Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Advanced Catalysis and Green Manufacturing Collaborative Innovation Center, School of Petrochemical Engineering, Changzhou University, Changzhou, Jiangsu 213164, China.
Inorg Chem. 2023 Feb 20;62(7):3170-3177. doi: 10.1021/acs.inorgchem.2c04086. Epub 2023 Feb 6.
The peak photoluminescence (PL) of conventional fluorophores is independent of the excitation wavelength (called Kasha's rule), while the search of metal-organic framework materials with the so-called anti-Kasha's rule emission remains very limited. Herein, we report the observation of anti-Kasha's rule emission in a multicomponent PL three-dimensional nanotubular metal-organic framework ( ), [Zn(μ-L)(μ-bix)]·0.33HO [HL = biphenyl-3,5-dicarboxylic acid; bix = 1,4-bis(imidazole-1-ylmethyl)benzene]. The crystalline sample represents a notable example of strong excitation-dependent fluorescence from the ultraviolet to the visible spectral region. Moreover, by virtue of electronic flexibility and high PL efficiency, shows a discriminative PL response between isomeric nitroaromatic compounds. The work demonstrated the intrinsic anti-Kasha's rule emission in the crystalline-state MOF materials, providing new visions for the development of advanced solid-state emissive materials.
常规荧光团的光致发光（PL）峰值不依赖于激发波长（称为 Kasha 规则），而具有所谓反 Kasha 规则发射的金属-有机骨架材料的研究仍然非常有限。在此，我们报告了在多组分 PL 三维纳米管状金属-有机骨架（）[Zn(μ-L)(μ-bix)]·0.33HO [HL = 联苯-3,5-二羧酸；bix = 1,4-双（咪唑-1-基甲基）苯]中观察到反 Kasha 规则发射。该晶体样品代表了从紫外到可见光谱区域强激发依赖性荧光的显著实例。此外，凭借电子灵活性和高 PL 效率，在异构体硝基芳烃化合物之间表现出有区别的 PL 响应。该工作证明了在晶态 MOF 材料中存在固有反 Kasha 规则发射，为开发先进的固态发光材料提供了新的思路。
