Homochiral diamond frameworks embedding helixes: Syntheses, structures and properties

Xu, Zhong-Xuan; Bai, Xiwen; Shi, Ming-Feng

doi:10.1016/j.jssc.2019.120896

Cited by 4 publications

(1 citation statement)

References 23 publications

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“…Especially, the different side groups of amino acids embedding in those ligands could delicately adjust the structure and performance of the resulting HMOFs. More importantly and intriguingly, the in situ formation of metal cluster subunits with different structural types was found during the assembly of Zn-, Cd-, or Eu-HMOF. − In contrast, metal clusters with specific geometry and more ligation sites may provide more opportunities for the construction of HMOFs with a novel structure and unique properties. − Continuing our work in exploring optical materials of HMOFs, ( S )-5-((2-carboxy-5-oxopyrrolidin-1-yl)methyl)isophthalic acid (H 3 L), which had been used by us to construct novel 3D porous helical Ln-HMOFs (Ln = Eu 3+ or Tb 3+ ) with interesting optical properties and excellent thermotolerance, was chosen and synthesized as the enantiopure chiral bridge. In this work, d 10 metal ions Zn 2+ and Cd 2+ were used as metal centers to construct H 3 L-based HMOFs because these metal ions are ideal candidates for fabricating HMOFs due to their flexible coordination number and configuration as well as their complexes’ appealing photoelectric properties. − Additionally, the crystalline samples of Zn 2+ and Cd 2+ metal–organic frameworks usually display high optical transparency and excellent physicochemical stability, which are conducive to greatly improving NLO performance .…”

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confidence: 97%

Homochiral Metallohelicates Based on Zinc(II) and Cadmium(II) Clusters with Excellent Thermostability and Remarkable Second-Harmonic Generation

Zuo

Wang

Dong

et al. 2022

Crystal Growth & Design

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Two interesting homochiral coordination polymers based on in situ produced zinc(II)/cadmium(II) clusters, namely, {[Zn4(L)2(OH)2(H2O)3]·3H2O} n (1) and {[Cd3(L)2(H2O)4]·4H2O} n (2), were hydro/solvothermally synthesized by the reaction of the designed enantiomerically pure chiral ligand (S)-5-((2-carboxy-5-oxopyrrolidin-1-yl)methyl)isophthalic acid (H3L) with Zn(OH)2 or Cd(OH)2. Complex 1 is a three-dimensional (3D) metallohelicate constructed from novel six-fold helical chain substructures based on tetranuclear zinc(II) clusters. Complex 2 is a 2D double-layered metallohelicate containing interesting four-fold helical chain substructures based on trinuclear cadmium(II) clusters. Topologically, 1 can be described as an interesting (3,4,7)-connected net with a point symbol of (42·6)(42·64)(44·615·82), while 2 can be reducible to a (3,6)-connected kgd net. Thermal analyses disclosed that the dehydrated frameworks of 1 and 2 had excellent thermostability. Clearly, the in situ produced zinc(II)/cadmium(II) clusters are of great significance not only in the formation of novel helical frameworks of 1 and 2 but also in the excellent thermostability of their frameworks. Furthermore, their solid-state optical properties, including CD spectra and nonlinear optical and luminescence properties, were also carried out. In particular, 1 and 2 show remarkable second harmonic generation with efficiencies about 1.15 and 0.95 times that of potassium dihydrogen phosphate, respectively. Even more important, the high thermostability and remarkable second harmonic generation response of colorless transparent crystalline materials 1 and 2 are meaningful for further exploring their optical applications.

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