Abstract
We report the synthesis and physical studies of a novel porphyrazine (pz) dimer {1[Ni,Cu]}2, which has Ni(II) ions incorporated into the pz cores and is linked by two Cu(II) ions coordinated to bis(picolinamide) chelates attached to the pz periphery. {1[Ni,Cu]}2 was prepared from precursor pz 2 with a selenodiazole ring fused to the pz core. This ring was deprotected to form the diamino-pz 3, which reacted with 2 mol of picolinoyl chloride hydrochloride to form pz 1[2H,2H], with peripheral bis(picolinamide) chelates; this was metalated to form {1[Ni,Cu]}2. The crystal structures of 1[2H,2H] and {1[Ni,Cu]}2 are presented. The latter is a dimer in which parallel, face-to-face pz's with an average separation of 3.30 Å are linked through the peripheral picolinamide ligands by a pair of peripheral Cu(II) ions. Each Cu(II) is coordinated with distorted square-planar geometry by a picolinamide from each pz. In this report, we focus on the interaction of these two peripheral Cu(II) ions. We discuss the preparation and magnetic properties of the pz dimer complex {1[Ni,Cu]}2 with two Cu(II) ions in the peripheral chelate but a diamagnetic metal ion Ni(II) in the pz core. Although {1[Ni,Cu]}2 contains two Cu(II) ions (S = 1/2), we could detect no electron paramagnetic resonance signal, which suggests very strong antiferromagnetic exchange between those two Cu(II) ions. Temperature-dependent magnetic susceptibility measurement gives an exchange splitting between the S = 0 ground state and the excited triplet state of Δ = 660 cm-1.
Original language | English (US) |
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Pages (from-to) | 8272-8276 |
Number of pages | 5 |
Journal | Inorganic chemistry |
Volume | 44 |
Issue number | 23 |
DOIs | |
State | Published - Nov 14 2005 |
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
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CCDC 291828: Experimental Crystal Structure Determination
Zhong, C. (Creator), Zhao, M. (Creator), Stern, C. (Creator), Barrett, A. G. M. (Creator) & Hoffman, B. M. (Creator), Cambridge Crystallographic Data Centre, 2006
DOI: 10.5517/cc9sntj, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc9sntj&sid=DataCite
Dataset
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CCDC 291829: Experimental Crystal Structure Determination
Zhong, C. (Creator), Zhao, M. (Creator), Stern, C. (Creator), Barrett, A. G. M. (Creator) & Hoffman, B. M. (Creator), Cambridge Crystallographic Data Centre, 2006
DOI: 10.5517/cc9snvk, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc9snvk&sid=DataCite
Dataset