Exploring the use of Rh-catalyzed cyclization reactions for the functionalization of fullerenes

ENG- Fullerenes are spherical carbon allotropes formed by an even number of carbon atoms organized in twelve pentagons and a variable number of hexagons, being C60 and C70 the two most widely known fullerenes of this family of compounds. Since their discovery, they have aroused great interest due to...

ver descrição completa

Detalhes bibliográficos
Autor: Castanyer Caballé, Cristina
Formato: tesis doctoral
Estado:Versión publicada
Fecha de publicación:2025
País:España
Recursos:CBUC, CESCA
Repositorio:TDR. Tesis Doctorales en Red
OAI Identifier:oai:www.tdx.cat:10803/693743
Acesso em linha:http://hdl.handle.net/10803/693743
Access Level:acceso abierto
Palavra-chave:Ful·lerens
Fullerenos
Fullerenes
Reaccions de ciclació
Reacciones de ciclación
Cyclization reactions
Catàlisi
Catalisi
Catalysis
Rodi
Rodio
Rhodium
Càlculs DFT
Cálculos DFT
DFT calculations
547
id ES_fbff440aff21a8ea17e8d2c9b11c2d09
oai_identifier_str oai:www.tdx.cat:10803/693743
network_acronym_str ES
network_name_str España
repository_id_str
dc.title.none.fl_str_mv Exploring the use of Rh-catalyzed cyclization reactions for the functionalization of fullerenes
title Exploring the use of Rh-catalyzed cyclization reactions for the functionalization of fullerenes
spellingShingle Exploring the use of Rh-catalyzed cyclization reactions for the functionalization of fullerenes
Castanyer Caballé, Cristina
Ful·lerens
Fullerenos
Fullerenes
Reaccions de ciclació
Reacciones de ciclación
Cyclization reactions
Catàlisi
Catalisi
Catalysis
Rodi
Rodio
Rhodium
Càlculs DFT
Cálculos DFT
DFT calculations
547
title_short Exploring the use of Rh-catalyzed cyclization reactions for the functionalization of fullerenes
title_full Exploring the use of Rh-catalyzed cyclization reactions for the functionalization of fullerenes
title_fullStr Exploring the use of Rh-catalyzed cyclization reactions for the functionalization of fullerenes
title_full_unstemmed Exploring the use of Rh-catalyzed cyclization reactions for the functionalization of fullerenes
title_sort Exploring the use of Rh-catalyzed cyclization reactions for the functionalization of fullerenes
dc.creator.none.fl_str_mv Castanyer Caballé, Cristina
author Castanyer Caballé, Cristina
author_facet Castanyer Caballé, Cristina
author_role author
dc.contributor.none.fl_str_mv Pla i Quintana, Anna
Solà i Puig, Miquel
Roglans i Ribas, Anna
Universitat de Girona. Departament de Química
Universitat de Girona. Institut de Química Computacional i Catàlisi
dc.subject.none.fl_str_mv Ful·lerens
Fullerenos
Fullerenes
Reaccions de ciclació
Reacciones de ciclación
Cyclization reactions
Catàlisi
Catalisi
Catalysis
Rodi
Rodio
Rhodium
Càlculs DFT
Cálculos DFT
DFT calculations
547
topic Ful·lerens
Fullerenos
Fullerenes
Reaccions de ciclació
Reacciones de ciclación
Cyclization reactions
Catàlisi
Catalisi
Catalysis
Rodi
Rodio
Rhodium
Càlculs DFT
Cálculos DFT
DFT calculations
547
description ENG- Fullerenes are spherical carbon allotropes formed by an even number of carbon atoms organized in twelve pentagons and a variable number of hexagons, being C60 and C70 the two most widely known fullerenes of this family of compounds. Since their discovery, they have aroused great interest due to their characteristics and properties, which make them attractive compounds for various applications in the fields of biomedicine and photovoltaic energy. However, one of the main disadvantages of their use is that they must be previously functionalized to make them more manipulable. Although significant progress has been achieved in the field of fullerene functionalization, there is still much to be discovered. Currently, the emphasis is on improving the selectivity of processes and efficiently synthesizing new derivatives using innovative methods, compounds which may be potentially interesting for applications. The use of cyclizations catalyzed or promoted by transition metals has become one of the efficient alternatives to synthesize fullerene derivatives fused with carbo- and heterocyclic rings of different sizes and varied functionality. Our research group has considerable experience in the development of transition metal-catalyzed cyclizations, specifically, rhodium-catalyzed [2+2+2] cycloadditions involving various unsaturations. Recently, this reaction has been applied to the functionalization of fullerenes, where a rhodium-catalyzed [2+2+2] cycloaddition reaction between 1,6-diynes and C60 has allowed the synthesis of new open-cage derivatives of C60. Some of the derivatives prepared have proven to be good electron transport materials in perovskite solar cells. The main objective of this