Slow magnetic relaxation and water oxidation activity of dinuclear CoIICoIIIand unique triangular CoIICoIICoIIImixed-valence complexes

Ritwik Modak, Biswajit Mondal, Yeasin Sikdar, Jayisha Banerjee, Enrique Colacio, Itziar Oyarzabal, Joan Cano, Sanchita Goswami

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12 Citations (SciVal)

Abstract

Construction of efficient multifunctional materials is one of the greatest challenges of our time. We herein report the magnetic and catalytic characterization of dinuclear [CoIIICoII(HL1)2(EtOH)(H2O)]Cl·2H2O (1) and trinuclear [CoIIICoII2(HL2)2(L2)Cl2]·3H2O (2) mixed valence complexes. Relevant structural features of the complexes have been mentioned to correlate with their magnetic and catalytic properties. Unique structural features, especially in terms of significant distortions around the CoIIcentre(s), prompted us to test both spin-orbit coupling (SOC) and zero field splitting (ZFS) methodologies for the systems. The positive sign ofDvalues has been established from X-band EPR spectra recorded in the 5-40 K temperature range and reaffirmed by CAS/NEVPT2 calculations. ZFS tensors are also extracted for the compounds along with CoIIGaIIIand CoIIZnIICoIIImodel species. Interestingly,1shows slow relaxation of magnetization below 6.5 K in the presence of a 1000 Oe external dc field with two relaxation processes (Ueff= 37.0 K withτ0= 1.57 × 10−8s for the SR process andUeff= 7 K withτ0= 1.66 × 10−6s for the FR process). As mixed valence cobalt complexes with various nuclearities are central to the quest for water oxidation catalysts, we were prompted to explore their features and to our surprise, water oxidation ability has been realized for both1and2with significant nuclearity control.

Original languageEnglish
Pages (from-to)6328-6340
Number of pages13
JournalDalton Transactions
Volume49
Issue number19
DOIs
Publication statusPublished - 21-05-2020

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

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