TY - JOUR
T1 - Spin Frustration in the Triradical Trianion of a Naphthalenediimide Molecular Triangle
AU - Wu, Yilei
AU - Krzyaniak, Matthew D.
AU - Stoddart, J. Fraser
AU - Wasielewski, Michael R.
N1 - Funding Information:
This research was supported by the National Science Foundation under grant no. CHE-1565925 (M.R.W.). This research is part of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdul-Aziz City for Science and Technology (KACST) and Northwestern University (NU) (J.F.S.). Y.W. thanks the Fulbright Scholars Program for a Graduate Research Fellowship and gratefully acknowledges support of a Ryan Fellowship from the NU International Institute for Nanotechnology (IIN). We thank Charlotte Stern for helping with carrying out single-crystal XRD analysis.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/3/1
Y1 - 2017/3/1
N2 - Crystalline supramolecular frameworks consisting of charged molecules, held together by hydrogen bonds and Coulomb interactions, have attracted great interest because of their unusual structural, chemical, electronic, and magnetic properties. Herein, we report the preparation, structure, and magnetic properties of the triradical trianion of a shape-persistent chiral equilateral molecular triangle having three naphthalene-1,4:5,8-bis(dicarboximide)s ((+)-NDI-Δ3(−•)). Single-crystal X-ray diffraction of its tris(cobaltocenium) salt ([(+)-NDI-Δ3(−•)(CoCp2+)3]) reveals accessible one-dimensional tubular cavities, and variable-temperature electron paramagnetic resonance spectroscopy shows that a dilute solution of [(+)-NDI-Δ3(−•)(CoCp2+)3] in an organic glass has a spin-frustrated doublet ground state and a thermally accessible quartet state. Furthermore, SQUID magnetometry from 5 to 300 K of solid [(+)-NDI-Δ3(−•)(CoCp2+)3] shows ferromagnetic ordering with a Curie temperature TC = 20 K. The successful preparation of hybrid ionic materials comprising macrocyclic triradical trianions with spin-frustrated ground states and accessible 1D pores offers routes to new organic spintronic materials.
AB - Crystalline supramolecular frameworks consisting of charged molecules, held together by hydrogen bonds and Coulomb interactions, have attracted great interest because of their unusual structural, chemical, electronic, and magnetic properties. Herein, we report the preparation, structure, and magnetic properties of the triradical trianion of a shape-persistent chiral equilateral molecular triangle having three naphthalene-1,4:5,8-bis(dicarboximide)s ((+)-NDI-Δ3(−•)). Single-crystal X-ray diffraction of its tris(cobaltocenium) salt ([(+)-NDI-Δ3(−•)(CoCp2+)3]) reveals accessible one-dimensional tubular cavities, and variable-temperature electron paramagnetic resonance spectroscopy shows that a dilute solution of [(+)-NDI-Δ3(−•)(CoCp2+)3] in an organic glass has a spin-frustrated doublet ground state and a thermally accessible quartet state. Furthermore, SQUID magnetometry from 5 to 300 K of solid [(+)-NDI-Δ3(−•)(CoCp2+)3] shows ferromagnetic ordering with a Curie temperature TC = 20 K. The successful preparation of hybrid ionic materials comprising macrocyclic triradical trianions with spin-frustrated ground states and accessible 1D pores offers routes to new organic spintronic materials.
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U2 - 10.1021/jacs.7b00515
DO - 10.1021/jacs.7b00515
M3 - Article
C2 - 28194969
AN - SCOPUS:85014175660
VL - 139
SP - 2948
EP - 2951
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 8
ER -