具有热激活延迟荧光和双光子吸收的顺反异构诱导共晶多晶型,Advanced Optical Materials

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具有热激活延迟荧光和双光子吸收的顺反异构诱导共晶多晶型
Advanced Optical Materials ( IF 8.0 ) Pub Date : 2022-05-29 , DOI: 10.1002/adom.202200286
Xiangyu Zhang ₁ , Jianbo De _{2,

3} , Haichao Liu ₁ , Qing Liao ₂ , Shi‐Tong Zhang _{1,

4} , Changjiang Zhou ₅ , Hongbing Fu _{2,

3} , Bing Yang ₁

Affiliation

2-(苯并[ d ]噻唑-2-基)-3-(芘-1-基)丙烯腈(Py-BZTCN)和1,2,4,5-四氰基苯(TCNB)通过分子间电荷构建共晶-供体和受体之间的转移（CT）相互作用。顺式和反式Py-BZTCN 的异构体诱导形成两种不同的晶体堆积，Py-BZTCN 和 TCNB 的化学计量比分别为 1:2 和 1:1，分别对应于 PCNTC-O 和 PCNTC-R 的共晶。PCNTC-O 共晶呈现橙黄色正常荧光，CT 从芘 (Py) 单体到 TCNB，而 PCNTC-R 共晶呈现红色热激活延迟荧光 (TADF)，CT 从 Py 二聚体到 TCNB。这种光物理差异源于相对于 Py 单体，Py 二聚体具有更高的最高占据分子轨道 (HOMO) 能级，这导致 PCNTC-R 共晶中的 CT 更强。两种共晶都具有独特的双光子吸收 (TPA) 特性，并且将单体转化为二聚体作为 CT 共晶中的供体有效地改变了超分子特性。值得注意的是，

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Cis-Trans Isomerism Inducing Cocrystal Polymorphism with Thermally Activated Delayed Fluorescence and Two-Photon Absorption

The cocrystals of 2-(benzo[d]thiazol-2-yl)-3-(pyren-1-yl)acrylonitrile (Py-BZTCN) and 1,2,4,5-tetracyanobenzene (TCNB) are constructed through intermolecular charge-transfer (CT) interactions between donor and acceptor. Cis- and trans-isomers of Py-BZTCN induce the formation of two different crystal packing with 1:2 and 1:1 stoichiometric ratios between Py-BZTCN and TCNB, corresponding to the cocrystals of PCNTC-O and PCNTC-R, respectively. PCNTC-O cocrystal exhibits orange-yellow normal fluorescence with a CT from pyrene (Py) monomer to TCNB, while PCNTC-R cocrystal presents red thermally activated delayed fluorescence (TADF) with a CT from Py dimer to TCNB. This photophysical difference originates from that, relative to Py monomer, Py dimer has an elevated energy level of highest occupied molecular orbital (HOMO), which results in a stronger CT in PCNTC-R cocrystal. Both cocrystals possess unique two-photon absorption (TPA) properties, and changing monomer into dimer as a donor in the CT cocrystal effectively alters the supramolecular properties. Noteworthily, PCNTC-R is a rare case in which TADF and TPA are integrated into a cocrystal, opening up a new supramolecular strategy to explore the multi-functional materials.

更新日期：2022-05-29

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