doctoral thesis is to focus on the development of new methodologies for the functionalization of fullerenes through cyclization processes catalyzed by rhodium involving different unsaturated substrates. The work begins by undertaking a revision of the cyclization processes catalyzed or promoted by transition metals used for the functionalization of fullerenes that have been reported in the literature, offering an overview of the main topic of the doctoral thesis. We then go on to describe the synthesis of open-cage derivatives of C70 from the use of 1,6-diynes, applying the methodology previously reported by our group, with special emphasis on the regioselectivity of the process. This is followed by an extensive study of cyclization reactions of C60 and/or C70 catalyzed by different rhodium-based catalytic systems involving unsaturated substrates such as 1,5-bisallenes, 1,6-enynes and 1,6-allenynes. In these studies, the catalytic process is optimized, the scope of the reaction is carried out by varying the unsaturated substrates and the mechanism of the new process is investigated through experiments and computational studies based on DFT calculations. The final result is to allow the efficient preparation of a wide range of new fullerene derivatives with 6,5-, 6,6- and 6,7-membered ring fusions
publishDate 2025
dc.date.none.fl_str_mv 2025
2025
2025
dc.type.none.fl_str_mv info:eu-repo/semantics/doctoralThesis
info:eu-repo/semantics/publishedVersion
format doctoralThesis
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10803/693743
url http://hdl.handle.net/10803/693743
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv http://creativecommons.org/licenses/by-nc-nd/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 325 p.
application/pdf
dc.publisher.none.fl_str_mv Universitat de Girona
publisher.none.fl_str_mv Universitat de Girona
dc.source.none.fl_str_mv TDX (Tesis Doctorals en Xarxa)
reponame:TDR. Tesis Doctorales en Red
instname:CBUC, CESCA
instname_str CBUC, CESCA
reponame_str TDR. Tesis Doctorales en Red
collection TDR. Tesis Doctorales en Red
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869425381670387712
spelling Exploring the use of Rh-catalyzed cyclization reactions for the functionalization of fullerenesCastanyer Caballé, CristinaFul·lerensFullerenosFullerenesReaccions de ciclacióReacciones de ciclaciónCyclization reactionsCatàlisiCatalisiCatalysisRodiRodioRhodiumCàlculs DFTCálculos DFTDFT calculations547ENG- Fullerenes are spherical carbon allotropes formed by an even number of carbon atoms organized in twelve pentagons and a variable number of hexagons, being C60 and C70 the two most widely known fullerenes of this family of compounds. Since their discovery, they have aroused great interest due to their characteristics and properties, which make them attractive compounds for various applications in the fields of biomedicine and photovoltaic energy. However, one of the main disadvantages of their use is that they must be previously functionalized to make them more manipulable. Although significant progress has been achieved in the field of fullerene functionalization, there is still much to be discovered. Currently, the emphasis is on improving the selectivity of processes and efficiently synthesizing new derivatives using innovative methods, compounds which may be potentially interesting for applications. The use of cyclizations catalyzed or promoted by transition metals has become one of the efficient alternatives to synthesize fullerene derivatives fused with carbo- and heterocyclic rings of different sizes and varied functionality. Our research group has considerable experience in the development of transition metal-catalyzed cyclizations, specifically, rhodium-catalyzed [2+2+2] cycloadditions involving various unsaturations. Recently, this reaction has been applied to the functionalization of fullerenes, where a rhodium-catalyzed [2+2+2] cycloaddition reaction between 1,6-diynes and C60 has allowed the synthesis of new open-cage derivatives of C60. Some of the derivatives prepared have proven to be good electron transport materials in perovskite solar cells. The main objective of this doctoral thesis is to focus on the development of new methodologies for the functionalization of fullerenes through cyclization processes catalyzed by rhodium involving different unsaturated substrates. The work begins by undertaking a revision of the cyclization processes catalyzed or promoted by transition metals used for the functionalization of fullerenes that have been reported in the literature, offering an overview of the main topic of the doctoral thesis. We then go on to describe the synthesis of open-cage derivatives