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A Triply Linked Copper(III) Dicarbacorrole Dimer
Ruijuan Jiao1, Ningchao Liu1, Zhaohui Zong1
1College of Chemistry, Beijing Normal University, Beijing, 100875, China.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|April 17, 2024
Summary
A novel triply linked dicarbacorrole dimer was synthesized, forming a short carbaporphyrinoid tape. This unique structure exhibits stable Cu(III) ions and strong electronic interactions, unlike previous corrole dimers.
Area of Science:
- Organic Chemistry
- Materials Science
- Supramolecular Chemistry
Background:
- Carbaporphyrinoids are synthetic porphyrin analogs with modified macrocyclic frameworks.
- Fully fused tetrapyrrolic dimers with multiple linkages are challenging to synthesize and characterize.
- Understanding the electronic properties of fused macrocycles is crucial for developing new functional materials.
Purpose of the Study:
- To synthesize a novel triply linked dicarbacorrole dimer.
- To characterize its structural, electronic, and spectroscopic properties.
- To investigate the stability of coordinated metal ions within the dicarbacorrole framework.
Main Methods:
- Oxidative fusion reaction using 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and trifluoromethanesulfonic acid (TfOH).
- Single crystal X-ray diffraction for structural determination.
- NMR spectroscopy and X-ray photoelectron spectroscopy (XPS) for electronic state confirmation.
Main Results:
- Successful synthesis of a triply linked dicarbacorrole dimer (7) from a meso-meso singly linked precursor (6).
- The dimer adopts a flat conformation, resembling a short carbaporphyrinoid tape (15.946 Å x 6.903 Å).
- Coordinated copper ions remain in the +3 oxidation state, a significant difference from related corrole dimers.
Conclusions:
- This work reports the first fully fused carbaporphyrinoid dimer with β-β, meso-meso, β-β triply linkages.
- The non-aromatic nature and strong electronic interactions lead to a decreased HOMO-LUMO gap and red-shifted absorption.
- The stable Cu(III) state in this dicarbacorrole system opens new avenues for metal-macrocycle complex research.
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