Dimensional effects of organic anion templates in modulating the assembly of water clusters in cucurbit[6]uril supramolecular systems

Two new supramolecular architectures {（HC2O4）2^2- [C6H（18）N2^2＋ C（36）H（36）N（24）O（12）]} 12H2O（1） and{（C6H5SO3）22 [C6H（18）N22＋ C（36）H（36）N（24）O（12）]} 12H2O（2） were synthesized and characterized by singlecrystal X-ray diffraction, thermogravimetric analysis and X-ray powder diffraction. Compound 1contains infinite two dimensional（2D） L18（8）14（8）8（4） type anion–water aggregates [（HC2O4）4（H2O）（22）]^4- and results in the construction of sandwich-like three dimensional（3D） networks. In compound 2, honeycomb-like three dimensional（3D） networks are fabricated by one dimensional（1D）＂W＂-like T5（0）A2 type anion–water clusters [（C6H5SO3）（H2O）6]^-. These results indicate that anionic groups play a crucial role in modulating the structures of water clusters with their spatial structure and binding sites. In these two structures, the majority of interactions are O...H and H...H interactions on the Hirshfeld surface, which means that hydrogen bonding and hydrophobic interactions are the dominate drive forces in forming these supramolecular systems.

A New Family of SO_(4)^(2–)-Templated 3d-4f High-Nuclearity Clusters:Syntheses,Structures,and Magnetic Properties

The precise syntheses of transition-rare-earth metal clusters with desired structures remain a great challenge.Herein,by utilizing SO_(4)^(2-)anion released by in-situ decomposition of sodium dodecyl sulfate(SDS)as a template,a series of novel high-nuclearity 3d-4f clusters,formulated as[Ni_(24)Pr_(22)(μ_(3)-OH)_(31)(pida)_(24)(SO_(4))_(4)(NO_(3))_(9)(CH_(3)COO)_(3)]·Br_(4)·(NO_(3))_(11)·_(16)H_(2)O·25CH_(3)OH(1,H_(2)pida=N-phenyliminodiacetic acid),[Ni_(24)Nd_(22)(μ3-OH)_(31)(pida)_(24)(SO_(4))_(4)(NO_(3))_(9)(CH_(3)COO)_(3)]·Br_(4)·(NO_(3))_(11)·14H_(2)O·24CH_(3)OH(2)and[Ni_(24)Gd_(22)(μ3-OH)_(36)(bida)_(24)(SO_(4))_(7)(NO_(3))_(3)(CH_(3)COO)_(3)]·(SO_(4))·Br_(4)·(NO_(3))_(4)·31H_(2)O·32CH_(3)OH(3,H_(2)bida=N-benzyliminodiacetic acid),have been successfully isolated.X-ray crystal structure analyses reveal that all the cationic{Ni_(24)RE_(22)}cores in 1-3 possess a ball-like structure with C_(3v)symmetry,and can be viewed as consisting of an inner{RE_(22)}core and an outer{Ni_(24)}shell.From 1 and 2 to 3,due to the lanthanide contraction effect,the coordination numbers for rare-earth metal centers in{RE_(22)}are different,resulting in different number of SO_(4)^(2-)and NO_(3)^(-)anions to support and stabilize the skeleton structures.Meanwhile,the magnetic properties of complexes 1-3 were also studied.The result revealed that complexes 1-3 show antiferromagnetic/ferrimagnetic interactions,and 3 exhibits magneto-caloric effect at ultralow temperatures with a maximum-ΔSm(magnetic entropy change)value of 33.03 J·kg^(−1)·K^(−1)at 3.0 K and 7 T.