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Synthesis, Crystal Structures and Magnetic Properties of Two Heterobridged µ‐Phenoxo‐µ 1,1 ‐Azide/Isocyanate Dinickel(II) Compounds: Experimental and Theoretical Exploration
Author(s) -
Mandal Shuvankar,
Majumder Samit,
Mondal Suraj,
Mohanta Sasankasekhar
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201800742
Subject(s) - chemistry , azide , isocyanate , crystallography , imine , morpholine , isostructural , denticity , density functional theory , crystal structure , medicinal chemistry , computational chemistry , organic chemistry , catalysis , polyurethane
This investigation deals with the syntheses, crystal structures and experimental and density functional theoretical magnetic properties of two heterobridged and isomorphous µ‐phenoxo‐µ 1,1 ‐azide/isocyanate dinickel(II) compounds of composition [Ni II 2 (L) 2 (µ 1,1 ‐N 3 )(CH 3 CN)(CH 3 OH)](ClO 4 ) · CH 3 CN ( 1 ) and [Ni II 2 (L) 2 (µ 1,1 ‐NCO)(CH 3 CN)(CH 3 OH)](ClO 4 ) · CH 3 CN ( 2 ), where HL is the 1:1 condensation product of 3‐ethoxysalicylaldehyde and 4‐(2‐aminoethyl)‐morpholine. The two compounds are isostructural as well, except that 1 contains end‐on azide and 2 contains end‐on isocyanate. One metal ion is surrounded by O(µ‐phenoxo), N(µ 1,1 ‐azide/µ 1,1 ‐isocyanate), N(imine), N(amine), O(ethoxy) and O(phenoxide, monodentate) atoms, while the second metal ion is surrounded by O(µ‐phenoxo), N(µ 1,1 ‐azide/µ 1,1 ‐isocyanate), N(imine), N(amine), O(methanol) and N(acetonitrile) atoms. Variable‐temperature (2–300 K) magnetic susceptibility and variable‐field (up to 5 T) magnetization data reveal ferromagnetic exchange interaction with J = 18.0 cm –1 for 1 and J = 11.4 cm –1 for 2 . Broken symmetry density functional calculations of exchange interaction have been performed on both complexes and the DFT‐computed J values are nicely matched with the experimental J values [ J (exp) = 18.0 cm –1 and J (DFT) = 17.2 cm –1 for 1 ; J (exp) = 11.4 cm –1 and J (DFT) = 8.9 cm –1 for 2 ]. The magnetic properties have been nicely rationalized in terms of spin density, magnetic orbitals and breakdown approach.