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Triazine derivatives, a class of electron-deficient π-conjugated molecules with high photochemical activity and excellent luminescent characteristics, have been utilized as a kind of electron-acceptor for the construction of molecular cages, luminescent and photochromic materials. In this paper, a novel and highly stable MOF with cubane-like clusters, [Co4(SO4)3(F)3(tpt)2(tatb)] (1) (tpt = 2,4,6-tris-(4-pyridyl)-1,3,5-triazine, H3tatb = 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl)tribenzoic acid), has been successfully synthesized based on a triazine derivative, and possesses unprecedented sulfate- and fluoride-bridged cubane-type tetranuclear cobalt clusters and a 3D + 3D → 3D open framework. Compound 1 shows a rather high BET surface area and exhibits excellent thermal stability and high chemical stability in common solvents and even in acidic or basic solutions (in a pH range from 4 to 12). Moreover, catalytic measurements show that compound 1 is an excellent heterogeneous catalyst for the selective oxidation of aryl alkenes to aldehydes or ketones with conversions of 97%. [ABSTRACT FROM AUTHOR]

Photochromic materials coupled with photoswitchable luminescence functionalities are of particular interest due to their potential applications in switches and optical memory devices. However, the construction of such materials, especially those with two-color emission states, is still challenging. In this context, a rare Zn7 cluster-based host–guest MOF material, (bbmp)[Zn7(IPA)6(OH)4(H2O)2] (1) (H2IPA = isophthalic acid, bbmp·2I = 4,4′-([1,1′-biphenyl]-4,4′-diyl)bis(1-methylpyridin-1-ium) diiodide), was prepared by encapsulating an organic cation into an anionic MOF produced from zinc cations and isophthalic acid ligands, which exhibits reversible naked detectable photochromic properties varying from yellow to green upon UV-Vis light irradiation. The photoactive guest bbmp2+ and the short O⋯N+ distances between the oxygen atoms of the carboxylate groups and the pyridine ring play a crucial role in the photochromism of this compound. More interestingly, the luminescence color of this cluster-based host–guest material can be reversibly switched from green to blue upon irradiation, exhibiting photoswitchable luminescence properties. [ABSTRACT FROM AUTHOR]

• A MOF based on electron-deficient naphthalene diimide dye is prepared. • The anion–π interactions between two-dimensional network and W6O192– is observed. • Complex 1 exhibits eye-detectable fast-responsive reversible photochromism and photoresponsive luminescence. • Photoinduced electron-transfer produces NDI radicals and W5+ species. Metal-organic frameworks that contain photoactive organic ligands or photoactive inorganic components are an emerging class of multifunctional hybrid materials that in recent years has gradually become an ideal platform for building photochromic complexes. In this paper, a metal-organic framework based on naphthalene diimide (NDI) ligand with Lindqvist-type W 6 O 19 2– polyanions, [Ce 2 (BINDI) (DMF) 8 ]·[W 6 O 19 ] (1), (H 4 BINDI = N, N '-bis(5-isophthalic acid)-1,4,5,8-naphthalene diimide) was synthesized and systematically characterized. It displays a cationic two-dimensional grid coordination network, featuring anion–π interactions between W 6 O 19 2– and expanded π–electron deficient naphthalene diimide (NDI) moieties. Moreover, because of the presence of electron-deficient NDI moieties and photoactive W 6 O 19 2–, this complex exhibits fast responsive reversible photochromism and photoresponsive tunable luminescence. UV–Vis, IR, PXRD, EPR, and XPS spectral studies indicate that the obviously photochromic phenomenon of complex 1 is derived from photoinduced electron-transfer form NDI radicals and W5+ species. [Display omitted]. [ABSTRACT FROM AUTHOR]

• Two isomeric metal-organic frameworks are prepared based on naphthalenediimide and naphthalenedicarboxylic acid. • Complexes 1 and 2 exhibit different photochromism and photocontrolled luminescence upon UV–Vis light irradiation. • Noncovalent interactions play an important role in the photochromic properties of MOFs. As a class of special type materials, photochromic metal-organic frameworks (MOFs) have attracted extensive attention because their usually show interesting color changes and coupled with the variation of some chemical and physical properties under light irradiation. In order to study the effect of secondary building on the photochromism of MOFs, two isomeric naphthalenediimide-based MOFs with different secondary building linkers, namely [Zn 2 (DPNDI)(2,6-NDC) 2 ] (1) and [Zn 2 (DPNDI)(1,4-NDC) 2 ] (2) (DPNDI = N, N '-di(3-pyridyl)-1,4,5,8-naphthalenediimide, 1,4-H 2 NDC = 1,4-naphthalenedicarboxylic acid, 2,6-H 2 NDC = 2,6-naphthalenedicarboxylic acid), were synthesized via solvothermal reaction and the structure were characterized by single-crystal X-ray diffraction, IR and TGA. Owing to the different C H···π interactions between the naphthalene moieties of dicarboxylic acid and electron-deficient DPNDI ligand, they showed different photochromic behaviors and photocontrolled luminescence upon ultraviolet-visible irradiation. Specifically, complex 2 was photochromic but complex 1 was not. The difference can be ascribed to the larger C H···π interaction in complex 1 than in complex 2. This work is expected to provide a new perspective for designing novel photochromic MOF materials Two isomeric naphthalenediimide-based MOFs with different secondary building linkers have been prepared, which exhibit different photochromic behaviors and photocontrolled luminescence upon ultraviolet-visible irradiation. [Display omitted] [ABSTRACT FROM AUTHOR]

The encapsulation of photoactive guests into a metal-organic framework is advantageous in endowing extra functionalities such as photochromism and photoswitchable luminescence. In this paper, a host-guest MOF material, [Zn 3 (IPA) 4 ​MV] (1) (H 2 IPA ​= ​isophthalic acid, MV·2NO 3 ​= ​1,1'-dimethyl-(4,4'-bipyridine)-1,1'-diium dinitrate) has been constructed by encapsulating simplest methyl viologen guest into the anionic MOF framework. This material exhibits reversible naked-eye detectable photochromic properties varying from colorless to blue upon UV–Vis light irradiation. The MV2+ and the short O⋯N distance between the oxygen atom and pyridine ring of MV2+ play a crucial role in the photochromism of this compound. This host-guest MOF compound shows photoswitchable luminescent properties in the solid state. More interestingly, this host-guest MOF material can be deposited on filter paper and can be employed as inkless print material by controlling the UV–Vis light irradiation with the stencil. A novel MOF-based host-guest compound was prepared by incorporating the photoactive methyl viologen into the anionic framework, which exhibit photochromism upon UV–Vis light irradiation and photocontrolled luminescence. Moreover, this compound can be used as inkless and erasable print media. [Display omitted] • A host-guest compound was prepared by incorporating the viologen into the anionic MOFs. • Compound 1 exhibits fast-responsive photochromism and reversible luminescence switching upon UV–Vis light irradiation. • Compound ​ 1 ​can be employed as inkless and erasable print media by controlling the UV-Vis light irradiation. [ABSTRACT FROM AUTHOR]