Toward controlling the solid state valence tautomeric interconversion character by solvation

Marcos Antônio Ribeiro; Daniel Earl Stasiw; Philip Pattison; Paul R. Raithby; David A. Shultz; Carlos Basílio Pinheiro

Please use this identifier to cite or link to this item: http://hdl.handle.net/1843/56368

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DC Field	Value	Language
dc.creator	Marcos Antônio Ribeiro	pt_BR
dc.creator	Daniel Earl Stasiw	pt_BR
dc.creator	Philip Pattison	pt_BR
dc.creator	Paul R. Raithby	pt_BR
dc.creator	David A. Shultz	pt_BR
dc.creator	Carlos Basílio Pinheiro	pt_BR
dc.date.accessioned	2023-07-17T12:34:57Z	-
dc.date.available	2023-07-17T12:34:57Z	-
dc.date.issued	2016	-
dc.citation.volume	16	pt_BR
dc.citation.issue	4	pt_BR
dc.citation.spage	2385	pt_BR
dc.citation.epage	2393	pt_BR
dc.identifier.doi	https://doi.org/10.1021/acs.cgd.6b00159	pt_BR
dc.identifier.issn	1528-7505	pt_BR
dc.identifier.uri	http://hdl.handle.net/1843/56368	-
dc.description.resumo	Crystals of [Co(diox)2 (4-NO 2-py) 2 ] (1) and [Co(diox)2(4-CN-py) 2] (2) where diox are the o-dioxolene 3,5-di-t-butylsemiquinonate (SQ•−) and/or 3,5-di-t-butylcatecholate (Cat 2−) ions, 4-NO 2-py is 4-nitro-pyridine, 4-CN-py is 4-cyano-pyridine, are among the few known crystals presenting both thermally induced and photoinduced ls-[M +3(SQ•−)(Cat 2−)] hs-[M 2+(SQ•−) 2] valence tautomeric interconversion (VTI). In 2, the thermal-induced VTI is cooperative, characterizing an abrupt conversion, and in 1 it is noncooperative. In this work, crystals of [Co(diox)2(4-NO 2 -py) 2]· benzene (1BZ), [Co(diox)2 (4-NO 2-py) 2]·toluene (1TL), [Co(diox)2(4-CN-py) 2]·benzene (2BZ), and [Co(diox)2(4-CN-py) 2]·toluene (2TL) have been prepared and analyzed by single crystal X-ray diffraction in order to investigate how solvation modulates thermally induced VTI. Crystallographic data were also successfully used together with the two-state equilibrium equation to estimate ΔH° and ΔS° VTI thermodynamic parameters. The solvate crystals, like the nonsolvated ones, present essentially reversible thermally induced VTI. The 1TL crystal presents the same monoclinic symmetry and the same intermolecular hydrogen-bonded network of 1, and both present a noncooperative thermal-induced VTI. The 1BZ crystal has triclinic symmetry and presents a cooperative VTI with a thermal hysteresis of ∼30 K. In contrast to 2, thermally induced VTI in 2BZ and 2TL is noncooperative despite the fact that 2, 2BZ, and 2TL crystals exhibit the same monoclinic symmetry and the same intermolecular hydrogen-bonded network. In 2BZ and 2TL benzene and toluene molecules as well as the t-butyl groups of the o-dioxolene molecules convert gradually from being dynamically disordered at about 300 K to a static disorder state below 150 K. The layer separation distance of interacting [Co(diox)2(4-X-py) 2], X = CN and NO 2, molecules in all solvate crystals is ∼15 Å, whereas in 2, which presents cooperative VTI, it is ∼12 Å. An order−disorder component might account for the stabilization of the metastable hs-Co 2+ state in 2BZ and in 2TL, but no disorder was found in the 1TL crystals. Therefore, the lack of cooperativity in the thermally induced VTI in these crystals seems to be due to the large distance between the layers of interacting molecules. Cooperativity in the VTI of 1BZ crystal is likely to be related with the unique molecular bond scheme network that connects neighboring active [Co(diox)2(4-NO 2-py) 2] molecules through the o-dioxolene oxygen atoms bonded directly to the Co ion.	pt_BR
dc.description.sponsorship	CNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico	pt_BR
dc.description.sponsorship	FAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais	pt_BR
dc.description.sponsorship	CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior	pt_BR
dc.language	eng	pt_BR
dc.publisher	Universidade Federal de Minas Gerais	pt_BR
dc.publisher.country	Brasil	pt_BR
dc.publisher.department	ICX - DEPARTAMENTO DE FÍSICA	pt_BR
dc.publisher.initials	UFMG	pt_BR
dc.relation.ispartof	Crystal Growth & Design	-
dc.rights	Acesso Restrito	pt_BR
dc.subject	Solid state valence tautomeric	pt_BR
dc.subject.other	Valência	pt_BR
dc.subject.other	Tautomeria	pt_BR
dc.title	Toward controlling the solid state valence tautomeric interconversion character by solvation	pt_BR
dc.type	Artigo de Periódico	pt_BR
dc.url.externa	https://pubs.acs.org/doi/10.1021/acs.cgd.6b00159	pt_BR
dc.identifier.orcid	https://orcid.org/0000-0003-0526-7372	pt_BR
dc.identifier.orcid	https://orcid.org/0000-0002-2944-0662	pt_BR
dc.identifier.orcid	https://orcid.org/0000-0001-8121-6812	pt_BR
dc.identifier.orcid	https://orcid.org/0000-0002-8674-1779	pt_BR
Appears in Collections:	Artigo de Periódico

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