Microwave-assisted preparation of intense luminescent BODIPY-containing hybrids with high photostability and low leachability
Microwave-assisted preparation of intense luminescent BODIPY-containing hybrids with high photostability and low leachability
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DOI：
10.1039/b923449g
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发表时间：
2010-01-01
影响因子：
--
通讯作者：
Chujo, Yoshiki
中科院分区：
文献类型：
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作者：
Kajiwara, Yuichi;Nagai, Atsushi;Chujo, Yoshiki
通过溶胶-凝胶缩合和自由基共聚合相结合，一锅法即可获得高发光性能的有机-无机杂化材料。以甲基丙烯酸酯系硼二吡咯亚甲基（BODIPY）染料1为单体，甲基丙烯酸酯系硼二吡咯亚甲基（BODIPY）染料与甲基丙烯酸钾反应，在微波辐射或常规加热条件下，进行甲基三甲氧基硅烷（MeTMOS）的溶胶-凝胶反应和甲基丙烯酸羟乙酯（HEMA）的自由基共聚反应。通过紫外可见光谱、光致发光光谱、差示扫描量热法（DSC）、热重分析（TGA）和扫描电子显微镜（SEM）对所得杂化材料进行了表征。微波辐射导致更快速和均匀的反应相比，传统的加热条件。因此，通过微波照射获得的杂化物由于抑制了源自BODIPY单元的pi-pi堆叠的聚集而显示出更高的透明度。所得杂化物的量子产率（Phi F =类似于94%）高于1在甲醇溶液中的量子产率。与聚（HEMA-co-1）膜相比，由于二氧化硅基质的屏蔽，杂化物的光稳定性得到改善;即，避免了氧在BODIPY单元的激发态中的进入。此外，由于HEMA聚合物和1之间的共价键，与不含甲基丙烯酸酯基团的BODIPY染料相比，BODIPY染料1从杂化物中的洗脱显著减少。
Organic-inorganic hybrids with high luminescence were facilely obtained by a one-pot process through the combination of sol-gel condensation and radicalcopolymerization. The sol-gel reaction of methyltrimethoxysilane (MeTMOS) was carried out together with radical copolymerization of 2-hydroxyethyl methacrylate (HEMA) with methacrylate-tethering boron dipyrromethene (BODIPY) dye 1, which was prepared by the reaction of a meso-butyl-substituted BODIPY dye and potassium methacrylate, under microwave irradiation or conventional heating conditions. The obtained hybrids were characterized by UV-vis and photoluminescence spectroscopies, and differential scanning calorimetry (DSC) thermogram, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) measurements. Microwave irradiation led to a more rapid and homogeneous reaction as compared to conventional heating conditions. Therefore, the obtained hybrids by means of microwave irradiation showed higher transparency owing to inhibition of aggregation derived from pi-pi stacking of BODIPY units. Quantum yields (Phi F = similar to 94%) of the obtained hybrids were higher than those of 1 in methanol solution. Photostability of the hybrids was improved in comparison with that of poly(HEMA-co-1) film due to shielding by silica matrices; i.e., the access of oxygen in the excited state of BODIPY units is avoided. Moreover, the elution of BODIPY dye 1 from the hybrids was significantly reduced as compared to BODIPY dye without the methacrylate group due to the covalent bond between HEMA polymer and 1.