Synthesis and Photophysical Evaluation of Isoleptic Pt(II) and Pd(II) Complexes Utilizing N^N^N Ligands as Luminophoric Chelators with Different Ancillary Ligands

Autores
Silpa Padmakumar Sheelakumari; Cappellari, María Victoria; Rivas Aiello, Maria Belen; Hepp, Alexander; Strassert, Cristian A.
Año de publicación
2024
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Abstract: We herein report on the synthesis and structural characterization, as well as on the photophysical properties, of a series of isoleptic Pt(II) and Pd(II) complexes featuring tridentate NˆNˆN chelators as luminophores while bearing diverse ancillary co-ligands. Six new palladium complexes were synthesized using 2,6-bis(3-(tert-butyl/trifluoromethyl)-1H-1,2,4-triazol-5-yl)pyridine (tbu or CF3, respectively) in combination with four distinct ancillary ligands, namely: 4-amylpyridine (AmPy), 2,6-dimethylphenyl isonitrile (CNR), triphenylphosphane (PPh3), and 1,3,5-triaza-7- phosphaadamantane (PTA). Thus, two novel Pt(II) complexes incorporating the co-ligands CNR and PTA were explored. The remaining platinum-based complexes, namely CF3-Pt-AmPy, tbu-Pt-AmPy, CF3-Pt-PPh3, and tbu-Pt-PPh3, were re-synthesized according to our previous work for a systematic comparison with their Pd(II) homologues. Thus, photophysical studies were performed in different solvents and conditions. The Pt(II) complexes demonstrated comparable or superior photophysical characteristics in toluene when compared with their solutions in liquid dichloromethane at room temperature. In contrast, the Pd(II) complexes exhibited no significant photoluminescence in dichloromethane, but a surprisingly clear emission was observed for tbu-Pd-AmPy, tbu-Pd-CNR, and tbu-Pd-PPh3 in liquid toluene at room temperature. The significant differences regarding excited state lifetimes and photoluminescence quantum yields underscore the impact of solvent selection on photophysical characteristics, emphasizing the need to consider metal-ligand interactions, as well as the surrounding microenvironment, for a comprehensive interpretation of their photophysical properties. In addition, it is clear that AmPy and CNR render better luminescence efficiencies, whereas PTA is only suitable in toluene.
Fil: Silpa Padmakumar Sheelakumari. Westfälische Wilhelms Universität; Alemania
Fil: Cappellari, María Victoria. Westfälische Wilhelms Universität; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Rivas Aiello, Maria Belen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Westfälische Wilhelms Universität; Alemania
Fil: Hepp, Alexander. Westfälische Wilhelms Universität; Alemania
Fil: Strassert, Cristian A.. Westfälische Wilhelms Universität; Alemania
Materia
Pt(II) and Pd(II) complexes
synthesis
structural characterization
steady-state and time-resolved photoluminescence spectroscopy
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/262279
Acceder
id CONICETDig_adfc25113dd201fd32905122ac7075ff
oai_identifier_str oai:ri.conicet.gov.ar:11336/262279
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Synthesis and Photophysical Evaluation of Isoleptic Pt(II) and Pd(II) Complexes Utilizing N^N^N Ligands as Luminophoric Chelators with Different Ancillary LigandsSilpa Padmakumar SheelakumariCappellari, María VictoriaRivas Aiello, Maria BelenHepp, AlexanderStrassert, Cristian A.Pt(II) and Pd(II) complexessynthesisstructural characterizationsteady-state and time-resolved photoluminescence spectroscopyhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Abstract: We herein report on the synthesis and structural characterization, as well as on the photophysical properties, of a series of isoleptic Pt(II) and Pd(II) complexes featuring tridentate NˆNˆN chelators as luminophores while bearing diverse ancillary co-ligands. Six new palladium complexes were synthesized using 2,6-bis(3-(tert-butyl/trifluoromethyl)-1H-1,2,4-triazol-5-yl)pyridine (tbu or CF3, respectively) in combination with four distinct ancillary ligands, namely: 4-amylpyridine (AmPy), 2,6-dimethylphenyl isonitrile (CNR), triphenylphosphane (PPh3), and 1,3,5-triaza-7- phosphaadamantane (PTA). Thus, two novel Pt(II) complexes incorporating the co-ligands CNR and PTA were explored. The remaining platinum-based complexes, namely CF3-Pt-AmPy, tbu-Pt-AmPy, CF3-Pt-PPh3, and