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Monitoring spin-crossover phenomena via Re(i) luminescence in hybrid Fe(ii) silica coated nanoparticles

Díaz-Ortega, Ismael Francisco, Fernández-Barbosa, Eva Luz, Titos-Padilla, Silvia, Pope, Simon J. A., Jiménez, Juan-Ramón, Colacio, Enrique and Herrera, Juan Manuel 2021. Monitoring spin-crossover phenomena via Re(i) luminescence in hybrid Fe(ii) silica coated nanoparticles. Dalton Transactions 50 , pp. 16176-16184. 10.1039/D1DT03334D

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Bare (1) and silica coated (1@SiO2) spin crossover (SCO) nanoparticles based on the polymer {[Fe(NH2Trz)3](BF4)2}n have been prepared following a water-in-oil synthetic procedure. For 1, the critical temperatures of the spin transition are TC↓ = 214.6 K and TC↑ = 220.9 K. For 1@SiO2, the abruptness of the transition is enhanced and the critical temperatures are centred at room temperature (TC↓ = 292.1 K and TC↑ = 296.3 K). An inert Re(I) complex of formula [Re(phen)(CO)3(PETES)](PF6) (phen = 1, 10-phenanthroline; PETES = 2(4-pyridylethyl)triethoxysilane) (Re) was also synthesized yielding intense green emission centred at λem = 560 nm. The grafting of this complex on the silica shell of 1@SiO2 led to a bifunctional SCO-luminescence composite (1@SiO2/Re) whose luminescence properties were tuned by the spin state switching. Temperature-variable photophysical studies showed that luminescence and spin transition were synchronized through a radiative (trivial) energy transfer mechanism between the Re(I) and the Fe(II)-LS (LS, Low Spin) centres.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Additional Information: This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence
Publisher: Royal Society of Chemistry
ISSN: 1477-9226
Date of First Compliant Deposit: 8 November 2021
Date of Acceptance: 22 October 2021
Last Modified: 11 Jan 2022 13:50

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