TY - JOUR
T1 - Ferro- to antiferromagnetic crossover angle in diphenoxido- and carboxylato-bridged trinuclear NiII2-MnII complexes
T2 - Experimental observations and theoretical rationalization
AU - Seth, Piya
AU - Figuerola, Albert
AU - Jover, Jesús
AU - Ruiz, Eliseo
AU - Ghosh, Ashutosh
PY - 2014/9/2
Y1 - 2014/9/2
N2 - Three new trinuclear heterometallic NiII-MnII complexes have been synthesized using a [NiL] metalloligand, where H 2L = N,N′-bis(salicylidene)-1,3-propanediamine. The complexes [(NiL)2Mn(OCnn)2(CH3OH)2] ·CH3OH (1), [(NiL)2Mn(OPh)2(CH 3OH)2][(NiL)2Mn(OPh)2]·H 2O (2), and [(NiL)2Mn(OSal)2(CH 3OH)2]·2[NiL] (3) (where OCnn = cinnamate, OPh = phenylacetate, OSal = salicylate) have been structurally characterized. In all three complexes, in addition to the double phenoxido bridge, the two terminal NiII atoms are linked to the central MnII by means of a syn-syn bridging carboxylate, giving rise to a linear structure. Complexes 1 and 2 with Ni-O-Mn angles of 97.24 and 96.43°, respectively, exhibit ferromagnetic interactions (JNi-Mn = +1.38 and +0.50 cm-1, respectively), whereas 3 is antiferromagnetic (JNi-Mn = -0.24 cm-1), having an Ni-O-Mn angle of 98.51°. DFT calculations indicate that there is a clear magneto-structural correlation between the Ni-O-Mn angle and JNi-Mn values, which is in agreement with the experimental results.
AB - Three new trinuclear heterometallic NiII-MnII complexes have been synthesized using a [NiL] metalloligand, where H 2L = N,N′-bis(salicylidene)-1,3-propanediamine. The complexes [(NiL)2Mn(OCnn)2(CH3OH)2] ·CH3OH (1), [(NiL)2Mn(OPh)2(CH 3OH)2][(NiL)2Mn(OPh)2]·H 2O (2), and [(NiL)2Mn(OSal)2(CH 3OH)2]·2[NiL] (3) (where OCnn = cinnamate, OPh = phenylacetate, OSal = salicylate) have been structurally characterized. In all three complexes, in addition to the double phenoxido bridge, the two terminal NiII atoms are linked to the central MnII by means of a syn-syn bridging carboxylate, giving rise to a linear structure. Complexes 1 and 2 with Ni-O-Mn angles of 97.24 and 96.43°, respectively, exhibit ferromagnetic interactions (JNi-Mn = +1.38 and +0.50 cm-1, respectively), whereas 3 is antiferromagnetic (JNi-Mn = -0.24 cm-1), having an Ni-O-Mn angle of 98.51°. DFT calculations indicate that there is a clear magneto-structural correlation between the Ni-O-Mn angle and JNi-Mn values, which is in agreement with the experimental results.
UR - http://www.scopus.com/inward/record.url?scp=84906846228&partnerID=8YFLogxK
U2 - 10.1021/ic501425x
DO - 10.1021/ic501425x
M3 - Article
AN - SCOPUS:84906846228
SN - 0020-1669
VL - 53
SP - 9296
EP - 9305
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 17
ER -