Kaczmarek Anna M, Esquivel Dolores, Ouwehand Judith, Van Der Voort Pascal, Romero-Salguero Francisco J, Van Deun Rik
L3 Luminescent Lanthanide Lab, Department of Inorganic and Physical Chemistry, Ghent University, Krijsglaan 281-S3, B-9000 Ghent, Belgium.
Departamento de Química Orgánica, Instituto Universitario de Investigación en Química Fina y Nanoquímica IUIQFN, Facultad de Ciencias, Universidad de Córdoba, Campus de Rabanales, Edificio Marie Curie, E-14071 Córdoba, Spain.
Dalton Trans. 2017 Jun 28;46(24):7878-7887. doi: 10.1039/c7dt01620d. Epub 2017 Jun 9.
Two materials - a mesoporous silica (MS) and a periodic mesoporous organosilica (PMO) functionalized with dipyridyl-pyridazine (dppz) units were grafted with near-infrared (NIR) emitting lanthanide (Nd, Er, Yb) complexes in an attempt to obtain hybrid NIR emitting materials. The parent materials: dppz-vSilica and dppz-ePMO were prepared by a hetero Diels-Alder reaction between 3,6-di(2-pyridyl)-1,2,4,5-tetrazine (dptz) and the double bonds of either ethenylene-bridged PMO (ePMO) or vinyl-silica (vSilica) and subsequent oxidation. The dppz-vSilica is reported here for the first time. The prepared lanthanide-PMO/silica hybrid materials were studied in depth for their luminescence properties at room temperature and chosen Nd and Yb samples also at low temperature (as low as 10 K). We show that both the dppz-vSilica and dppz-ePMO materials can be used as "platforms" for obtaining porous materials showing NIR luminescence. To obtain NIR emission these materials can be excited either in the UV or Vis region (into the π→π* transitions of the ligands or directly into the f-f transitions of the Ln ions). More interestingly, when functionalized with Nd or Ybβ-diketonate complexes these materials showed interesting luminescence properties over a wide temperature range (10-360 K). The Yb materials were investigated for their potential use as ratiometric temperature sensors.
两种材料——一种介孔二氧化硅（MS）和一种用联吡啶哒嗪（dppz）单元功能化的周期性介孔有机硅（PMO），与近红外（NIR）发光镧系元素（Nd、Er、Yb）配合物接枝，试图获得近红外发光杂化材料。母体材料：dppz - vSilica和dppz - ePMO是通过3,6 - 二（2 - 吡啶基）- 1,2,4,5 - 四嗪（dptz）与乙烯桥联PMO（ePMO）或乙烯基二氧化硅（vSilica）的双键之间的杂环狄尔斯 - 阿尔德反应以及随后的氧化反应制备的。本文首次报道了dppz - vSilica。对制备的镧系元素 - PMO/二氧化硅杂化材料在室温下的发光性质进行了深入研究，还选择了Nd和Yb样品在低温（低至10 K）下进行研究。我们表明，dppz - vSilica和dppz - ePMO材料都可以用作获得近红外发光多孔材料的“平台”。为了获得近红外发射，这些材料可以在紫外或可见光区域被激发（进入配体的π→π*跃迁或直接进入Ln离子的f - f跃迁）。更有趣的是，当用Nd或Ybβ - 二酮配合物功能化时，这些材料在很宽的温度范围（10 - 360 K）内表现出有趣的发光性质。对Yb材料作为比率温度传感器的潜在用途进行了研究。