tbu-Pt-PPh3, were re-synthesized according to our previous work for a systematic comparison with their Pd(II) homologues. Thus, photophysical studies were performed in different solvents and conditions. The Pt(II) complexes demonstrated comparable or superior photophysical characteristics in toluene when compared with their solutions in liquid dichloromethane at room temperature. In contrast, the Pd(II) complexes exhibited no significant photoluminescence in dichloromethane, but a surprisingly clear emission was observed for tbu-Pd-AmPy, tbu-Pd-CNR, and tbu-Pd-PPh3 in liquid toluene at room temperature. The significant differences regarding excited state lifetimes and photoluminescence quantum yields underscore the impact of solvent selection on photophysical characteristics, emphasizing the need to consider metal-ligand interactions, as well as the surrounding microenvironment, for a comprehensive interpretation of their photophysical properties. In addition, it is clear that AmPy and CNR render better luminescence efficiencies, whereas PTA is only suitable in toluene.Fil: Silpa Padmakumar Sheelakumari. Westfälische Wilhelms Universität; AlemaniaFil: Cappellari, María Victoria. Westfälische Wilhelms Universität; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Rivas Aiello, Maria Belen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Westfälische Wilhelms Universität; AlemaniaFil: Hepp, Alexander. Westfälische Wilhelms Universität; AlemaniaFil: Strassert, Cristian A.. Westfälische Wilhelms Universität; AlemaniaMDPI2024-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/262279Silpa Padmakumar Sheelakumari; Cappellari, María Victoria; Rivas Aiello, Maria Belen; Hepp, Alexander; Strassert, Cristian A. ; Synthesis and Photophysical Evaluation of Isoleptic Pt(II) and Pd(II) Complexes Utilizing N^N^N Ligands as Luminophoric Chelators with Different Ancillary Ligands; MDPI; Inorganics; 12; 2; 2-2024; 1-112304-6740CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.mdpi.com/2304-6740/12/2/58info:eu-repo/semantics/altIdentifier/doi/10.3390/inorganics12020058info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:50:24Zoai:ri.conicet.gov.ar:11336/262279instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 09:50:24.763CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Synthesis and Photophysical Evaluation of Isoleptic Pt(II) and Pd(II) Complexes Utilizing N^N^N Ligands as Luminophoric Chelators with Different Ancillary Ligands
title Synthesis and Photophysical Evaluation of Isoleptic Pt(II) and Pd(II) Complexes Utilizing N^N^N Ligands as Luminophoric Chelators with Different Ancillary Ligands
spellingShingle Synthesis and Photophysical Evaluation of Isoleptic Pt(II) and Pd(II) Complexes Utilizing N^N^N Ligands as Luminophoric Chelators with Different Ancillary Ligands
Silpa Padmakumar Sheelakumari
Pt(II) and Pd(II) complexes
synthesis
structural characterization
steady-state and time-resolved photoluminescence spectroscopy
title_short Synthesis and Photophysical Evaluation of Isoleptic Pt(II) and Pd(II) Complexes Utilizing N^N^N Ligands as Luminophoric Chelators with Different Ancillary Ligands
title_full Synthesis and Photophysical Evaluation of Isoleptic Pt(II) and Pd(II) Complexes Utilizing N^N^N Ligands as Luminophoric Chelators with Different Ancillary Ligands
title_fullStr Synthesis and Photophysical Evaluation of Isoleptic Pt(II) and Pd(II) Complexes Utilizing N^N^N Ligands as Luminophoric Chelators with Different Ancillary Ligands
title_full_unstemmed Synthesis and Photophysical Evaluation of Isoleptic Pt(II) and Pd(II) Complexes Utilizing N^N^N Ligands as Luminophoric Chelators with Different Ancillary Ligands
title_sort Synthesis and Photophysical Evaluation of Isoleptic Pt(II) and Pd(II) Complexes Utilizing N^N^N Ligands as Luminophoric Chelators with Different Ancillary Ligands
dc.creator.none.fl_str_mv Silpa Padmakumar Sheelakumari
Cappellari, María Victoria
Rivas Aiello, Maria Belen
Hepp, Alexander
Strassert, Cristian A.
author Silpa Padmakumar Sheelakumari
author_facet Silpa Padmakumar Sheelakumari
Cappellari, María Victoria
Rivas Aiello, Maria Belen
Hepp, Alexander
Strassert, Cristian A.
author_role author
author2 Cappellari, María Victoria
Rivas Aiello, Maria Belen
Hepp, Alexander
Strassert, Cristian A.
