The Black Polymorph of TTF-CA: TTF Polymorphism and Solvent Effects in Mechanochemical and Vapor Digestion Syntheses, FT-IR, Crystal Packing, and Electronic Structure

Autores
Lapidus, Saul H.; Naik, Amit; Wixtrom, Alex; Massa, Nestor Emilio; Ta Phuoc, Vinh; del Campo, Leire; Lebegue, Sebestien; Aygyayn, Jaynos G.; Abdel Fattah, Tarek; Pagola, Silvina
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Tetrathiafulvalene-chloranil (TTF-CA) was synthesized by two methods, liquid assisted grinding (LAG) and vapor digestion (VD), which largely reduce the use of reaction solvents. The effects of the small quantities of LAG solvent and solvent vapors in VD toward the formation of a particular TTF-CA product polymorph were studied from both tetrathiafulvalene forms (orange and brown) as reactants. It was concluded that a high solvent polarity index favors the formation of the ionic black polymorph of TTF-CA vs the quasineutral green form, whereas the crystal structure and crystal habit of the orange tetrathiafulvalene polymorph also favors the formation of the black TTF-CA. The crystal structure of the black TTF-CA was determined from synchrotron X-ray powder diffraction (XRPD), and it consists of dimerized TTF+• and CA−• radical ions, in agreement with room temperature magnetic susceptibility measurements indicating the material is diamagnetic. FT-IR showed that the compound is a semiconductor with a small band gap of ∼0.198 eV and it remains ionic at low temperatures. The latter was confirmed by XRPD showing the black TTF-CA does not undergo a phase transition in the range 298−20 K. Band structure calculations are in good agreement with the measured band gap.
Fil: Lapidus, Saul H.. Stony Brook University; Estados Unidos
Fil: Naik, Amit. Thomas Nelson Community College; Estados Unidos
Fil: Wixtrom, Alex. Christopher Newport University; Estados Unidos
Fil: Massa, Nestor Emilio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Ta Phuoc, Vinh. UniversitéFrancois Rabelais Tours; Francia
Fil: del Campo, Leire. Université d’Orleans; Francia
Fil: Lebegue, Sebestien. Université de Lorraine; Francia
Fil: Aygyayn, Jaynos G.. Université de Lorraine; Francia
Fil: Abdel Fattah, Tarek. Christopher Newport University; Estados Unidos
Fil: Pagola, Silvina. College of William and Mary; Estados Unidos
Materia
Tetrathiafulvalene-Chloranil (Ttf-Ca)
Crystal Packing,
Ft-Ir
Electronic Structure
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/24976
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/24976
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling The Black Polymorph of TTF-CA: TTF Polymorphism and Solvent Effects in Mechanochemical and Vapor Digestion Syntheses, FT-IR, Crystal Packing, and Electronic StructureLapidus, Saul H.Naik, AmitWixtrom, AlexMassa, Nestor EmilioTa Phuoc, Vinhdel Campo, LeireLebegue, SebestienAygyayn, Jaynos G.Abdel Fattah, TarekPagola, SilvinaTetrathiafulvalene-Chloranil (Ttf-Ca)Crystal Packing,Ft-IrElectronic Structurehttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Tetrathiafulvalene-chloranil (TTF-CA) was synthesized by two methods, liquid assisted grinding (LAG) and vapor digestion (VD), which largely reduce the use of reaction solvents. The effects of the small quantities of LAG solvent and solvent vapors in VD toward the formation of a particular TTF-CA product polymorph were studied from both tetrathiafulvalene forms (orange and brown) as reactants. It was concluded that a high solvent polarity index favors the formation of the ionic black polymorph of TTF-CA vs the quasineutral green form, whereas the crystal structure and crystal habit of the orange tetrathiafulvalene polymorph also favors the formation of the black TTF-CA. The crystal structure of the black TTF-CA was determined from synchrotron X-ray powder diffraction (XRPD), and it consists of dimerized TTF+• and CA−• radical ions, in agreement