Coordination Chemistry of Mixed-Donor Pyridine-Containing Macrocyclic Ligands: From Optical to Redox Chemosensors for Heavy Metal Ions
2,8-Dithia-5-aza-2,6-pyridinophane (<b>L1</b>) has been used as a receptor unit in the construction of the conjugated redox chemosensor 5-ferrocenylmethyl-2,8-dithia-5-aza-2,6-pyridinophane (<b>L3</b>). In order to further explore the coordination chemistry of <b>L1<...
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2024-12-01
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| author | Alessandra Garau Alexander J. Blake Maria Carla Aragoni Massimiliano Arca Claudia Caltagirone Francesco Demartin Vito Lippolis Giacomo Picci Enrico Podda |
| author_facet | Alessandra Garau Alexander J. Blake Maria Carla Aragoni Massimiliano Arca Claudia Caltagirone Francesco Demartin Vito Lippolis Giacomo Picci Enrico Podda |
| author_sort | Alessandra Garau |
| collection | DOAJ |
| description | 2,8-Dithia-5-aza-2,6-pyridinophane (<b>L1</b>) has been used as a receptor unit in the construction of the conjugated redox chemosensor 5-ferrocenylmethyl-2,8-dithia-5-aza-2,6-pyridinophane (<b>L3</b>). In order to further explore the coordination chemistry of <b>L1</b>, and comparatively, that of its structural analogue 2,11-dithia-5,8-diaza-2,6-pyridinophane (<b>L2</b>), featuring two secondary nitrogen atoms in the macrocyclic unit, the crystal structures of the new synthesised complexes [Pb(<b>L1</b>)(ClO<sub>4</sub>)<sub>2</sub>]·½CH<sub>3</sub>CN, [Cu(<b>L2</b>)](ClO<sub>4</sub>)<sub>2</sub>·CH<sub>3</sub>CN and [Cd(<b>L2</b>)(NO<sub>3</sub>)]NO<sub>3</sub> were determined by X-ray diffraction analysis. The electrochemical response of <b>L3</b> towards the metal ions Cu<sup>2+</sup>, Zn<sup>2+</sup>, Cd<sup>2+</sup>, Hg<sup>2+</sup>, and Pb<sup>2+</sup> was investigated by cyclic voltammetry (CV) in CH<sub>2</sub>Cl<sub>2</sub>/CH<sub>3</sub>CN 0.25:1 (<i>v</i>/<i>v</i>) mixture. Upon addition to <b>L3</b> of increasing amounts of the aforementioned metal cations, the wave corresponding to the Fc<sup>+</sup>/Fc redox couple of the un-complexed <b>L3</b> was gradually replaced by a new reversible wave at more positive potentials and corresponding to the Fc<sup>+</sup>/Fc redox couple of the complexed ligand. The maximum anodic shift of the ferrocene oxidation wave is observed in the presence of Pb<sup>2+</sup> (230 mV), to which corresponds a reaction coupling efficiency (RCE) value as large as 7.9 × 10<sup>3</sup>. The response selectivity of <b>L3</b> is discussed in reference to the optical selectivity observed for conjugated chemosensors featuring <b>L1</b> as receptor unit and different fluorogenic fragments as signalling units. |
| format | Article |
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| spelling | doaj-art-c061662725024c2faa3bdca75790a7a72025-01-10T13:18:58ZengMDPI AGMolecules1420-30492024-12-0130113010.3390/molecules30010130Coordination Chemistry of Mixed-Donor Pyridine-Containing Macrocyclic Ligands: From Optical to Redox Chemosensors for Heavy Metal IonsAlessandra Garau0Alexander J. Blake1Maria Carla Aragoni2Massimiliano Arca3Claudia Caltagirone4Francesco Demartin5Vito Lippolis6Giacomo Picci7Enrico Podda8Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 Bivio per Sestu, 09042 Monserrato, ItalySchool of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UKDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 Bivio per Sestu, 09042 Monserrato, ItalyDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 Bivio per Sestu, 09042 Monserrato, ItalyDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 Bivio per Sestu, 09042 Monserrato, ItalyDipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133 