author2_role author
author
author
author
dc.subject.none.fl_str_mv Pt(II) and Pd(II) complexes
synthesis
structural characterization
steady-state and time-resolved photoluminescence spectroscopy
topic Pt(II) and Pd(II) complexes
synthesis
structural characterization
steady-state and time-resolved photoluminescence spectroscopy
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Abstract: We herein report on the synthesis and structural characterization, as well as on the photophysical properties, of a series of isoleptic Pt(II) and Pd(II) complexes featuring tridentate NˆNˆN chelators as luminophores while bearing diverse ancillary co-ligands. Six new palladium complexes were synthesized using 2,6-bis(3-(tert-butyl/trifluoromethyl)-1H-1,2,4-triazol-5-yl)pyridine (tbu or CF3, respectively) in combination with four distinct ancillary ligands, namely: 4-amylpyridine (AmPy), 2,6-dimethylphenyl isonitrile (CNR), triphenylphosphane (PPh3), and 1,3,5-triaza-7- phosphaadamantane (PTA). Thus, two novel Pt(II) complexes incorporating the co-ligands CNR and PTA were explored. The remaining platinum-based complexes, namely CF3-Pt-AmPy, tbu-Pt-AmPy, CF3-Pt-PPh3, and tbu-Pt-PPh3, were re-synthesized according to our previous work for a systematic comparison with their Pd(II) homologues. Thus, photophysical studies were performed in different solvents and conditions. The Pt(II) complexes demonstrated comparable or superior photophysical characteristics in toluene when compared with their solutions in liquid dichloromethane at room temperature. In contrast, the Pd(II) complexes exhibited no significant photoluminescence in dichloromethane, but a surprisingly clear emission was observed for tbu-Pd-AmPy, tbu-Pd-CNR, and tbu-Pd-PPh3 in liquid toluene at room temperature. The significant differences regarding excited state lifetimes and photoluminescence quantum yields underscore the impact of solvent selection on photophysical characteristics, emphasizing the need to consider metal-ligand interactions, as well as the surrounding microenvironment, for a comprehensive interpretation of their photophysical properties. In addition, it is clear that AmPy and CNR render better luminescence efficiencies, whereas PTA is only suitable in toluene.
Fil: Silpa Padmakumar Sheelakumari. Westfälische Wilhelms Universität; Alemania
Fil: Cappellari, María Victoria. Westfälische Wilhelms Universität; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Rivas Aiello, Maria Belen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Westfälische Wilhelms Universität; Alemania
Fil: Hepp, Alexander. Westfälische Wilhelms Universität; Alemania
Fil: Strassert, Cristian A.. Westfälische Wilhelms Universität; Alemania
description Abstract: We herein report on the synthesis and structural characterization, as well as on the photophysical properties, of a series of isoleptic Pt(II) and Pd(II) complexes featuring tridentate NˆNˆN chelators as luminophores while bearing diverse ancillary co-ligands. Six new palladium complexes were synthesized using 2,6-bis(3-(tert-butyl/trifluoromethyl)-1H-1,2,4-triazol-5-yl)pyridine (tbu or CF3, respectively) in combination with four distinct ancillary ligands, namely: 4-amylpyridine (AmPy), 2,6-dimethylphenyl isonitrile (CNR), triphenylphosphane (PPh3), and 1,3,5-triaza-7- phosphaadamantane (PTA). Thus, two novel Pt(II) complexes incorporating the co-ligands CNR and PTA were explored. The remaining platinum-based complexes, namely CF3-Pt-AmPy, tbu-Pt-AmPy, CF3-Pt-PPh3, and tbu-Pt-PPh3, were re-synthesized according to our previous work for a systematic comparison with their Pd(II) homologues. Thus, photophysical studies were performed in different solvents and conditions. The Pt(II) complexes demonstrated comparable or superior photophysical characteristics in toluene when compared with their solutions in liquid dichloromethane at room temperature. In contrast, the Pd(II) complexes exhibited no significant photoluminescence in dichloromethane, but a surprisingly clear emission was observed for tbu-Pd-AmPy, tbu-Pd-CNR, and tbu-Pd-PPh3 in liquid toluene at room temperature. The significant differences regarding excited state lifetimes and photoluminescence quantum yields underscore the impact of solvent selection on photophysical characteristics, emphasizing the need to consider metal-ligand interactions, as well as the surrounding microenvironment, for a comprehensive interpretation of their photophysical properties. In addition, it is clear that AmPy and CNR render better luminescence efficiencies, whereas PTA is only suitable in toluene.
publishDate 2024
dc.date.none.fl_str_mv 2024-02
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/262279
Silpa Padmakumar Sheelakumari; Cappellari, María Victoria; Rivas Aiello, Maria Belen; Hepp, Alexander; Strassert, Cristian A. ; Synthesis and Photophysical Evaluation of Isoleptic Pt(II) and Pd(II) Complexes Utilizing N^N^N Ligands as Luminophoric Chelators with Different Ancillary Ligands; MDPI; Inorganics; 12; 2; 2-2024; 1-11
2304-6740
CONICET Digital
CONICET
url http://hdl.handle.net/11336/262279
identifier_str_mv Silpa Padmakumar Sheelakumari; Cappellari, María Victoria; Rivas Aiello, Maria Belen; Hepp, Alexander; Strassert, Cristian A. ; Synthesis and Photophysical Evaluation of Isoleptic Pt(II) and Pd(II) Complexes Utilizing N^N^N Ligands as Luminophoric Chelators with Different Ancillary Ligands; MDPI; Inorganics; 12; 2; 2-2024; 1-11
2304-6740
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.mdpi.com/2304-6740/12/2/58
info:eu-repo/semantics/altIdentifier/doi/10.3390/inorganics12020058
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv MDPI
publisher.none.fl_str_mv MDPI
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.070432

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