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Novel Topology in Semiconducting Tetrathiafulvalene Lanthanide Metal‐Organic Frameworks
Author(s) -
Xie Lilia S.,
Dincă Mircea
Publication year - 2018
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.201800068
Subject(s) - chemistry , tetrathiafulvalene , lanthanide , metal organic framework , topology (electrical circuits) , metal , nanotechnology , combinatorial chemistry , organic chemistry , molecule , ion , mathematics , adsorption , combinatorics , materials science
Tetrathiafulvalene tetrabenzoate (TTFTB) and several lanthanide ions self‐assemble into metal‐organic frameworks (MOFs) that exhibit a novel topology, a (3,3,3,6,6)‐coordinated net, which features an unusual ligand coordination mode and stacking motif. The Yb and Lu MOFs are electrically conductive, with pellet conductivity values of 9(7) × 10 −7 and 3(2) × 10 −7 S/cm, respectively. The crystallographically‐determined bond lengths indicate partial oxidation of the ligand, with close S ⋅ ⋅ ⋅ S contacts between ligands providing likely charge transport pathways in the material. Magnetometry reveals temperature‐independent paramagnetism, consistent with the presence of ligand‐based radicals, as well as weak antiferromagnetic coupling between Yb 3+ centers. These results illustrate the diversity of MOF structures and properties that are accessible with the TTFTB ligand owing to its electroactive nature, propensity for intermolecular interactions, and conformational flexibility.