Nanoparticles of Low Optical Band Gap Conjugated Polymers
Nanoparticles of Low Optical Band Gap Conjugated Polymers
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DOI：
10.1021/ma3013459
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发表时间：
2012-09
期刊：
影响因子：
5.5
通讯作者：
J. Huber;C. Jung;S. Mecking
中科院分区：
文献类型：
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作者：
J. Huber;C. Jung;S. Mecking
9，9-双Sonogashira偶联（2-乙基己基）-2，7-二乙炔基-9H-芴（I）与2，7-二溴-9，9-双（2-乙基己基）-9H-芴（2）和二溴取代的电子接受亚芳基5，7-双（5-溴噻吩-2-基）-2，3-二己基噻吩并（3，4-B）吡嗪（3），4，7-双（5-溴-4-（2-乙基己基）噻吩-2-基）双（苯并噻二唑）（4）或4，9-双（5-溴-4-（2-乙基己基）噻吩-2-基）-6，7-二己基噻二唑并（3，4-g）喹喔啉（5），在细乳液聚合方法中，得到平均尺寸在50至120 nm范围内的聚（亚芳基亚乙炔基）纳米颗粒的胶体稳定分散体。对于这些聚（（1-alt-（2-co-X））/（X = 3、4或5）、聚（1-alt-3）、聚（1-alt-4）和聚（1-alt-5）水性纳米颗粒分散体，随着受体单体的掺入增加，吸收在红色和NIR区域中越来越多地发生，对于聚（1-alt-4）分散体，直到Aabs = 1 μ m都有强吸收。对于聚（1-alt-（2- co-3））纳米颗粒，在Aem = ca下也观察到荧光。700.nm处，由于能量转移到低能发色团，这在该长波长处发生，特别是即使在仅掺入1mol%3的情况下。通过改变溶剂质量的替代后聚合方法产生自稳定纳米颗粒的稀水性分散体。一种两亲性嵌段共聚物，聚乙二醇-嵌段-聚（1-alt-6）-嵌段-聚乙二醇，通过叠氮化物-炔偶联的炔封端的聚（1-alt-6）（6 = 4，7-双（5-溴-4-（2-乙基己基）噻吩-2-基）苯并噻二唑），其在λ emmal ≤ 672 nm处发荧光。
Sonogashira coupling of 9,9-bis(2-ethylhexyI)- 2,7-diethynyl-9H-fluorene (I) with 2,7-dibromo-9,9-bis(2- ethylhexyl)-9H-fluorene (2) and dibromo-substituted electron accepting arylenes 5,7-bis(5-bromothiophen-2-yl)-2,3- dihexylthieno(3,4-b)pyrazine (3), 4,7-bis(5-bromo-4-(2- ethylhexyl)thiophene-2-yI)bis(benzothiadiazole) (4) or 4,9- bis (5-bromo-4-{2-ethylhexyl)thiophen-2-yl)-6, 7- dihexylthiadiazolo(3,4-g)quinoxaline (5), respectively, in a miniemulsion polymerization process afforded colloidally stable dispersions of poly(arylene ethynylene) nanoparticles with an average size in the range of SO to 120 nm. For these poly((1-alt-(2-co-X)J (X = 3, 4, or 5), poly(l-alt-3), poly(l-alt-4), and poly(l-alt-5) aqueous nanoparticle dispersions absorption occurs increasingly in the red and NIR regime with increasing incorporation of acceptor monomer, with a strong absorption up to Aabs = 1 Jlm for poly(l-alt-4) dispersions. For poly(l-alt-(2- co-3)) nanoparticles fluorescence is also observed at Aem = ca. 700.nm, which occurs at this long wavelength exclUSively even at an incorporation of only 1 mol % of 3 due to energy transfer to the Iow-energy chromophores. An alternative postpolymerization approach by change of solvent quality yielded dilute aqueous dispersions of self-stabilized nanoparticles from. an amphiphilic block copolymer, poly{ethylene glycoI)-block-poly(l-alt-6)-block-poly(ethylene glycol) generated from. alkyne-tenninated poly(l-alt-6) via azide-alkyne coupling (6 = 4,7-bis(5-bromo-4-(2-ethylhexyI)thiophene-2-yl)benzothiadiazole), which fluoresce at Aem mal< = 672 nm.