近日，中山大学潘梅团队报道了金属-有机框架（MOF）中双光子/多光子激发发光的探索。相关论文发表在2025年12月22日出版的《中国化学》杂志上。

近年来，双光子激发发光（TPEL）与多光子激发发光（MPEL）材料因其独特的非线性光学性质，尤其在金属有机框架（MOFs）领域受到日益广泛的关注。MOFs作为一类通过配位键连接、蓬勃发展的框架材料，以其优异的TPEL/MPEL性能脱颖而出，为探索非线性光学的奥秘及其潜在应用提供了创新工具。

研究组系统介绍了TPEL/MPEL材料的基本机理，重点阐述了光致发光量子产率（PLQY）、双光子吸收（TPA）/多光子吸收（MPA）截面以及光稳定性在材料设计中的作用。随后，重点论述了近年来具有定制化非线性光学性质的MOFs材料的理性构建进展，包括线性/三足/四足配体工程、客体@MOF主客体体系以及合成后修饰等策略。这些进展推动了多项应用的发展，例如基于三维编码与图案化的防伪技术、兼具深层组织穿透能力与高空间分辨率的生物成像、用于低阈值激光的受激发射，以及光学数据存储等。

此外，研究组进一步探讨了提升MOFs非线性光学效率、结构稳定性和生物相容性方面可能面临的挑战，并对该领域未来的发展前景进行了展望。文中提出的观点旨在启发多学科交叉背景下MOFs基非线性光学材料设计与应用的创新思路，推动光子学、生物医学工程及材料科学领域的进步。

附：英文原文

Title: Exploration of Two-photon/Multi-photon Excited Luminescence in Metal−Organic Frameworks (MOFs)†

Author: Shi-Cheng Wang, Qiang-Sheng Zhang, Cheng-Yi Zhu, Si-Yi Chen, Mei Pan

Issue&Volume: 2025-12-22

Abstract: Comprehensive SummaryIn recent years, two-photon excited luminescence (TPEL) and multi-photon excited luminescence (MPEL) materials have attracted increasing attention due to their unique nonlinear optical (NLO) properties, particularly in the realm of metalorganic frameworks (MOFs). MOFs, as a type of flourishing framework materials linked by coordination bonds, have distinguished themselves with their outstanding TPEL/MPEL performances, providing innovative tools for the exploration of mysterious nonlinear optics and promising applications. This review systematically introduces the basic mechanisms of TPEL/MPEL materials, emphasizing the role of photoluminescence quantum yield (PLQY), two-photon absorption (TPA)/multi-photon absorption (MPA) cross-sections, and photostability in material design. Then, recent progresses in the rational construction of MOFs with tailored NLO properties is highlighted, including strategies such as linear/tripodal/quadrupodal ligand engineering, guest@MOF host-guest systems, and post-synthetic modifications. These advancements have unlocked diverse applications, such as anti-counterfeiting via 3D coding and patterning, bioimaging with deep-tissue penetration and high spatial resolution, stimulated emission for low-threshold lasing, and optical data storage. Furthermore, the potential challenges in enhancing MOFs’ NLO efficiency, structural stability, and biocompatibility are addressed, and perspectives in the forthcoming development of this field are proposed. The insights presented herein aim to inspire innovative approaches in the design and application of MOF-based NLO materials across disciplines, fostering advancements in photonics, biomedical engineering, and materials science.Key ScientistsThe field of TPEL/MPEL and MOF research has been significantly advanced by a group of outstanding scientists. In 1931, Gppert-Mayer made the theoretical prediction of the two-photon absorption (TPA) phenomenon, laying the cornerstone for future research in this area.[1] Decades later, in 1990, Denk and co-workers developed the first two-photon excitation microscope, which revolutionized imaging techniques in biological and materials science.[2] In 2012, the Pan group contributed to the development of functional MOF materials by working on lanthanide MOFs with TPEL.[3] In 2013, the Qian group pushed the boundaries of MOF applications in optoelectronics by developing a two-photon-pumped micro-laser using dye-encapsulated MOFs.[4] In 2014, the Zhou group achieved a remarkable feat by synthesizing a MOF with a photoluminescent quantum yield (PLQY) of 99.9%.[5] In 2015, Vittal and co-workers further enhanced the optical properties of MOFs by improving 4PEL via Frster resonance energy transfer (FRET).[6] In 2017, Fischer and co-workers deepened the understanding of photophysical properties of MOFs by studying intrinsic stimulated emission (STE) and MPEL.[7-8] In 2022, the Jiang group set a new record by achieving the highest TPA action cross-section value of MOFs to date.[9] In the same year, Wang and co-workers introduced interpretable machine learning techniques to TPA research, opening up new avenues for data analysis in this field.[10] More recently, in 2024, the Bu group provided new insights into the TPA process by investigating its mechanism under low-power density non-coherent excitation.[11] Collectively, these contributions have significantly propelled the field forward.

DOI: 10.1002/cjoc.70354

Source: https://onlinelibrary.wiley.com/doi/10.1002/cjoc.70354