Highly Efficient Room-Temperature Phosphorescence from Halogen-Bonding-Assisted Doped Organic Crystals,The Journal of Physical Chemistry A

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Highly Efficient Room-Temperature Phosphorescence from Halogen-Bonding-Assisted Doped Organic Crystals
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-11-07 00:00:00 , DOI: 10.1021/acs.jpca.7b10160
Lu Xiao _{1,

2} , Yishi Wu ₁ , Jianwei Chen _{1,

2} , Zhenyi Yu _{1,

2} , Yanping Liu _{1,

2} , Jiannian Yao _{1,

2} , Hongbing Fu _{1,

3,

4}

Affiliation

The development of metal-free organic room temperature phosphorescence (RTP) materials has attracted increasing attention because of their applications in sensors, biolabeling (imaging) agents and anticounterfeiting technology, but remains extremely challenging owing to the restricted spin-flip intersystem crossing (ISC) followed by low-yield phosphorescence that cannot compete with nonradiative relaxation processes. Here, we report a facile strategy to realize highly efficient RTP by doping iodo difluoroboron dibenzoylmethane (I-BF₂dbm-R) derivatives into a rigid crystalline 4-iodobenzonitrile (Iph-C≡N) matrix. We found that halogen bonding between cyano group of Iph-C≡N matrix and iodine atom of I-BF₂dbm-R dopant is formed in doped crystals, i.e., Iph-C≡N···I-BF₂dbm-R, which not only suppresses nonradiative relaxation of triplets but also promotes the spin–orbit coupling (SOC). As a result, the doped crystals show intense RTP with an efficiency up to 62.3%. By varying the substituent group R in I-BF₂dbm-R from electron donating −OCH₃ to electron accepting −F, −CN groups, the ratio between phosphorescence and fluorescence intensities has been systematically increased from 3.8, 15, to 50.

中文翻译：

卤素键合掺杂有机晶体的高效室温磷光

由于无金属有机室温磷光（RTP）材料在传感器，生物标记（成像）剂和防伪技术中的应用，引起了越来越多的关注，但由于自旋翻转系统间交叉（ISC）受限制，仍然极具挑战性其次是不能与非辐射弛豫过程竞争的低产率磷光。在这里，我们报告了一种通过将碘代二氟硼二苯甲酰甲烷（I-BF ₂ dbm-R）衍生物掺杂到刚性结晶的4-碘苯甲腈（Iph-C≡N）基质中来实现高效RTP的简便策略。发现在Iph-C≡N···I-BF ₂掺杂晶体中，Iph-C≡N基体的氰基与I-BF ₂ dbm-R掺杂剂的碘原子之间形成卤素键。dbm-R不仅抑制三联体的非辐射弛豫，而且促进自旋轨道耦合（SOC）。结果，掺杂的晶体表现出强烈的RTP，效率高达62.3％。通过将I-BF ₂ dbm-R中的取代基R从供电子的-OCH ₃变为接受电子的-F，-CN基团，磷光和荧光强度之比已系统地从3.8、15增加到50。

更新日期：2017-11-08

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