Tuning the structure and photoinduced linkage isomerism of tetrapyridine nitrosyl ruthenium(ii) complexes by changing the trans-to-NO coordinated ligand

Ruthenium nitrosyl complexes were prepared with various trans-to-NO ligands. These compounds form Ru–ON metastable states upon blue-light excitation and the corresponding thermal stabilities were determined.

Combining photoinduced linkage isomerism and nonlinear optical properties in ruthenium nitrosyl complexes

The complex trans-[RuNO(NH3)4F]SiF6 was synthesized in quantitative yield and the structure was characterized by X-ray diffraction and spectroscopic methods. The complex crystallizes in the non-centrosymmetric space group Pn. Hirshfeld surface analysis revealed that the dominant intermolecular interactions are of types H...F and F...O, which are likely to be responsible for the packing of the molecules in a non-centrosymmetric structure. Irradiation with blue light leads to the formation of Ru–ON (metastable state MS1) and Ru–η2-(NO) (metastable state MS2) bond isomers, as shown by IR and UV–Vis spectroscopy. The structural features of the MS1 isomer were elucidated by photocrystallography. The complex exhibits exceptionally good thermal stability of the metastable state MS1, such that it can be populated by light at 290–300 K, which is important for potential applications. The second harmonic (SH) emission can be generated by femtosecond-pulsed irradiation of the complex. The generated SH is rather efficient and stable under long-term exposure. Finally, since both metastable states and harmonic generation can be generated at room temperature, an attempt to drive the SH response by photoisomerization of the nitrosyl ligand was made and is discussed.

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

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 2–4 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 2–4, respectively). Similar small antiferromagnetic interactions between diruthenium units (zJ = −0.93, −0.79 and −1.11 cm−1 for 2–4, respectively) are estimated for all the polymers, suggesting an analogous zigzag arrangement of the chains for 4.