Electronic delocalization in coordination polymers based on bimetallic carboxylates
Computational methods (DFT at the B3LYP, PBE0 and m06 levels, MO fragments decomposition, and the broken symmetry approach) have been used to evaluate the influence of the bridging ligand (BL) on the extent of electron delocalization in coordination polymers based on diruthenium tetracarboxylates. T...
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| Acceso en línea: | http://hdl.handle.net/20.500.12110/paper_15499618_v9_n6_p2609_Castro |
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todo:paper_15499618_v9_n6_p2609_Castro2023-10-03T16:23:24Z Electronic delocalization in coordination polymers based on bimetallic carboxylates Castro, M.A. Roitberg, A.E. Cukiernik, F.D. Computational methods (DFT at the B3LYP, PBE0 and m06 levels, MO fragments decomposition, and the broken symmetry approach) have been used to evaluate the influence of the bridging ligand (BL) on the extent of electron delocalization in coordination polymers based on diruthenium tetracarboxylates. The efficiency of three different nitrogenated axial ligands, namely pyrazine (pz), phenazine (phz), and tetrazine (tz), to mediate electron coupling between Ru 2 (II,II) or Ru 2 (II,III) centers has been estimated through four different parameters: calculated Ru-N distances, HOMO-LUMO gaps, HOMO and LUMO compositions, and magnetic coupling constants J. All these parameters pointed toward a coordination polymer based on Ru 2 (II,II) centers axially linked by tetrazine being the best candidate for exhibiting electron delocalization through the Ru 2 -BL framework. Such a compound has been synthesized and characterized; its vis-NIR spectrum exhibited the predicted features, mainly an intense low-energy MLCT band, assigned to the expected Ru 2 (II,II) → tz process associated with electron delocalization. © 2013 American Chemical Society. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_15499618_v9_n6_p2609_Castro |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
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R-134 |
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| description |
Computational methods (DFT at the B3LYP, PBE0 and m06 levels, MO fragments decomposition, and the broken symmetry approach) have been used to evaluate the influence of the bridging ligand (BL) on the extent of electron delocalization in coordination polymers based on diruthenium tetracarboxylates. The efficiency of three different nitrogenated axial ligands, namely pyrazine (pz), phenazine (phz), and tetrazine (tz), to mediate electron coupling between Ru 2 (II,II) or Ru 2 (II,III) centers has been estimated through four different parameters: calculated Ru-N distances, HOMO-LUMO gaps, HOMO and LUMO compositions, and magnetic coupling constants J. All these parameters pointed toward a coordination polymer based on Ru 2 (II,II) centers axially linked by tetrazine being the best candidate for exhibiting electron delocalization through the Ru 2 -BL framework. Such a compound has been synthesized and characterized; its vis-NIR spectrum exhibited the predicted features, mainly an intense low-energy MLCT band, assigned to the expected Ru 2 (II,II) → tz process associated with electron delocalization. © 2013 American Chemical Society. |
| format |
JOUR |
| author |
Castro, M.A. Roitberg, A.E. Cukiernik, F.D. |
| spellingShingle |
Castro, M.A. Roitberg, A.E. Cukiernik, F.D. Electronic delocalization in coordination polymers based on bimetallic carboxylates |
| author_facet |
Castro, M.A. Roitberg, A.E. Cukiernik, F.D. |
| author_sort |
Castro, M.A. |
| title |
Electronic delocalization in coordination polymers based on bimetallic carboxylates |
| title_short |
Electronic delocalization in coordination polymers based on bimetallic carboxylates |
| title_full |
Electronic delocalization in coordination polymers based on bimetallic carboxylates |
| title_fullStr |
Electronic delocalization in coordination polymers based on bimetallic carboxylates |
| title_full_unstemmed |
Electronic delocalization in coordination polymers based on bimetallic carboxylates |
| title_sort |
electronic delocalization in coordination polymers based on bimetallic carboxylates |
| url |
http://hdl.handle.net/20.500.12110/paper_15499618_v9_n6_p2609_Castro |
| work_keys_str_mv |
AT castroma electronicdelocalizationincoordinationpolymersbasedonbimetalliccarboxylates AT roitbergae electronicdelocalizationincoordinationpolymersbasedonbimetalliccarboxylates AT cukiernikfd electronicdelocalizationincoordinationpolymersbasedonbimetalliccarboxylates |
| _version_ |
1782029803923177472 |