with room temperature magnetic susceptibility measurements indicating the material is diamagnetic. FT-IR showed that the compound is a semiconductor with a small band gap of ∼0.198 eV and it remains ionic at low temperatures. The latter was confirmed by XRPD showing the black TTF-CA does not undergo a phase transition in the range 298−20 K. Band structure calculations are in good agreement with the measured band gap.Fil: Lapidus, Saul H.. Stony Brook University; Estados UnidosFil: Naik, Amit. Thomas Nelson Community College; Estados UnidosFil: Wixtrom, Alex. Christopher Newport University; Estados UnidosFil: Massa, Nestor Emilio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Ta Phuoc, Vinh. UniversitéFrancois Rabelais Tours; FranciaFil: del Campo, Leire. Université d’Orleans; FranciaFil: Lebegue, Sebestien. Université de Lorraine; FranciaFil: Aygyayn, Jaynos G.. Université de Lorraine; FranciaFil: Abdel Fattah, Tarek. Christopher Newport University; Estados UnidosFil: Pagola, Silvina. College of William and Mary; Estados UnidosAmerican Chemical Society2014-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/24976Lapidus, Saul H.; Naik, Amit; Wixtrom, Alex; Massa, Nestor Emilio; Ta Phuoc, Vinh; et al.; The Black Polymorph of TTF-CA: TTF Polymorphism and Solvent Effects in Mechanochemical and Vapor Digestion Syntheses, FT-IR, Crystal Packing, and Electronic Structure; American Chemical Society; Crystal Growth & Design; 14; 1; 1-2014; 91-1001528-7483CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/cg401203rinfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/cg401203rinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:06:12Zoai:ri.conicet.gov.ar:11336/24976instacron: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 10:06:12.522CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv The Black Polymorph of TTF-CA: TTF Polymorphism and Solvent Effects in Mechanochemical and Vapor Digestion Syntheses, FT-IR, Crystal Packing, and Electronic Structure
title The Black Polymorph of TTF-CA: TTF Polymorphism and Solvent Effects in Mechanochemical and Vapor Digestion Syntheses, FT-IR, Crystal Packing, and Electronic Structure
spellingShingle The Black Polymorph of TTF-CA: TTF Polymorphism and Solvent Effects in Mechanochemical and Vapor Digestion Syntheses, FT-IR, Crystal Packing, and Electronic Structure
Lapidus, Saul H.
Tetrathiafulvalene-Chloranil (Ttf-Ca)
Crystal Packing,
Ft-Ir
Electronic Structure
title_short The Black Polymorph of TTF-CA: TTF Polymorphism and Solvent Effects in Mechanochemical and Vapor Digestion Syntheses, FT-IR, Crystal Packing, and Electronic Structure
title_full The Black Polymorph of TTF-CA: TTF Polymorphism and Solvent Effects in Mechanochemical and Vapor Digestion Syntheses, FT-IR, Crystal Packing, and Electronic Structure
title_fullStr The Black Polymorph of TTF-CA: TTF Polymorphism and Solvent Effects in Mechanochemical and Vapor Digestion Syntheses, FT-IR, Crystal Packing, and Electronic Structure
title_full_unstemmed The Black Polymorph of TTF-CA: TTF Polymorphism and Solvent Effects in Mechanochemical and Vapor Digestion Syntheses, FT-IR, Crystal Packing, and Electronic Structure
title_sort The Black Polymorph of TTF-CA: TTF Polymorphism and Solvent Effects in Mechanochemical and Vapor Digestion Syntheses, FT-IR, Crystal Packing, and Electronic Structure
dc.creator.none.fl_str_mv Lapidus, Saul H.
Naik, Amit
Wixtrom, Alex
Massa, Nestor Emilio
Ta Phuoc, Vinh
del Campo, Leire
Lebegue, Sebestien
Aygyayn, Jaynos G.
Abdel Fattah, Tarek
Pagola, Silvina
author Lapidus, Saul H.
author_facet Lapidus, Saul H.
Naik, Amit
Wixtrom, Alex
Massa, Nestor Emilio
Ta Phuoc, Vinh
del Campo, Leire
Lebegue, Sebestien
Aygyayn, Jaynos G.
Abdel Fattah, Tarek
Pagola, Silvina
author_role author
author2 Naik, Amit
Wixtrom, Alex
Massa, Nestor Emilio
Ta Phuoc, Vinh
del Campo, Leire
Lebegue, Sebestien
Aygyayn, Jaynos G.
