Amide-driven secondary building unit structural transformations between Zn(II) coordination polymers

The behavior of coordination polymers (CPs) against external stimuli has witnessed remarkable attention, especially when the resulting CPs present reversible molecular arrays. Accordingly, CPs with these characteristics can lead to differences in their properties owing to these structural difference...

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Detalles Bibliográficos
Autores: Ejarque, Daniel|||0000-0002-1014-1128, Calvet, Teresa|||0000-0002-4058-7171, Font-Bardia, Mercè|||0000-0002-7892-8744, Pons Picart, Josefina|||0000-0003-1834-9326
Tipo de recurso: artículo
Fecha de publicación:2022
País:España
Institución:Universitat Autònoma de Barcelona
Repositorio:Dipòsit Digital de Documents de la UAB
Idioma:inglés
OAI Identifier:oai:ddd.uab.cat:265988
Acceso en línea:https://ddd.uab.cat/record/265988
https://dx.doi.org/urn:doi:10.1021/acs.cgd.2c00520
Access Level:acceso abierto
Palabra clave:Amide moieties
Coordination Polymers
Coordination-polymers
External stimulus
Molecular arrays
Molecular switches
Property
Secondary building units
Structural differences
Structural transformation
Descripción
Sumario:The behavior of coordination polymers (CPs) against external stimuli has witnessed remarkable attention, especially when the resulting CPs present reversible molecular arrays. Accordingly, CPs with these characteristics can lead to differences in their properties owing to these structural differences, being promising for their use as potential molecular switches with diverse applications. Herein, we have synthesized four Zn(II) CPs bearing α-acetamidocinnamic acid (HACA) and 4,4'-bipyridine (4,4'-bipy). The reaction between Zn(OAc)2·2H2O, HACA, and 4,4'-bipy yields {[Zn(ACA)2(4,4'-bipy)]·EtOH}n (1), which was used for the formation of three CPs through dissolution-recrystallization structural transformations (DRSTs): {[Zn(ACA)2(4,4'-bipy)]·2MeOH}n (2), {[Zn2(μ-ACA)2(ACA)2(4,4'-bipy)]·2H2O}n (3), and {[Zn3(μ-ACA)6(4,4'-bipy)]·0.75CHCl3}n (4). The study of the four crystal structures revealed that their secondary building units (SBUs) comprise monomeric, dimeric, and trimeric arrangements linked by 4,4'-bipy ligands. The fundamental role of the utilized solvent and/or temperature, as well as their effect on the orientation of the amide moieties driving the formation of the different SBUs is discussed. Furthermore, the reversibility and interconversion between the four CPs have been assayed. Finally, their solid-state photoluminescence has evinced that the effect of the amide moieties not only predetermine a different SBU but also lead to a different emission in 4 compared with 1-3.