TY - JOUR
T1 - Constructing "Closed" and "Open" {Mn8} Clusters
AU - Tziotzi, Thomais G.
AU - Mavromagoulos, Athanasios
AU - Murrie, Mark
AU - Dalgarno, Scott J.
AU - Evangelisti, Marco
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 (HFRI) under the “First Call for HFRI Research Projects to support Faculty members and Researchers and the procurement of high-cost research equipment grant” (Project No. 400). E.K.B. thanks the EPSRC for financial support under Grant No. EP/V010573/1. M.E. thanks the Ministerio de Ciencia e Innovación (RTI2018-098537-B-C22) and Gobierno de Aragón (E11_20R). M.M. thanks the University of Glasgow for financial support.
Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/8/3
Y1 - 2022/8/3
N2 - Use of the 1,3,5-tri(2-hydroxyethyl)-1,3,5-triazacyclohexane
ligand, LH3, in manganese chemistry affords access to two
structurally related {Mn8} clusters: a “closed” {MnIII6MnII2}
puckered square wheel of formula [Mn8L2(LH)O3(OH)2(MeO)2Br(imH)(H2O)3](Br)3 (1;
imH = imidazole) and an “open” {MnIII8} rod of formula
[MnΙΙΙ8L2O4(aibH)2(aib)2(MeO)6(MeOH)2](NO3)2 (2,
aibH = 2-amino-isobutyric acid). In each case the triaza ligands, L/LH, direct
the formation of {Mn3} triangles with their N atoms preferentially
bonding to the Jahn–Teller axes of the MnIII ions. Subsequent
self-assembly is dependent on the anion of the Mn salt and the identity of the
organic coligand employed─the terminally bonded imidazole and the
chelating/bridging amino acid. The {Mn3} triangles fold up on
themselves in 1, forming a wheel. However, the syn, syn-bridging
carboxylates in 2 prevent this from happening, instead
directing the formation of a linear rod. Magnetic susceptibility and
magnetization measurements reveal competing ferro- and antiferromagnetic
interactions in both complexes, the exchange being somewhat weaker in 1 due
to the presence of MnII ions.
AB - Use of the 1,3,5-tri(2-hydroxyethyl)-1,3,5-triazacyclohexane
ligand, LH3, in manganese chemistry affords access to two
structurally related {Mn8} clusters: a “closed” {MnIII6MnII2}
puckered square wheel of formula [Mn8L2(LH)O3(OH)2(MeO)2Br(imH)(H2O)3](Br)3 (1;
imH = imidazole) and an “open” {MnIII8} rod of formula
[MnΙΙΙ8L2O4(aibH)2(aib)2(MeO)6(MeOH)2](NO3)2 (2,
aibH = 2-amino-isobutyric acid). In each case the triaza ligands, L/LH, direct
the formation of {Mn3} triangles with their N atoms preferentially
bonding to the Jahn–Teller axes of the MnIII ions. Subsequent
self-assembly is dependent on the anion of the Mn salt and the identity of the
organic coligand employed─the terminally bonded imidazole and the
chelating/bridging amino acid. The {Mn3} triangles fold up on
themselves in 1, forming a wheel. However, the syn, syn-bridging
carboxylates in 2 prevent this from happening, instead
directing the formation of a linear rod. Magnetic susceptibility and
magnetization measurements reveal competing ferro- and antiferromagnetic
interactions in both complexes, the exchange being somewhat weaker in 1 due
to the presence of MnII ions.
UR - http://www.scopus.com/inward/record.url?scp=85136177729&partnerID=8YFLogxK
U2 - 10.1021/acs.cgd.2c00489
DO - 10.1021/acs.cgd.2c00489
M3 - Article
C2 - 35971413
SN - 1528-7483
VL - 22
SP - 4935
EP - 4940
JO - Crystal Growth and Design
JF - Crystal Growth and Design
IS - 8
ER -