Milano, ItalyDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 Bivio per Sestu, 09042 Monserrato, ItalyDipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 Bivio per Sestu, 09042 Monserrato, ItalyCentre for Research University Services (CeSAR), Università degli Studi di Cagliari, S.S. 554 Bivio per Sestu, 09042 Monserrato, Italy2,8-Dithia-5-aza-2,6-pyridinophane (<b>L1</b>) has been used as a receptor unit in the construction of the conjugated redox chemosensor 5-ferrocenylmethyl-2,8-dithia-5-aza-2,6-pyridinophane (<b>L3</b>). In order to further explore the coordination chemistry of <b>L1</b>, and comparatively, that of its structural analogue 2,11-dithia-5,8-diaza-2,6-pyridinophane (<b>L2</b>), featuring two secondary nitrogen atoms in the macrocyclic unit, the crystal structures of the new synthesised complexes [Pb(<b>L1</b>)(ClO<sub>4</sub>)<sub>2</sub>]·½CH<sub>3</sub>CN, [Cu(<b>L2</b>)](ClO<sub>4</sub>)<sub>2</sub>·CH<sub>3</sub>CN and [Cd(<b>L2</b>)(NO<sub>3</sub>)]NO<sub>3</sub> were determined by X-ray diffraction analysis. The electrochemical response of <b>L3</b> towards the metal ions Cu<sup>2+</sup>, Zn<sup>2+</sup>, Cd<sup>2+</sup>, Hg<sup>2+</sup>, and Pb<sup>2+</sup> was investigated by cyclic voltammetry (CV) in CH<sub>2</sub>Cl<sub>2</sub>/CH<sub>3</sub>CN 0.25:1 (<i>v</i>/<i>v</i>) mixture. Upon addition to <b>L3</b> of increasing amounts of the aforementioned metal cations, the wave corresponding to the Fc<sup>+</sup>/Fc redox couple of the un-complexed <b>L3</b> was gradually replaced by a new reversible wave at more positive potentials and corresponding to the Fc<sup>+</sup>/Fc redox couple of the complexed ligand. The maximum anodic shift of the ferrocene oxidation wave is observed in the presence of Pb<sup>2+</sup> (230 mV), to which corresponds a reaction coupling efficiency (RCE) value as large as 7.9 × 10<sup>3</sup>. The response selectivity of <b>L3</b> is discussed in reference to the optical selectivity observed for conjugated chemosensors featuring <b>L1</b> as receptor unit and different fluorogenic fragments as signalling units.https://www.mdpi.com/1420-3049/30/1/130macrocyclic ligandferroceneredox chemosensorleadheavy metal ions |
| spellingShingle | Alessandra Garau Alexander J. Blake Maria Carla Aragoni Massimiliano Arca Claudia Caltagirone Francesco Demartin Vito Lippolis Giacomo Picci Enrico Podda Coordination Chemistry of Mixed-Donor Pyridine-Containing Macrocyclic Ligands: From Optical to Redox Chemosensors for Heavy Metal Ions Molecules macrocyclic ligand ferrocene redox chemosensor lead heavy metal ions |
| title | Coordination Chemistry of Mixed-Donor Pyridine-Containing Macrocyclic Ligands: From Optical to Redox Chemosensors for Heavy Metal Ions |
| title_full | Coordination Chemistry of Mixed-Donor Pyridine-Containing Macrocyclic Ligands: From Optical to Redox Chemosensors for Heavy Metal Ions |
| title_fullStr | Coordination Chemistry of Mixed-Donor Pyridine-Containing Macrocyclic Ligands: From Optical to Redox Chemosensors for Heavy Metal Ions |
| title_full_unstemmed | Coordination Chemistry of Mixed-Donor Pyridine-Containing Macrocyclic Ligands: From Optical to Redox Chemosensors for Heavy Metal Ions |
| title_short | Coordination Chemistry of Mixed-Donor Pyridine-Containing Macrocyclic Ligands: From Optical to Redox Chemosensors for Heavy Metal Ions |
| title_sort | coordination chemistry of mixed donor pyridine containing macrocyclic ligands from optical to redox chemosensors for heavy metal ions |
| topic | macrocyclic ligand ferrocene redox chemosensor lead heavy metal ions |
| url | https://www.mdpi.com/1420-3049/30/1/130 |
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