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Zwitterionic {Fe(I)Pc(-2)-}·(TMP+) assemblies comprising anionic iron(I) phthalocyanines and coordinating
Dmitri V Konarev1, Alexey V Kuzmin, Salavat S Khasanov
1Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow region, 142432 Russia.
Dalton Transactions (Cambridge, England : 2003)
|May 22, 2013
Summary
This study reports novel iron(I) and cobalt(I) phthalocyanine salts. A unique zwitterionic assembly was formed with N,N,N'-trimethylpiperazinium cations coordinating to iron(I) centers.
Area of Science:
- Coordination Chemistry
- Inorganic Chemistry
- Materials Science
Background:
- Phthalocyanines are versatile macrocyclic compounds with diverse applications.
- Low-valent metal phthalocyanines are of interest due to their unique electronic properties.
- Zwitterionic structures in coordination compounds can lead to novel properties.
Purpose of the Study:
- To synthesize and characterize novel iron(I) and cobalt(I) phthalocyanine salts.
- To investigate the structural and electronic properties of these new compounds.
- To explore the formation of zwitterionic coordination assemblies.
Main Methods:
- Single crystal X-ray diffraction for structural determination.
- Electron Paramagnetic Resonance (EPR) spectroscopy for electronic characterization.
- Variable temperature studies of EPR spectra.
Main Results:
- Synthesis of {[Fe(I)Pc(-2)(-)]·(TMP(+))}·0.5C6H14 and {Co(i)Pc(-2)(-)}·(TMP(+)) salts.
- Observation of a novel zwitterionic assembly with a weak N(TMP(+))-Fe bond in the iron(I) complex.
- EPR analysis revealed a low-spin Fe(I) (d7) state and a temperature-dependent metastable state in the iron(I) complex; the cobalt(I) complex is EPR silent.
Conclusions:
- The first zwitterionic coordination assembly containing iron(I) phthalocyanine anions and N,N,N '-trimethylpiperazinium cations has been successfully synthesized.
- The iron(I) phthalocyanine complex exhibits unique EPR spectral features attributed to its electronic configuration and a metastable low-temperature state.
- The coordination behavior differs between iron(I) and cobalt(I) phthalocyanine salts, with cations coordinating to iron but not cobalt.
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