Bis(2,6-pyrazolyl)pyridines as a New Scaffold for Coordination Polymers
Igor A Nikovskiy1, Pavel V Dorovatovskii2, Valentin V Novikov3
1Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova Street 28, 119991 Moscow, Russia.
Molecules (Basel, Switzerland)
|June 10, 2023
Summary
Researchers developed a novel proton-coupled electron transfer (PCET) strategy to synthesize coordination polymers. This method enables the creation of unique metal-organic frameworks with specific SCO-active cores.
Area of Science:
- Inorganic Chemistry
- Materials Science
- Supramolecular Chemistry
Background:
- Coordination polymers and metal-organic frameworks (MOFs) are crucial in materials science.
- The synthesis of novel structures with specific functionalities, such as spin crossover (SCO) activity, remains a key challenge.
- Ligand design and controlled reaction conditions are essential for tailoring material properties.
Purpose of the Study:
- To explore a novel proton-coupled electron transfer (PCET) assisted synthesis route.
- To investigate the formation of coordination polymers using 2,6-bis(pyrazol-3-yl)pyridine-based ligands.
- To create novel coordination polymers and MOFs with the SCO-active core N3(L)MN3(L).
Main Methods:
- Utilizing a PCET-assisted process involving a hydroxy-pyrazolyl ligand and an iron(II) ion.
- Employing mild reactant diffusion conditions to yield heterometallic compounds.
- Applying harsh solvothermal conditions to induce chemical transformations.
Main Results:
- Two distinct coordination polymers, [Fe(LOBF3)(CH3COO)(CH3CN)2]n•nCH3CN and [Fe(LO-)2AgNO3BF4•CH3OH]n•1.75nCH3OH•nH2O, were successfully synthesized.
- The first coordination polymer of 2,6-bis(pyrazol-3-yl)pyridines retaining the N3(L)MN3(L) core was obtained under mild conditions.
- Harsh solvothermal conditions led to the transformation of hydroxyl groups into OBF3 via hydrogen atom transfer to the tetrafluoroborate anion.
Conclusions:
- The PCET-assisted approach is a viable strategy for synthesizing coordination polymers and MOFs.
- This method allows for the controlled formation of the SCO-active core N3(L)MN3(L) using pyrazolone- and hydroxy-pyridine-based ligands.
- The findings open new avenues for designing functional materials with tunable properties.
Keywords:
2,6-bis(pyrazol-3-yl)pyridinecoordination polymermolecular designproton-coupled electron transferspin crossoverMore Related Videos
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