Synthesis and Optical Properties of Red and Deep-Red Emissive Polymeric and Copolymeric BODIPY Dyes
Synthesis and Optical Properties of Red and Deep-Red Emissive Polymeric and Copolymeric BODIPY Dyes
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DOI：
10.1021/cm900276r
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发表时间：
2009-05-26
影响因子：
8.6
通讯作者：
Liu, Haiying
中科院分区：
文献类型：
--
作者：
Donuru, Venkat R.;Vegesna, Giri K.;Liu, Haiying
深红色发光聚合物 BODIPY 染料（聚合物 A 和 B），即聚（2,6-BODIPY-乙炔基），是通过 2,6-二碘官能化 BODIPY 单体与 2,6-二乙炔基官能化 BODIPY 单体在钯催化 Sonogashira 聚合反应中制备的。聚 (2,6-BODIPY-乙炔基) 在深红色区域发射，发射光谱最大值在 680 nm 左右，并且由于π共轭的显着延伸，与最初的 BODIPY 染料相比，吸收和发射最大值都表现出显着的红移（高达 163 和 172 nm）。红色发射共聚 BODIPY 染料（聚合物 C、D 和 E）也是通过二乙炔基官能化 BODIPY 单体与 9,9-双(6'-(己硫基)己基)-2,7-二碘-9H-芴的钯催化 Sonogashira 聚合制备的， 分别为1,4-二碘2,5-二癸氧基苯和2,5-二碘-3-癸基噻吩。将不同带隙单体单元掺入聚（2,6-BODIPY-乙炔）中产生了发射波长范围为 641 至 664 nm 的共聚物。这些聚合物（聚合物 A-D）的荧光寿命为 2.8 至 3.8 ns，但具有噻吩部分的共聚物（聚合物 E）除外，由于硫的重原子效应诱导的有效系间窜越，其寿命短得多，为 0.23 ns，且荧光量子产率低。
Deep-red emissive polymeric BODIPY dyes (polymers A and B), poly(2,6-BODIPY-ethynylene)s, were prepared by palladium-catalyzed Sonogashira polymerization of 2,6-diiodo-functionalized BODIPY monomers with 2,6-diethynyl-functionalized BODIPY monomers. Poly(2,6-BODIPY-ethynylene)s emit in the deep-red region with emission spectral maxima at around 680 nm and exhibit significant red shifts (up to 163 and 172 nm) of both absorption and emission maxima compared with their initial BODIPY dyes due to significant extension of pi-conjugation. Red emissive copolymeric BODIPY dyes (polymers C, D, and E) were also prepared by palladium-catalyzed Sonogashira polymerization of a diethynyl-functionalized BODIPY monomer with 9,9-bis(6'-(hexylthio)hexyl)-2,7-diiodo-9H-fluorene, 1,4-diiodo2,5-didecyloxybenzene, and 2,5-diiodo-3-decylthiophene, respectively. Incorporation of different band gap monomer units into poly(2,6-BODIPY-ethynylene)s resulted in copolymers with a range of emission wavelengths from 641 to 664 nm. The fluorescence lifetimes of these polymers (polymers A-D) are from 2.8 to 3.8 ns except the copolymer with thiophene moieties (polymer E), which displays a much shorter lifetime of 0.23 ns with low fluorescence quantum yield due to efficient intersystem crossing induced by the heavy atom effect of sulfur.