Issue 17, 2018

The impact of metal ions on photoinduced electron-transfer properties: four photochromic metal–organic frameworks based on a naphthalenediimide chromophore

Abstract

Four novel photochromic metal–organic frameworks (MOFs) self-assembled from a naphthalenediimide-based ligand and different metal cations, [Zn2(BINDI)(DMA)2]·2DMA (1), [Cd(H4BINDI)(H2BINDI)]·4DMF (2), [Ca2(HBINDI)Cl(DMA)3]·DMA (3), [Ba4(BINDI)2(DMF)7]·7DMF (4) (H4BINDI = N,N′-bis(5-isophthalic acid)naphthalenediimide), have been synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, IR spectroscopy and TG analyses. Compound 1 exhibits a 3D porous framework with an lvt topology based on paddle-wheel Zn2(COO)4 clusters and BINDI as four-connected nodes. Compound 2 features a porous threefold interpenetrating diamondoid framework. Compound 3 shows a microporous 2D double-layer architecture and compound 4 displays a porous twofold interpenetrated 3D network. Interestingly, these four MOFs exhibit reversible photochromic behaviors with a concomitant eye-detectable color change, but different coloration degrees. The comparison of these MOFs indicates that the electron-withdrawing capabilities of metal cations play a significant role in tuning the photosensitive properties of photochromic MOFs; this result may provide a feasible route for the design and synthesis of photochromic MOFs with controllable photoinduced electron-transfer properties. Moreover, the photomodulated photoluminescence properties of compounds 1–4, as well as the solvatochromic behaviors of 3 and 4 were also investigated. Additionally, compounds 1–3 are found to be useful as indicators for the qualitative detection of nitrite by naked eye recognition of color change.

Graphical abstract: The impact of metal ions on photoinduced electron-transfer properties: four photochromic metal–organic frameworks based on a naphthalenediimide chromophore

Supplementary files

Article information

Article type
Paper
Submitted
09 Feb 2018
Accepted
25 Mac 2018
First published
26 Mac 2018

CrystEngComm, 2018,20, 2430-2439

The impact of metal ions on photoinduced electron-transfer properties: four photochromic metal–organic frameworks based on a naphthalenediimide chromophore

H. Xu, X. Zeng, J. Li, Y. Xu, H. Qiu and D. Xiao, CrystEngComm, 2018, 20, 2430 DOI: 10.1039/C8CE00213D

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