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The intricate paramagnetic state of [Os(Q)(2)(bpy)](+), Q=4,6-di-tert-butyl-o-iminobenzoquinone

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Title The intricate paramagnetic state of [Os(Q)(2)(bpy)](+), Q=4,6-di-tert-butyl-o-iminobenzoquinone
 
Creator DAS, D
SCHERER, TM
DAS, A
MONDAL, TK
MOBIN, SM
FIEDLER, J
PRIEGO, JL
JIMENEZ-APARICIO, R
KAIM, W
LAHIRI, GK
 
Subject DENSITY-FUNCTIONAL THEORY
TRANSITION-METAL-COMPLEXES
NON-INNOCENT LIGANDS
ELECTRONIC-STRUCTURE
CARBOXYLATE COMPOUNDS
EXCITATION-ENERGIES
MAGNETIC-PROPERTIES
OXIDATION-STATES
REDOX SERIES
MOLECULES
 
Description The combination of two highly non-innocent ligands with a third-row transition metal produces the title complex ion which was crystallised as [Os(Q)(2)(bpy)](ClO4)center dot C6H6 (Q = 4,6-di-tert-butyl-o-iminobenzoquinones, bpy = 2,2'-bipyridine) and could be structurally characterised to exhibit a trischelate situation at the metal with trans-positioned N and cis-positioned O donor atoms. The metrical ligand parameters are in agreement with two partially reduced ligands. A 3-spin interaction (Q(center dot-)) Os-III(Q(center dot-)) can rationalise the observed S = 1/2 situation with ligand-centred resulting spin. Ligand-based spin is confirmed by DFT (calculated spin populations Q: 1.113; Os: -0.113; bpy: 0.001) and is also apparent from the EPR signal (g(1) 1.981, g(2) 1.955, g(3) 1.803, Delta g 0.178, < g > 1.915) which is influenced by the high spin-orbit coupling constant of the osmium centre. The susceptibility measurements reveal antiferromagnetic behaviour. A one-electron oxidation and two one-electron reductions could be monitored spectroelectrochemically (UV-VIS-NIR) and analysed by TD-DFT, in comparison with the results from the ruthenium analogue. The analysis reflects the strong orbital mixing between the metal and the two Q-ligand MOs.
 
Publisher ROYAL SOC CHEMISTRY
 
Date 2014-10-16T15:01:29Z
2014-10-16T15:01:29Z
2012
 
Type Article
 
Identifier DALTON TRANSACTIONS, 41(38)11675-11683
1477-9226
1477-9234
http://dx.doi.org/10.1039/c2dt30903c
http://dspace.library.iitb.ac.in/jspui/handle/100/15850
 
Language en