Quantum yield and morphology control of BODIPY-based supramolecular self-assembly with a chiral polymer inhibitor
Quantum yield and morphology control of BODIPY-based supramolecular self-assembly with a chiral polymer inhibitor
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DOI：
10.1038/pj.2009.302
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发表时间：
2010
期刊：
影响因子：
2.8
通讯作者：
A. Nagai;K. Kokado;J. Miyake;Y. Chujo
中科院分区：
文献类型：
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作者：
A. Nagai;K. Kokado;J. Miyake;Y. Chujo
手性棒线圈型有机硼聚合物 S-poly 和 R-poly 通过钯催化的二吡咯亚甲基硼基单体 1 的 Sonogashira-Hagihara 偶联反应制备，该单体 1 具有双碘苯基和癸基以及 S-或 R-6、6'-二乙炔基-2、2'-二辛氧基-1、1'-联萘基（S-2 和R-2)，在溶剂混合物(四氢呋喃(THF)/三乙胺＝2/1(v/v))中于40℃反应24小时。所得聚合物通过氢1核磁共振(NMR)、碳13 NMR(13 C NMR)、硼11 NMR(11 B NMR)和红外光谱进行表征。正如我们所预期的那样，对每种手性聚合物的扫描电子显微镜（SEM）分析清楚地揭示了由每个颗粒聚集形成的微米尺寸的纤维状结构。接下来，我们研究了通过动态光散射分析测量的光致发光（PL）强度之比（I/I 0= R-poly/S-poly）和粒径之间的关系，与 S-poly 和 R-poly 在 THF 中的混合聚合物的 R-poly 含量（从 0% 到 100% 变化）之间的关系。结果，PL强度和直径在70%含量时分别显示出最大值和最小值（约32 nm），这取决于手性特征的分子量和绝对值之间的差异。这些结果表明，S-poly 的 PL 强度通过添加 R-poly 影响形态变化；也就是说，R-poly 充当 S-poly 聚集的抑制剂。此外，混合聚合物（S-poly/R-poly= 30/70）的SEM图像显示出从纳米到微米尺寸的完整颗粒结构，直径约为480 nm至1.19 μm，并且混合聚合物的Φ F 显着较高（0.98）。
Chiral rod-coil-type organoboron polymers S-poly and R-poly were prepared from the palladium-catalyzed Sonogashira–Hagihara coupling reaction of boron dipyrromethene-based monomer 1, which has bisiodophenyl and decyl groups with S-or R-6, 6′-diethynyl-2, 2′-dioctyloxy-1, 1′-binaphthyls (S-2 and R-2), in a solvent mixture (tetrahydrofuran (THF)/triethylamine= 2/1 (v/v)) at 40 C for 24 h. The obtained polymers were characterized by hydrogen-1 nuclear magnetic resonance (NMR), carbon-13 NMR (13 C NMR), boron-11 NMR (11 B NMR) and infrared spectroscopy. The scanning electron microscopy (SEM) analysis of each chiral polymer clearly revealed micrometer-sized fiber-like structures formed by the aggregation of each particle, as we expected. Next, we examined the relationship between the ratio of photoluminescence (PL) intensity (I/I 0= R-poly/S-poly) and particle diameter, measured by dynamic light scattering analysis, versus the R-poly content of the mixed polymer of S-poly and R-poly in THF, which varied from 0 to 100%. As a result, the PL intensity and diameter showed maximum and minimum (about 32 nm) values, respectively, at 70% content, depending on the differences between both the molecular weights and absolute values of the chiral characters. These findings indicate that the PL intensity of S-poly influences morphology change by adding R-poly; that is, R-poly acts as an inhibitor toward the aggregation of S-poly. Furthermore, the SEM image of the mixed polymer (S-poly/R-poly= 30/70) showed complete particle structures from nano-to micrometer sizes, which were roughly 480 nm to 1.19 μm in diameter, and the Φ F of the mixed polymer was significantly high (0.98).