TY - JOUR
T1 - Assembling Hexagonal-Bipyramidal {Mn8Zn2} and {Mn8Zn4} Clusters
AU - Tziotzi, Thomais G.
AU - Andreou, Evangelos K.
AU - Mavromagoulos, Athanasios
AU - Murrie, Mark
AU - Dalgarno, Scott J.
AU - Brechin, Euan K.
AU - Milios, Constantinos J.
N1 - Funding Information:
C.J.M. and T.G.T. thank the Hellenic Foundation for Research and Innovation (H.F.R.I.) under the “First Call for H.F.R.I. Research Projects to support Faculty members and Researchers and the procurement of high‐cost research equipment grant” (Project Number: 400). E.K.B. thanks the EPSRC for financial support under grant reference number EP/V010573/1. M.M. thanks the University of Glasgow for financial support.
Publisher Copyright:
© 2022 Wiley-VCH GmbH.
PY - 2022/11/17
Y1 - 2022/11/17
N2 - Reaction between Mn(NO3)2 ⋅ 6H2O, Zn(NO3)2 ⋅ 6H2O, 1,3,5-tri(2-hydroxyethyl)-1,3,5-triazacyclohexane (H3L) and pyrazole in MeOH under basic conditions leads to the formation of the decanuclear complex [MnIII6MnII2ZnII2(L)2(pyr)4O4(OH)4(NO3)2 (MeOH)2(H2O)4](NO3)2 ⋅ Η2Ο (1 ⋅ Η2Ο). The metallic core of the cationic cluster consists of a central hexagonal-bipyramidal {MnIII4MnII2ZnII2} unit connected to two peripheral trivalent Mn centers arranged in a “trans” fashion, with one MnIII center lying above and one MnIII center below the hexagonal plane. Replacing Mn(NO3)2 ⋅ 6H2O with MnBr2 ⋅ 4H2O and repeating the same reaction leads to the formation of the related, neutral decanuclear complex [MnIII6MnII2ZnII2(L)2(pyr)4O4(OH)4Br4(H2O)2] (2), displaying the same metallic core as 1. Addition of THF to the reaction mixture that produces (2) affords the neutral dodecanuclear complex [MnIII6MnII2ZnII4(L)2(pyr)6O4(OH)4Br6(H2O)4] ⋅ 8THF (3 ⋅ 8THF), whose metallic skeleton retains the central hexagonal-bipyramidal {MnIII4MnII2ZnII2} unit found in 1 and 2 but is now connected to two peripheral {MnIIIZnII} units. Magnetic susceptibility and magnetization measurements carried out in the T=2–300 K temperature range and in fields up to B=7.0 T for all three complexes reveal dominant antiferromagnetic exchange interactions.
AB - Reaction between Mn(NO3)2 ⋅ 6H2O, Zn(NO3)2 ⋅ 6H2O, 1,3,5-tri(2-hydroxyethyl)-1,3,5-triazacyclohexane (H3L) and pyrazole in MeOH under basic conditions leads to the formation of the decanuclear complex [MnIII6MnII2ZnII2(L)2(pyr)4O4(OH)4(NO3)2 (MeOH)2(H2O)4](NO3)2 ⋅ Η2Ο (1 ⋅ Η2Ο). The metallic core of the cationic cluster consists of a central hexagonal-bipyramidal {MnIII4MnII2ZnII2} unit connected to two peripheral trivalent Mn centers arranged in a “trans” fashion, with one MnIII center lying above and one MnIII center below the hexagonal plane. Replacing Mn(NO3)2 ⋅ 6H2O with MnBr2 ⋅ 4H2O and repeating the same reaction leads to the formation of the related, neutral decanuclear complex [MnIII6MnII2ZnII2(L)2(pyr)4O4(OH)4Br4(H2O)2] (2), displaying the same metallic core as 1. Addition of THF to the reaction mixture that produces (2) affords the neutral dodecanuclear complex [MnIII6MnII2ZnII4(L)2(pyr)6O4(OH)4Br6(H2O)4] ⋅ 8THF (3 ⋅ 8THF), whose metallic skeleton retains the central hexagonal-bipyramidal {MnIII4MnII2ZnII2} unit found in 1 and 2 but is now connected to two peripheral {MnIIIZnII} units. Magnetic susceptibility and magnetization measurements carried out in the T=2–300 K temperature range and in fields up to B=7.0 T for all three complexes reveal dominant antiferromagnetic exchange interactions.
KW - Heterometallic clusters
KW - Magnetic properties
KW - Manganese
KW - Synthesis design
KW - Zinc
UR - http://www.scopus.com/inward/record.url?scp=85137348217&partnerID=8YFLogxK
U2 - 10.1002/ejic.202200434
DO - 10.1002/ejic.202200434
M3 - Article
SN - 1434-1948
VL - 2022
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 32
M1 - e202200434
ER -