Construction of Naphthalenediimide Lanthanide(III)‐MOFs and Composites Incorporated Electron‐Rich Pyrene Derivative as Multifunctional Fluorescence Sensing for Nitro Aromatic Compounds and Aldehydes

Comprehensive Summary The development of host‐guest MOF luminescent composites has attracted considerable attention. However, it is still a challenge to reasonably design large scale conjugated polycarboxylic acids metal‐organic framework (MOF) and modulate donor‐acceptor interaction. Herein, a series of isostructural 3D porous lanthanide MOF [Ln 2 (BINDI) 0.5 (NO 3 )(DMA)(H 2 O)]∙DMA∙2.5H 2 O (Ln = La ( 1 ), Ce ( 2 ), Pr ( 3 ) and Nd ( 4 ); H 4 BINDI ( N , N ’‐bis(5‐isophthalic acid)‐1,4,5,8‐naphthalenediimide) were synthesized. Considering the electron‐deficient performances of Ln‐BINDI MOFs, D‐A type composites Ln‐MOFs ( 1 — 4 @H 4 TBAPy) were prepared via the incorporation of electron‐rich H 4 TBAPy (1,3,6,8‐tetrakis( p ‐benzoic acid) pyrene), which more improved the luminescence performance of complexes 1 — 4 and can be used as fluorescence sensors for the detection of nitro compounds and aldehydes. High sensitivity of 1 @H 4 TBAPy towards pNBA, pNA PNP, DNP, and TNP could be achieved through hydrogen bond interactions between MOF and analytes, as well as the π‐π interaction between H 4 TBAPy and the naphthalene ring of BINDI, thus the fluorescence quenching efficiency of 1 @H 4 TBAPy was better than that of the complex 1 . In addition, it is found that 1 @H 4 TBAPy has high selectivity and sensitivity to aromatic aldehyde SA, 5‐Mesal and HMBA. Such strategy to enhance the emission of NDI based Ln‐BINDI MOFs, will open up an avenue to obtain more fluorescent MOFs for sensing.