Electronic Control of the Position of the Pb Atom on the Surface of B 8 Borozene in the PbB 8 Cluster
- Award ID(s):
- 2403841
- PAR ID:
- 10565876
- Publisher / Repository:
- ACS
- Date Published:
- Journal Name:
- The Journal of Physical Chemistry A
- Volume:
- 128
- Issue:
- 18
- ISSN:
- 1089-5639
- Page Range / eLocation ID:
- 3564 to 3570
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract A novel transition metal chalcohalide [Cr7S8(en)8Cl2]Cl3 ⋅ 2H2O, with [Cr7S8]5+dicubane cationic clusters, has been synthesized by a low temperature solvothermal method, using dimethyl sulfoxide (DMSO) and ethylenediamine (en) solvents. Ethylenediamine ligand exhibits bi‐ and monodentate coordination modes; in the latter case ethylenediamine coordinates to Cr atoms of adjacent clusters, giving rise to a 2D polymeric structure. Although magnetic susceptibility shows no magnetic ordering down to 1.8 K, a highly negative Weiss constant,θ=−224(2) K, obtained from Curie‐Weiss fit of inverse susceptibility, suggests strong antiferromagnetic (AFM) interactions betweenS=3/2 Cr(III) centers. Due to the complexity of the system with (2S+1)7=16384 microstates from seven Cr3+centers, a simplified model with only two exchange constants was used for simulations. Density‐functional theory (DFT) calculations yielded the two exchange constants to beJ1=−21.4 cm−1andJ2=−30.2 cm−1, confirming competing AFM coupling between the shared Cr3+center and the peripheral Cr3+ions of the dicubane cluster. The best simulation of the experimental data was obtained withJ1=−20.0 cm−1andJ2=−21.0 cm−1, in agreement with the slightly stronger AFM exchange within the triangles of the peripheral Cr3+ions as compared to the AFM exchange between the central and peripheral Cr3+ions. This compound is proposed as a synthon towards magnetically frustrated systems assembled by linking dicubane transition metal‐chalcogenide clusters into polymeric networks.more » « less
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