Luminescent Thermochromism of 2D Coordination Polymers Based on Copper(I) Halides with 4-Hydroxythiophenol.
Solvothermal reactions between copper(I) halides and 4-mercaptophenol give rise to the formation of three coordination polymers with general formula [Cu3X(HT)2]n(X=Cl, 1; Br, 2; and I, 3). The structures of these coordination polymers have been determined by X-ray diffraction at both room- and low temperature (110 K), showing a general shortening in Cu-S, Cu-X and Cu-Cu bond lengths at low temperatures. 1 and 2 are isostructural, consisting of layers in which the halogen ligands act as μ3-bridges joining two Cu1 and one Cu2 atoms whereas in 3 the iodine ligands is as μ4-mode but the layers are quasi-isostructural with 1 or 2. These compounds show a reversible thermochromic luminescence, with strong orange emission for 1 and 2, but weaker for 3 at room temperature, whereas upon cooling at 77 K 1 and 2 show stronger yellow emission, and 3 displays stronger green emission. DFT calculations have been used to rationalize these observations. These results suggest a high potential for this novel and promising stimuli-responsive materials.
Departamento de Química Inorgánica, Universidad Autónoma de Madrid, Madrid, 28049, Spain.
Javier
J
Troyano
Laboratorio de Difracción de Rayos X de Monocristal, Servicio Interdepartamental de Investigación, Universidad Autónoma de Madrid, 28049, Madrid, Spain.
Josefina
J
Perles
Departamento de Química Inorgánica, Universidad Autónoma de Madrid, Madrid, 28049, Spain.
Pilar
P
Amo-Ochoa
ESISNA Group, Department of Surfaces, Coatings and Molecular Astrophysics, Institute of Material Science of Madrid (ICMM-CSIC), 28049, Madrid, Spain.
Jose Ignacio
JI
Martínez
Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad de Zaragoza, 50009, Zaragoza, Spain.
Maria
M
Concepción Gimeno
Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad de Zaragoza, 50009, Zaragoza, Spain.
Vanesa
V
Fernández-Moreira
Departamento de Química Inorgánica, Universidad Autónoma de Madrid, Madrid, 28049, Spain.|Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA Nanociencia), Cantoblanco, 28049, Madrid, Spain.|Condensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid, 28049, Madrid, Spain.
Félix
F
Zamora
Departamento de Química Inorgánica, Universidad Autónoma de Madrid, Madrid, 28049, Spain.
Salomé
S
Delgado
coordination polymers; luminescent materials; multifunctional materials; stimuli-responsive materials; thermochromic coordination polymers