Six organic−inorganic hybrid pyridine-4-carboxylate-decorated organotin (OT)−lanthanide (Ln) heterometallic antimotungstates 3+ (2), Pr 3+ (3), Nd 3+ (4), Sm 3+ (5), Eu 3+ (6); Hpca = isonicotinic acid] have been prepared with the help of the structuredirecting effect of the trivacant [B-α-SbW 9 O 33 ] 9− segment toward [(CH 3 ) 2 Sn] 2+ and Ln 3+ ions in an acidic water medium. The prominent architecture characteristic is that their structural units consist of a trivacant [B-β-SbW 9 O 33 ] 9− segment stabilized by three [Sn-(CH 3 ) 2 (H 2 O)] 2+ groups and a [Ln(H 2 O) 6 (pca)] 2+ cation, which are interconnected to propagate an intriguing two-dimensional (2D) network. For all we know, 1−6 stand for the first 2D OT−Ln heterometallic polyoxometalates. Furthermore, luminescence performances of solid-state 3−6 were deeply surveyed at ambient temperature. Energy migration from [B-β-SbW 9 O 33 ] 9− and pca − to Sm 3+ centers in 5 was also studied. Comparative studies demonstrate that the contribution of [B-β-SbW 9 O 33 ] 9− sensitizing the emission of Sm 3+ is prominently larger than that of pca − sensitizing the emission of Sm 3+ in the emission process of 5. Most interestingly, 6 as a fluorescence probe exhibits high selectability and sensitivity for recognizing Zn 2+ and Cu 2+ in water.

Two unprecedented 1-D double chain germanomolybdates containing hepta-nuclear Cu–RE–pic heterometallic clusters were prepared and the adsorption capacity of 1 toward dyes in aqueous solutions was investigated.

By virtue of combining an in-situ assembly process with a stepwise synthesis in conventional aqueous solution, two series of unique organic-inorganic hybrid heteropolyoxomolybdates were constructed from plenary Keggin germanomolybdates and Cu-Ln heterometallic units and fully characterized: [H INA] H [LnCu(INA) (H O) ] [α-GeMo O ] ⋅52 H O (Ln=La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6); HINA=isonicotinic acid) and (NH )[Cu(PA) ][Cu(PA) Ln(H O) ][α-GeMo O ]⋅10 H O (Ln=Nd (7), Sm (8), Eu (9); HPA=picolinic acid). The most remarkable structural characteristic of compounds 1-6 was that their molecular units were defined by three discrete plenary Keggin [α-GeMo O ] polyoxoanions and two organic-inorganic hybrid heterometallic [LnCu(INA) (H O) ] moieties, whereas compounds 7-9 exhibited a nice-looking 1D chain-like structure that was built from plenary [α-GeMo O ] polyoxoanions, pendent [Cu(PA) ] complexes, and bridging {[Cu(PA) ][Ln(H O) ]} heterometallic groups. Notably, two different pyridine carboxylic acid ligands led to the discrepancy between the two structure types. To the best of our knowledge, compounds 1-9 constitute the first examples of plenary Keggin heterometallic germanomolybdates that include Cu-Ln-organic subunits. Further studies revealed that compounds 3 and 8 exhibited fast adsorption capacity for cationic dyes methylene blue (MB) and rhodamine B (RhB) in water. Moreover, compounds 3 and 8 could quickly and selectively adsorb MB from a mixture of MB/methyl orange (MO) or MB/azophloxine (Apo).

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Ionic co-assembly of tetra-anionic porphyrins has been extensively researched in the construction of hierarchically organized architectures with potential application value in organic semiconductors, sunlight catalysts and supramolecular chirality systems. However, such architectures are difficult to grow to a size suitable for single-crystal X-ray diffraction (SCXRD); the lack of single-crystal structures of these architectures leads to challenges in gaining deeper comprehension about that. This study reports a hierarchically organized cocrystal of meso-tetra(4-sulfonato-phenyl)-por-phyrin (TSPP 4À ) and N, N'-diethyl-viologen (DEV 2 + ), wherein wave-like and saddle-like TSPP 4À ions co-aggregate at a stoichiometric ratio of 1 : 2 to form unique porphyrin arrays; the spectrum characteristics and calculated coulombic exciton coupling energy show that these porphyrin arrays are Jaggregates. We prove that the distortion of porphyrin ring of TSPP 4À strongly correlates with the deflection of its phenyl groups. The crystal comprises six different ionic conformations, and the multiplicity of ionic conformation leads to intricate supramolecular interactions.