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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Publicado: 2013
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15499618_v9_n6_p2609_Castro
http://hdl.handle.net/20.500.12110/paper_15499618_v9_n6_p2609_Castro
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_15499618_v9_n6_p2609_Castro
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spelling paper:paper_15499618_v9_n6_p2609_Castro2023-06-08T16:21:32Z 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. 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. 2013 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15499618_v9_n6_p2609_Castro http://hdl.handle.net/20.500.12110/paper_15499618_v9_n6_p2609_Castro
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection 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.
title Electronic delocalization in coordination polymers based on bimetallic carboxylates
spellingShingle 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
publishDate 2013
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_15499618_v9_n6_p2609_Castro
http://hdl.handle.net/20.500.12110/paper_15499618_v9_n6_p2609_Castro
_version_ 1768542333822828544

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