Base‐ and Metal‐Dependent Self‐Assembly of Lathanide‐Organic Coordination Polymers or Macrocycles with Tetradentate Acylhydrazone‐based Ditopic Ligands

Herein, we report a comprehensive study on the lanthanide‐directed coordination self‐assembly with two bis‐tetradentate acylhydrazone ligands H4L1 and H4L2. Multifarious outcomes, which are base‐ and metal‐dependent, were revealed by NMR, ESI‐TOF‐MS and X‐ray crystallography. In the absence of base,...

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Bibliographic Details
Published in:Chemistry, an Asian journal an Asian journal, 2021-06, Vol.16 (11), p.1392-1397
Main Authors: Feng, Xiao‐Shan, Li, Xiao‐Zhen, Hu, Shao‐Jun, Yan, Dan‐Ni, Zhou, Li‐Peng, Sun, Qing‐Fu
Format: Article
Language:English
Subjects:
Assembly
Base- and metal-dependent
Chemistry
Coordination polymers
Crystallography
Deprotonated assembly
Isomers
Lathanide-organic complex
Ligands
NIR emission
NMR
Nuclear magnetic resonance
Stereoisomerism
Ytterbium
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Summary:Herein, we report a comprehensive study on the lanthanide‐directed coordination self‐assembly with two bis‐tetradentate acylhydrazone ligands H4L1 and H4L2. Multifarious outcomes, which are base‐ and metal‐dependent, were revealed by NMR, ESI‐TOF‐MS and X‐ray crystallography. In the absence of base, bent H4L1 was assembled into dinuclear double‐strand helicate Ln2(H2L1)2 by partially‐deprotonated assembly with La, Sm or Eu, while trinuclear Ln3(H2L1)3 with Yb or Lu. For linear H4L2, infinite 1D zig‐zag metal‐organic polymeric chain (Ln2H2L2)n was obtained. However, complete deprotonated L1 and L2 assembled into discrete trinuclear Ln3(L1/2)3 and tetranuclear Ln4(L1/2)4 macrocyclic structures under the basic condition. For these, there are multiple possible isomers coexisting in the solution which were enumerated and simulated with molecular mechanic modeling. Visible‐light sensitized NIR emissions on the Yb complexes have been observed, endowing them potential application in photofunctional materials. We showcase here a complicated scenario for the condition‐dependent self‐assembly of two bis‐tetradentate acylhydrazone ligands with lanthanide ions, where formation of polymeric chains, discrete dinuclear helicate, and trinuclear/tetranuclear macrocycles can be selectively obtained. Visible‐light sensitized NIR emissions on the Yb complexes endow their potential application as photofunctional materials.
ISSN:1861-4728
1861-471X
DOI:10.1002/asia.202100256