Abdel Fattah, Tarek
Pagola, Silvina
author2_role author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Tetrathiafulvalene-Chloranil (Ttf-Ca)
Crystal Packing,
Ft-Ir
Electronic Structure
topic Tetrathiafulvalene-Chloranil (Ttf-Ca)
Crystal Packing,
Ft-Ir
Electronic Structure
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Tetrathiafulvalene-chloranil (TTF-CA) was synthesized by two methods, liquid assisted grinding (LAG) and vapor digestion (VD), which largely reduce the use of reaction solvents. The effects of the small quantities of LAG solvent and solvent vapors in VD toward the formation of a particular TTF-CA product polymorph were studied from both tetrathiafulvalene forms (orange and brown) as reactants. It was concluded that a high solvent polarity index favors the formation of the ionic black polymorph of TTF-CA vs the quasineutral green form, whereas the crystal structure and crystal habit of the orange tetrathiafulvalene polymorph also favors the formation of the black TTF-CA. The crystal structure of the black TTF-CA was determined from synchrotron X-ray powder diffraction (XRPD), and it consists of dimerized TTF+• and CA−• radical ions, in agreement with room temperature magnetic susceptibility measurements indicating the material is diamagnetic. FT-IR showed that the compound is a semiconductor with a small band gap of ∼0.198 eV and it remains ionic at low temperatures. The latter was confirmed by XRPD showing the black TTF-CA does not undergo a phase transition in the range 298−20 K. Band structure calculations are in good agreement with the measured band gap.
Fil: Lapidus, Saul H.. Stony Brook University; Estados Unidos
Fil: Naik, Amit. Thomas Nelson Community College; Estados Unidos
Fil: Wixtrom, Alex. Christopher Newport University; Estados Unidos
Fil: Massa, Nestor Emilio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Ta Phuoc, Vinh. UniversitéFrancois Rabelais Tours; Francia
Fil: del Campo, Leire. Université d’Orleans; Francia
Fil: Lebegue, Sebestien. Université de Lorraine; Francia
Fil: Aygyayn, Jaynos G.. Université de Lorraine; Francia
Fil: Abdel Fattah, Tarek. Christopher Newport University; Estados Unidos
Fil: Pagola, Silvina. College of William and Mary; Estados Unidos
description Tetrathiafulvalene-chloranil (TTF-CA) was synthesized by two methods, liquid assisted grinding (LAG) and vapor digestion (VD), which largely reduce the use of reaction solvents. The effects of the small quantities of LAG solvent and solvent vapors in VD toward the formation of a particular TTF-CA product polymorph were studied from both tetrathiafulvalene forms (orange and brown) as reactants. It was concluded that a high solvent polarity index favors the formation of the ionic black polymorph of TTF-CA vs the quasineutral green form, whereas the crystal structure and crystal habit of the orange tetrathiafulvalene polymorph also favors the formation of the black TTF-CA. The crystal structure of the black TTF-CA was determined from synchrotron X-ray powder diffraction (XRPD), and it consists of dimerized TTF+• and CA−• radical ions, in agreement with room temperature magnetic susceptibility measurements indicating the material is diamagnetic. FT-IR showed that the compound is a semiconductor with a small band gap of ∼0.198 eV and it remains ionic at low temperatures. The latter was confirmed by XRPD showing the black TTF-CA does not undergo a phase transition in the range 298−20 K. Band structure calculations are in good agreement with the measured band gap.
publishDate 2014
dc.date.none.fl_str_mv 2014-01
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/11336/24976
Lapidus, Saul H.; Naik, Amit; Wixtrom, Alex; Massa, Nestor Emilio; Ta Phuoc, Vinh; et al.; The Black Polymorph of TTF-CA: TTF Polymorphism and Solvent Effects in Mechanochemical and Vapor Digestion Syntheses, FT-IR, Crystal Packing, and Electronic Structure; American Chemical Society; Crystal Growth & Design; 14; 1; 1-2014; 91-100
1528-7483
CONICET Digital
CONICET
url http://hdl.handle.net/11336/24976
identifier_str_mv Lapidus, Saul H.; Naik, Amit; Wixtrom, Alex; Massa, Nestor Emilio; Ta Phuoc, Vinh; et al.; The Black Polymorph of TTF-CA: TTF Polymorphism and Solvent Effects in Mechanochemical and Vapor Digestion Syntheses, FT-IR, Crystal Packing, and Electronic Structure; American Chemical Society; Crystal Growth & Design; 14; 1; 1-2014; 91-100
1528-7483
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/cg401203r
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/cg401203r
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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
_version_ 1844613907707068416
score 13.070432

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