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Turning a "useless" ligand into a "useful" ligand: a magneto-structural study of an unusual family of Cu-II wheels derived from functionalised phenolic oximes

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Title Turning a "useless" ligand into a "useful" ligand: a magneto-structural study of an unusual family of Cu-II wheels derived from functionalised phenolic oximes
 
Creator FROST, JM
STIRLING, RJ
SANZ, S
VYAS, N
NICHOL, GS
RAJARAMAN, G
BRECHIN, EK
 
Subject DINUCLEAR COPPER(II) COMPLEXES
GAUSSIAN-BASIS SETS
CRYSTAL-STRUCTURE
STRUCTURAL-CHARACTERIZATION
LANCZOS METHOD
MAGNETIC-PROPERTIES
METAL-COMPLEXES
ATOMS LI
DIMERS
COORDINATION
 
Description While the phenolic oximes (R-saoH(2)) are well known for producing monometallic complexes of the type [MII(R-saoH)(2)] with Cu-II ions in near quantitative yield, their derivatisation opens the door to much more varied and interesting coordination chemistry. Here we show that combining the complimentary diethanolamine and phenolic oxime moieties into one organic framework (H4L1 and H4L2) allows for the preparation and isolation of an unusual family of [Cu-II](n) wheels, including saddle-shaped, single-stranded [Cu-8(II)] wheels of general formula [Cu-8(HL1)(4)(X)(4)] n[Y] (when n = 0, X = Cl-, NO3-, AcO-, N-3(-); when n = 2+X = (OAc)(2)/(2,2'-bpy)(2) and Y = [BF4](2)) and [Cu-8(HL2)(4)(X)(4)](X = Cl-, Br-), a rectangular [Cu-6(HL1)(4)] wheel, and a heterometallic [Cu4Na2(HL1)2(H2L1)(2)] hexagon. Magnetic studies show very strong antiferromagnetic exchange between neighbouring metal ions, leading to diamagnetic ground states in all cases. DFT studies reveal that the magnitude of the exchange constants are correlated to the Cu-N-O-Cu dihedral angles, which in turn are correlated to the planarity/puckering of the [Cu-II](n) rings.
 
Publisher ROYAL SOC CHEMISTRY
 
Date 2016-01-15T07:07:19Z
2016-01-15T07:07:19Z
2015
 
Type Article
 
Identifier DALTON TRANSACTIONS, 44(22)10177-10187
1477-9226
1477-9234
http://dx.doi.org/10.1039/c5dt00884k
http://dspace.library.iitb.ac.in/jspui/handle/100/18009
 
Language en