Tunable third-order nonlinear optical effect via modifying Ti4(embonate)6 cage-based ionic pairs

作者：Chen, Guang-Hui; He, Yan-Ping^*; Wang, Zi-Rui; Li, Qiao-Hong; Ma, Zhi-Zhou; Zhang, Jian^*

来源：Inorganic Chemistry Frontiers, 2022, 9(9): 1984-1991.

DOI：10.1039/d2qi00138a

• REVERSE SATURABLE ABSORPTION
• INDIUM TIN OXIDE
• PORPHYRIN
• POLYMERS
• FILM

Benefiting from the strong inherent pi-conjugation properties, the integration of Ti4L6 (L = embonate) cages and various N,N-chelated transition-metal cations into tightly packed structures accurately leads to high-performance materials with adjustable nonlinear optical (NLO) effects. These cage-based ionic pairs possess different supramolecular packing structures, including a pi MIDLINE HORIZONTAL ELLIPSIS pi stacked porous framework where the Ti4L6 cages are tactically located at the channels. Interestingly, by introducing the large pi-conjugated 1,10-phenanthroline type ligands and adjusting the aromatic ring electron cloud density, we have effectively regulated their third-order NLO properties, realizing nonlinear absorption responses from reverse saturated absorption (RSA) to saturated absorption (SA). This work not only presents an extraordinary coordination cage-based assembly, but also provides new insights into the function of cage materials.

• 单位
  结构化学国家重点实验室; 中国科学院福建物质结构研究所; 中国科学院大学