Ultrastrong Alkali-Resisting Lanthanide-Zeolites Assembled by [Ln₆₀] Nanocages

Zeolites, as one of the most important porous materials, are most widely utilized in sorbents, catalysis, and ion-exchange fields. However, the multi-functional lanthanide-zeolites constructed exclusively by lanthanide ions and oxygen linkers are to our knowledge unknown hitherto. Herein, we, for the first time, report the unique structure and multifunctions of lanthanide zeolites (<b>1·Gd</b>, <b>1·Tb</b>, <b>1·Dy</b>), featuring 60 nuclear [Ln₆₀] nanocages as building blocks and ultrastrong alkali-resisting. These compounds possess extremely high stability and still retain single crystallinity after treatment in boiling water, 0.1 M HCl, and 20 M NaOH aqueous solutions. Magnetic studies revealed <b>1·Gd</b> has large magnetocaloric effect with −Δ<i>S</i>_m^max = 66.5 J kg^–1 K^–1, falling among the largest values known to date. Importantly, these lanthanide-zeolites themselves can efficiently catalyze the cycloaddition of CO₂ with epoxides under mild conditions. Our finding extends the conventional zeolites to lanthanide counterparts, opening a new space for seeking novel and/or multifunctional zeolites

Structural Diversity, Luminescence, and Magnetic Property: Series of Coordination Polymers with 2,2′-Bipyridyl-4,4′-Dicarboxylic Acid

Eight coordination polymers associated with the organic ligand 2,2′-bipyridyl-4,4′-dicarboxylic acid (abbreviated H2BPDC): {[Zn­(BPDC)­(H2O)3]·3H2O}n (1), [Zn­(BPDC)­(H2O)2]n (2), [Co­(BPDC)­(H2O)3]n (3), [Co­(BPDC)­(H2O)2]n (3a), [Cu­(BPDC)­(H2O)]n (4), {[Cu­(BPDC)­(H2O)2]·2H2O}n (4a), [Mn­(BPDC)­(H2O)2]n (5), and {[Mn­(BPDC)]·2H2O}n (5a) were prepared by hydrothermal methods and structurally characterized. The structure analyses reveal that 1 exhibits a one-dimension chain, and 2, 3a, 5, and 5a are complicated 3D structures. 2 displays a 2-fold interpenetrating chiral 3D framework with the rare (12,3) topology and 5 is a chiral 3D framework. 4 and 4a are two-dimensional networks, and 3 is a chiral 1D chain. The structural contrasts between 1 and 2, 3 and 3a, 4 and 4a, and 5 and 5a display the transformations from low to high dimensional motif, and/or from achiral to chiral structures. Interestingly, the large structure divergences mainly originated from the different reaction temperature (It should be noted that 3a, 4a, and 5a were also obtained independently by us, although they had been reported. Herein, they were only used to discuss the structural comparison investigations). The luminescent properties of 1 and 2 have been explored and compared with that of the ligand. The Cotton effect in solid circular dichroism (CD) spectra of 2 was significantly observed, indicative of the chirality of 2. Magnetic properties analyses for 3 and 5 were performed

Structural Diversity, Luminescence, and Magnetic Property: Series of Coordination Polymers with 2,2′-Bipyridyl-4,4′-Dicarboxylic Acid

Eight coordination polymers associated with the organic ligand 2,2′-bipyridyl-4,4′-dicarboxylic acid (abbreviated H₂BPDC): {[Zn­(BPDC)­(H₂O)₃]·3H₂O}_<i>n</i> (<b>1</b>), [Zn­(BPDC)­(H₂O)₂]_<i>n</i> (<b>2</b>), [Co­(BPDC)­(H₂O)₃]_<i>n</i> (<b>3</b>), [Co­(BPDC)­(H₂O)₂]_<i>n</i> (<b>3a</b>), [Cu­(BPDC)­(H₂O)]_<i>n</i> (<b>4</b>), {[Cu­(BPDC)­(H₂O)₂]·2H₂O}_<i>n</i> (<b>4a</b>), [Mn­(BPDC)­(H₂O)₂]_<i>n</i> (<b>5</b>), and {[Mn­(BPDC)]·2H₂O}_<i>n</i> (<b>5a</b>) were prepared by hydrothermal methods and structurally characterized. The structure analyses reveal that <b>1</b> exhibits a one-dimension chain, and <b>2</b>, <b>3a</b>, <b>5</b>, and <b>5a</b> are complicated 3D structures. <b>2</b> displays a 2-fold interpenetrating chiral 3D framework with the rare (12,3) topology and <b>5</b> is a chiral 3D framework. <b>4</b> and <b>4a</b> are two-dimensional networks, and <b>3</b> is a chiral 1D chain. The structural contrasts between <b>1</b> and <b>2</b>, <b>3</b> and <b>3a</b>, <b>4</b> and <b>4a</b>, and <b>5</b> and <b>5a</b> display the transformations from low to high dimensional motif, and/or from achiral to chiral structures. Interestingly, the large structure divergences mainly originated from the different reaction temperature (It should be noted that <b>3a</b>, <b>4a</b>, and <b>5a</b> were also obtained independently by us, although they had been reported. Herein, they were only used to discuss the structural comparison investigations). The luminescent properties of <b>1</b> and <b>2</b> have been explored and compared with that of the ligand. The Cotton effect in solid circular dichroism (CD) spectra of <b>2</b> was significantly observed, indicative of the chirality of <b>2</b>. Magnetic properties analyses for <b>3</b> and <b>5</b> were performed