Liao Pei-Yu, Li Jia-Xin, Liu Jia-Chuan, Xiong Qi, Ruan Ze-Yu, Li Tao, Deng Wei, Jiang Shang-Da, Jia Jian-Hua, Tong Ming-Liang
Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, IGCME, GBRCE for Functional Molecular Engineering, Sun Yat-Sen University, Guangzhou, 510006, P. R. China.
Spin-X Institute, School of Chemistry and Chemical Engineering, State Key Laboratory of Luminescent Materials and Devices, Guangdong-Hong Kong-Macao Joint Laboratory of Optoelectronic and Magnetic Functional Materials, South China University of Technology, Guangzhou, 510640, P. R. China.
Angew Chem Int Ed Engl. 2024 Jul 1;63(27):e202401448. doi: 10.1002/anie.202401448. Epub 2024 Jun 3.
Photogenerated radicals are an indispensable member of the state-of-the-art photochromic material family, as they can effectively modulate the photoluminescence and photothermal conversion performance of radical-induced photochromic complexes. Herein, two novel radical-induced photochromic metal-organic frameworks (MOFs), Ag(TEPE) ⋅ /HO ⋅ /EtOH (1) and Ag(TEPE) ⋅ 3HO ⋅ EtOH (2), are reported. Distinctly different topological networks can be obtained by judiciously introducing alternative π-conjugated anionic guests, including a new topological structure (named as sfm) first reported in this work, describing as 4,4,4,4-c net. EPR data and UV-Vis spectra prove the radical-induced photochromic mechanism. Dynamic photochromism exhibits tunability in a wide CIE color space, with a linear segment from yellow to red for 1, while a curved coordinate line for 2, resulting in colorful emission from blue to orange. Moreover, photogenerated TEPE* radicals effectively activate the near-infrared (NIR) photothermal conversion effect of MOFs. Under 1 W cm 808 nm laser irradiation, the surface temperatures of photoproducts 1* and 2* can reach ~160 °C and ~120 °C, respectively, with competitive NIR photothermal conversion efficiencies η=51.8 % (1*) and 36.2 % (2*). This work develops a feasible electrostatic compensation strategy to accurately introduce photoactive anionic guests into MOFs to construct multifunctional radical-induced photothermal conversion materials with tunable photoluminescence behavior.
光生自由基是先进光致变色材料家族中不可或缺的一员，因为它们可以有效调节自由基诱导的光致变色配合物的光致发光和光热转换性能。在此，报道了两种新型自由基诱导的光致变色金属有机框架（MOF），Ag(TEPE) ⋅ /HO ⋅ /EtOH (1) 和 Ag(TEPE) ⋅ 3HO ⋅ EtOH (2)。通过明智地引入替代的π共轭阴离子客体，可以获得截然不同的拓扑网络，包括在本工作中首次报道的一种新拓扑结构（命名为sfm），描述为4,4,4,4-c网络。电子顺磁共振（EPR）数据和紫外可见光谱证明了自由基诱导的光致变色机理。动态光致变色在宽广的CIE颜色空间中表现出可调性，对于1，有一段从黄色到红色的线性线段，而对于2则是一条曲线坐标线，从而产生从蓝色到橙色的多彩发射。此外，光生TEPE自由基有效地激活了MOF的近红外（NIR）光热转换效应。在1 W cm 808 nm激光照射下，光产物1和2的表面温度分别可达到160 °C和120 °C，近红外光热转换效率具有竞争力，η=51.8 %（1）和36.2 %（2*）。这项工作开发了一种可行的静电补偿策略，以准确地将光活性阴离子客体引入MOF中，构建具有可调光致发光行为的多功能自由基诱导光热转换材料。
