Cunning defects: Emission control by structural point defects on Cu(i)I double chain coordination polymers
Entity
UAM. Departamento de Química InorgánicaPublisher
The Royal Society of ChemistryDate
2020-01-01Citation
10.1039/c9tc05185f
Journal of Materials Chemistry C 8.4 (2020): 1448-1458
ISSN
2050-7526 (Print); 2050-7534 (Online)DOI
10.1039/c9tc05185fFunded by
The authors thank financial support from the Spanish Ministerio de Economıa y Competitividad (MAT2016-77608-C3-1-P, MAT2016-75883-C2-2-P, MAT2010-20843-C02-01, CTQ2016-75816- C2-1P, MAT2016-75586-C4-4-P) and by EU-FEDER funds. JGP thanks to Servicios Generales de Apoyo a la Investigacion (SEGAI) at La Laguna University. J. I. M. acknowledges the financial support by the ‘‘Ramo´n y Cajal’’ Program of MINECO (Grant RYC-2015- 17730) and the EU via the ERC-Synergy Program (Grant ERC-2013- SYG-610256 NANOCOSMOS). J. C. E. acknowledges the financialsupport by the ‘‘FPI-MINECO’’ Program of MINECO (Grant BES2015-071534). R. D. C. acknowledges the program ‘‘Ayudas para la atraccio´n de talento investigador—Modalidad 1 of the Consejerı´a de Educacio´n, Juventud y Deporte—Comunidad de Madrid with the Reference No. 2016-T1/IND-1463.’’, Spanish MINECO for the Ramo´n y Cajal program (RYC-2016-20891), the Europa Excelencia program (ERC2019-092825), and HYNANOSC (RTI2018-099504-A-C22). R. D. C. also acknowledges the 2018 Leonardo Grant for Researchers and Cultural Creators from BBVA Foundation and the FOTOART-CM project funded by Madrid region under programm P2018/NMT-4367. J. F.-C. acknowledges the Marie Skłodowska-Curie Individual Fellowships (H2020-MSCA-IF-2017). This paper is dedicated to Dmitri Mendele´yev in honour of the 150th anniversary of the discovery of the periodic tableProject
Gobierno de España. MAT2016-77608-C3-1-P; Gobierno de España. MAT2016-75883-C2-2-P; Gobierno de España. MAT2010-20843-C02-01; Gobierno de España. CTQ2016-75816- C2-1P; Gobierno de España. MAT2016-75586-C4-4-P; info:eu-repo/grantAgreement/ERC/FP7/610256; Gobierno de España. RTI2018-099504-A-C22; Comunidad de Madrid. P2018/NMT-4367/FotoArt-CMEditor's Version
https://doi.org/10.1039/C9TC05185FSubjects
Cuprous Iodide; Xantphos; Complex; QuímicaNote
The following version is an accepted manuscript in Journal of Materials Chemistry C 8.4 (2020): 1448-1458 and may be found at ttps://doi.org/10.1039/C9TC05185FRights
© The Royal Society of Chemistry 2020Abstract
The direct reaction between CuI and 3,5-dichloropyridine, in acetonitrile at room temperature, gives rise to [Cu(Cl2-py)I]n (Cl2-py = 3,5-dichloropyridine), which consists of a Cu(i)-I double chain based coordination polymer (CP) grafted with 3,5-dichloropyridine. In this simple one-pot process, the modulation of the reaction conditions, i.e. slight variations in the CuI and Cl2-py ratio caused by in situ disproportion, can, however, produce significant changes in the physical properties of the materials. For instance, the reaction carried out in a 1 : 1 ratio under ambient conditions leads to compound 1, while compound 1′ is obtained upon a solvothermal process of stoichiometric reaction mixture, Cl2-py and CuI, which produces partial disproportion (<0.5% in weight) of the initial Cu(i). Interestingly, compounds 1 and 1′ show an identical chemical composition and structure as determined by both single crystal and powder X-ray diffraction. However, they display remarkable differences in the luminescence behavior, featuring broad emission bands centered at 515 and 670 nm and associated to photoluminescence quantum yields of 12 and 5% for 1 and 1′, respectively. Density functional theory (DFT) calculations allowed us to rationalize the nature of this rare behavior. This is attributed to structural defects related to the weaker coordination bond present in these structures that provoke the strong red-shifted emission
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Google Scholar:Conesa-Egea, Javier
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González-Platas, Javier
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Rodríguez-Mendoza, Ulises R.
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Martínez, José Ignacio
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Ocón Esteban, Pilar
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Fernández-Moreira, Vanesa
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Costa, Rubén D.
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Fernández-Cestau, Julio
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Zamora Abanades, Félix Juan
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Amo Ochoa, María Pilar
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