of C70 from the use of 1,6-diynes, applying the methodology previously reported by our group, with special emphasis on the regioselectivity of the process. This is followed by an extensive study of cyclization reactions of C60 and/or C70 catalyzed by different rhodium-based catalytic systems involving unsaturated substrates such as 1,5-bisallenes, 1,6-enynes and 1,6-allenynes. In these studies, the catalytic process is optimized, the scope of the reaction is carried out by varying the unsaturated substrates and the mechanism of the new process is investigated through experiments and computational studies based on DFT calculations. The final result is to allow the efficient preparation of a wide range of new fullerene derivatives with 6,5-, 6,6- and 6,7-membered ring fusionsCAT- Els ful·lerens són al·lòtrops esfèrics del carboni formats per un nombre parell d’àtoms de carboni organitzats en dotze pentàgons i un nombre variable d’hexàgons, sent el C60 i el C70 els dos ful·lerens més representatius d’aquesta família de compostos. Des del seu descobriment, han despertat un gran interès degut a les seves característiques i propietats, convertint-los en compostos atractius per diverses aplicacions, com ara en l’àmbit de la biomedicina o de l’energia fotovoltaica. No obstant això, un dels principals desavantatges pel seu ús és el fet que han d’estar prèviament funcionalitzats per tal de que siguin més manipulables. Tot i que s’han realitzat progressos en el camp de la funcionalització de ful·lerens, encara queda molt per descobrir. Actualment, les investigacions es centren en millorar la selectivitat dels processos i sintetitzar de manera eficient nous derivats a través de mètodes innovadors, compostos que poden ser potencialment interessants per a certes aplicacions. L’ús de les ciclacions catalitzades o promogudes per metalls de transició han esdevingut una de les alternatives eficients per sintetitzar derivats de ful·lerè fusionats amb anells carbo- i heterocíclics de diferents mides i variada funcionalitat. El nostre grup de recerca presenta una sòlida experiència en el desenvolupament de ciclacions catalitzades per metalls de transició, concretament, en les cicloaddicions [2+2+2] catalitzades per rodi involucrant diverses insaturacions. Recentment, s’ha aplicat aquesta reacció a la funcionalització de ful·lerens, on mitjançant una reacció de cicloaddició [2+2+2] catalitzada per rodi entre 1,6-diïns i C60 ha permès la síntesi de nous derivats open-cage de C60. Alguns dels derivats preparats han demostrat ser bons materials transportadors d’electrons en cel·les solars de perovskita. L’objectiu principal d’aquesta tesi doctoral es centra en el desenvolupament de noves metodologies per a la funcionalització de ful·lerens mitjançant processos de ciclació catalitzats per rodi involucrant diferents substrats insaturats. S’inicia el treball amb un recull dels processos de ciclació catalitzats o promoguts per metalls de transició emprats per a la funcionalització de ful·lerens reportats a la bibliografia, oferint una visió del tema principal de la tesi doctoral. Seguidament, es descriu la síntesi de derivats open-cage de C70 a partir de l’ús de 1,6-diïns aplicant la metodologia reportada prèviament pel nostre grup, fent especial èmfasi a la regioselectivitat del procés. Tot seguit, es duu a terme un ampli estudi de reaccions de ciclació catalitzades per diferents sistemes catalítics basats en rodi involucrant C60 i/o C70 i substrats insaturats tals com 1,5-bisal.lens, 1,6-enins i 1,6-allenins. En aquests estudis s’optimitzen el procés catalític, es dur a terme l’abast de la reacció variant els substrats insaturats i s’investiga el mecanisme del nou procés mitjançant experiments i estudis computacionals basats en càlculs DFT. Aquests estudis permeten la preparació eficient d’un variat ventall de nous derivats de ful·lerè amb fusions d’anells de 6,5-, 6,6- i 6,7-membresPrograma de Doctorat en QuímicaUniversitat de GironaPla i Quintana, AnnaSolà i Puig, MiquelRoglans i Ribas, AnnaUniversitat de Girona. Departament de QuímicaUniversitat de Girona. Institut de Química Computacional i Catàlisi202520252025info:eu-repo/semantics/doctoralThesisinfo:eu-repo/semantics/publishedVersion325 p.application/pdfhttp://hdl.handle.net/10803/693743TDX (Tesis Doctorals en Xarxa)reponame:TDR. Tesis Doctorales en Redinstname:CBUC, CESCAInglésL'accés als continguts d'aquesta tesi queda condicionat a l'acceptació de les condicions d'ús establertes per la següent llicència Creative Commons: http://creativecommons.org/licenses/by-nc-nd/4.0/http://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:www.tdx.cat:10803/6937432026-06-14T12:46:07Z
score 15,81155

Registos relacionados