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Magnetostructural Studies on Zigzag One-Dimensional Coordination Polymers Formed by Tetraamidatodiruthenium(II,III) Paddlewheel Units Bridged by SCN Ligands

1
Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Ciudad Universitaria, E-28040 Madrid, Spain
2
Centro de Asistencia a la Investigación Difracción de Rayos X, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, E-28040 Madrid, Spain
*
Authors to whom correspondence should be addressed.
Magnetochemistry 2019, 5(3), 40; https://doi.org/10.3390/magnetochemistry5030040
Received: 27 May 2019 / Revised: 11 June 2019 / Accepted: 12 June 2019 / Published: 1 July 2019
We report herein on three zigzag one-dimensional coordination polymers of {[Ru2(μ-NHOCR)4](μ-SCN)}n (R = o-Me-C6H4 (2), m-Me-C6H4 (3), p-Me-C6H4 (4)) formula. These new compounds have been obtained by reaction of the corresponding [Ru2(μ-NHOR)4(THF)2](BF4) complex with (NBu4)(SCN) under different synthetic conditions. The crystal structure of [Ru2(μ-NHOCC6H4-o-Me)4(THF)2](BF4) (1), 2 and 3 are presented. A cis-(2,2) arrangement of the amidate ligands of the [Ru2(μ-NHOCR)4]+ units is observed in all cases. Interestingly, the structures of 2 and 3 show linkage isomerism in alternated tetraamidatodiruthenium units whose axial positions are occupied by the same type of donor atom of the SCN ligands. This results in zigzag chains with a Ru-S-C angle of 98.97° and Ru-N-C angle of 169.36° in the case of 2 and 97.99° and 159.26°, respectively, in the case of 3. The magnetic data obtained for 24 are indicative of a σ2π4δ2(π*δ*)3 ground state (S = 3/2) and a large zero-field splitting (ZFS) in all cases (D = 54.57, 62.72 and 43.00 cm−1 for 24, respectively). Similar small antiferromagnetic interactions between diruthenium units (zJ = −0.93, −0.79 and −1.11 cm−1 for 24, respectively) are estimated for all the polymers, suggesting an analogous zigzag arrangement of the chains for 4. View Full-Text
Keywords: diruthenium; 1-D zigzag compounds; coordination polymers; antiferromagnetic interactions; amidate complexes; thiocyanate compounds diruthenium; 1-D zigzag compounds; coordination polymers; antiferromagnetic interactions; amidate complexes; thiocyanate compounds
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Moreno-Da Silva, S.; Delgado-Martínez, P.; Cortijo, M.; González-Prieto, R.; Priego, J.L.; Herrero, S.; Jiménez-Aparicio, R. Magnetostructural Studies on Zigzag One-Dimensional Coordination Polymers Formed by Tetraamidatodiruthenium(II,III) Paddlewheel Units Bridged by SCN Ligands. Magnetochemistry 2019, 5, 40.

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