-Methoxy-17α-ethynylestradiol or mestranol is a prodrug for ethynylestradiol and the estrogen component of some oral contraceptive formulations. We demonstrate here that a single core multimodal probe for imaging-SCoMPI-can be efficiently grafted onto mestranol allowing its tracking in two breast cancer cell lines, MDA-MB-231 and MCF-7 fixed cells. Correlative imaging studies based on luminescence (synchrotron UV spectromicroscopy, wide field and confocal fluorescence microscopies) and vibrational (AFMIR, synchrotron FTIR spectromicroscopy, synchrotron-based multiple beam FTIR imaging, confocal Raman microspectroscopy) spectroscopies were consistent with one another and showed a Golgi apparatus distribution of the SCoMPI-mestranol conjugate in both cell lines. © The Royal Society of Chemistry.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
3-Methoxy-17α-ethynylestradiol or mestranol is a prodrug for ethynylestradiol and the estrogen component of some oral contraceptive formulations. We demonstrate here that a single core multimodal probe for imaging-SCoMPI-can be efficiently grafted onto mestranol allowing its tracking in two breast cancer cell lines, MDA-MB-231 and MCF-7 fixed cells. Correlative imaging studies based on luminescence (synchrotron UV spectromicroscopy, wide field and confocal fluorescence microscopies) and vibrational (AFMIR, synchrotron FTIR spectromicroscopy, synchrotron-based multiple beam FTIR imaging, confocal Raman microspectroscopy) spectroscopies were consistent with one another and showed a Golgi apparatus distribution of the SCoMPI-mestranol conjugate in both cell lines. © The Royal Society of Chemistry. |
Polypyrrole functionalized with new copper complex as platform for His-tag antibody immobilization and direct antigen detection Article de journal S Chebil; A Miodek; V Ambike; H Sauriat-Dorizon; C Policar; H Korri-Youssoufi Sensors and Actuators, B: Chemical, 185 , p. 762–770, 2013. @article{Chebil:2013,
title = {Polypyrrole functionalized with new copper complex as platform for His-tag antibody immobilization and direct antigen detection},
author = {S Chebil and A Miodek and V Ambike and H Sauriat-Dorizon and C Policar and H Korri-Youssoufi},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84879243477&doi=10.1016%2fj.snb.2013.05.024&partnerID=40&md5=3d177c3bfb5d34b53cdc0265fd462968},
doi = {10.1016/j.snb.2013.05.024},
year = {2013},
date = {2013-01-01},
journal = {Sensors and Actuators, B: Chemical},
volume = {185},
pages = {762--770},
abstract = {A biomaterial based on a copper complex covalently attached to a polypyrrole backbone was designed for monitoring a glycoprotein, D-dimer, used as a marker of the deep vein thrombosis (DVT) condition. For this purpose a new copper complex has been developed based on the ligand N-(2-hydroxybenzyl)- N′-(6-aminohexyl)-N,N′-bis[2-(N-methylimidazolyl)methyl]ethane-1, 2-diamine (3) that is able to coordinate copper ions through two imidazole, two amine and one phenolato moieties - this coordination sphere will be labeled enPI2. The complex conjugated with a polypyrrole layer allows the His-tag antibody immobilization onto the conducting polymer substrate and immunosensor evaluation. The biomaterial shows a remarkable variation in redox activity of the Cu(II) complex after the D-dimer interaction. The redox activity of the [(enPi2)Cu(II)] complex decreases after the antigen interaction providing a linear response between 0.01 and 500 ng mL-1 with a detection limit of 10 pg mL-1. The chemical structure of copper complex demonstrates the ability to avoid non specific-interaction leading to anti fouling surface. Such biolayer architecture offers high measurement stability over time and the biomaterial could be stocked for several weeks without any modification of the electrochemical properties. © 2013 Elsevier B.V.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
A biomaterial based on a copper complex covalently attached to a polypyrrole backbone was designed for monitoring a glycoprotein, D-dimer, used as a marker of the deep vein thrombosis (DVT) condition. For this purpose a new copper complex has been developed based on the ligand N-(2-hydroxybenzyl)- N′-(6-aminohexyl)-N,N′-bis[2-(N-methylimidazolyl)methyl]ethane-1, 2-diamine (3) that is able to coordinate copper ions through two imidazole, two amine and one phenolato moieties - this coordination sphere will be labeled enPI2. The complex conjugated with a polypyrrole layer allows the His-tag antibody immobilization onto the conducting polymer substrate and immunosensor evaluation. The biomaterial shows a remarkable variation in redox activity of the Cu(II) complex after the D-dimer interaction. The redox activity of the [(enPi2)Cu(II)] complex decreases after the antigen interaction providing a linear response between 0.01 and 500 ng mL-1 with a detection limit of 10 pg mL-1. The chemical structure of copper complex demonstrates the ability to avoid non specific-interaction leading to anti fouling surface. Such biolayer architecture offers high measurement stability over time and the biomaterial could be stocked for several weeks without any modification of the electrochemical properties. © 2013 Elsevier B.V. |
Synchrotron radiation FTIR detection of a metal-carbonyl tamoxifen analog. Correlation with luminescence microscopy to study its subcellular distribution Article de journal S Clède; F Lambert; C Sandt; Z Gueroui; N Delsuc; P Dumas; A Vessières; C Policar Biotechnology Advances, 31 (3), p. 393–395, 2013. @article{Clede:2013,
title = {Synchrotron radiation FTIR detection of a metal-carbonyl tamoxifen analog. Correlation with luminescence microscopy to study its subcellular distribution},
author = {S Cl\`{e}de and F Lambert and C Sandt and Z Gueroui and N Delsuc and P Dumas and A Vessi\`{e}res and C Policar},
url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84875055388&doi=10.1016%2fj.biotechadv.2012.01.023&partnerID=40&md5=064b36e2db4e1260e17d3abc8b07bbd6},
doi = {10.1016/j.biotechadv.2012.01.023},
year = {2013},
date = {2013-01-01},
journal = {Biotechnology Advances},
volume = {31},
number = {3},
pages = {393--395},
abstract = {1,1-Di(4-hydroxyphenyl)-2-cyrhetrenylbut-1-ene 1 is an organometallic conjugate where a [(Cp)Re(CO)3] unit is linked to a hydroxytamoxifen-like structure. Its subcellular nuclear distribution was previously observed in a single cell using the near-field technique AFMIR. We show here that synchrotron radiation FTIR spectromicroscopy (SR-FTIR-SM) enabled the mapping of 1 based on its IR-signature (characteristic bands in the 1850-2200cm-1 range) and pointed out the colocalization of 1 with an area of high amide density. Fluorescence microscopy using DAPI staining performed on the same cells confirmed that this area corresponds to the cell nucleus. © 2012 Elsevier Inc.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
1,1-Di(4-hydroxyphenyl)-2-cyrhetrenylbut-1-ene 1 is an organometallic conjugate where a [(Cp)Re(CO)3] unit is linked to a hydroxytamoxifen-like structure. Its subcellular nuclear distribution was previously observed in a single cell using the near-field technique AFMIR. We show here that synchrotron radiation FTIR spectromicroscopy (SR-FTIR-SM) enabled the mapping of 1 based on its IR-signature (characteristic bands in the 1850-2200cm-1 range) and pointed out the colocalization of 1 with an area of high amide density. Fluorescence microscopy using DAPI staining performed on the same cells confirmed that this area corresponds to the cell nucleus. © 2012 Elsevier Inc. |
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. |
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
|
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. |
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. |
2010
|
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
|
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}
}
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. |
