Bifunctional Materials Based on the Photochromic Cation [RuNO(NH₃)₅]³⁺ with Paramagnetic Metal Complex Anions.

Abstract

Ruthenium I 7800 Bifunctional Materials Based on the Photochromic Cation [RuNO(NH 3 ) 5 ] 3+ with Paramagnetic Metal Complex Anions. -The crystal structures of compounds (IVa) and (VIa) are determined by single crystal XRD. (IVa) crystallizes in the hexagonal space group R3 with Z = 3 and (VIa) in the hexagonal space group P31c with Z = 6. The structures contain three-dimensional networks of hydrogen bonds. Both compounds exhibit reversible photochromic properties. Illumination of (IVb) and (VIb) results in an irreversible photochemical reaction. Compound (VIII) is not photochromic at all. The prepared compounds are further characterized by magnetic measurements. -(KUSHCH*, L. A.; et al.; Eur.

The Ruthenium Nitrosyl Moiety in Clusters: Trinuclear Linear μ-Hydroxido Magnesium(II)-Diruthenium(II), μ3-Oxido Trinuclear Diiron(III)–Ruthenium(II), and Tetranuclear μ4-Oxido Trigallium(III)-Ruthenium(II) Complexes

“…In particular, the ruthenium complexes [RuNO-(NH 3 ) 5 ] 3+ , [RuNO(NH 3 ) 4 OH] 2+ , and [RuNO(en) 2 Cl] 2+ with paramagnetic anions based on chromium, cobalt, and manganese have been synthesized and characterized. 43,44 The light-induced transition of the ground state (GS) Ru-NO unit to its metastable isomer Ru-ON (MS1) was observed in all cases. MS1 is stable only at low temperature, although an increase in back-isomerization (MS1 to GS) temperature of 20−25 K was found, depending on the identity of the counteranion.…”

“…Ruthenium nitrosyl complexes show interesting redox activity , and are of inherent interest as potential anticancer drugs. − As discussed in a recent “Forum of Renaissance in NO Chemistry”, nitric oxide release both in the solid state and in aqueous solution is relevant for biomedical applications. , Light-induced Ru–NO bond dissociation in solution may involve the formation of the intermediate metastable linkage isomers MS1 (Ru-ON) and MS2 (Ru-η 2 -NO). − These photoisomerization processes in the solid state have potential uses in data storage − and in the design of photochromic materials or hologram gratings on the basis of the difference in refractive indexes between the ground and metastable states . Another interest is the use of ruthenium nitrosyl complexes as building blocks for the assembly of systems combining a photoswitchable unit with a paramagnetic moiety in the same crystal. ,, Such systems may allow for light-induced linkage isomerization, which will trigger changes in magnetic behavior, leading potentially to novel functional materials. In particular, the ruthenium complexes [RuNO­(NH 3 ) 5 ] 3+ , [RuNO­(NH 3 ) 4 OH] 2+ , and [RuNO­(en) 2 Cl] 2+ with paramagnetic anions based on chromium, cobalt, and manganese have been synthesized and characterized. , The light-induced transition of the ground state (GS) Ru-NO unit to its metastable isomer Ru-ON (MS1) was observed in all cases.…”

“…Another interest is the use of ruthenium nitrosyl complexes as building blocks for the assembly of systems combining a photoswitchable unit with a paramagnetic moiety in the same crystal. ,, Such systems may allow for light-induced linkage isomerization, which will trigger changes in magnetic behavior, leading potentially to novel functional materials. In particular, the ruthenium complexes [RuNO­(NH 3 ) 5 ] 3+ , [RuNO­(NH 3 ) 4 OH] 2+ , and [RuNO­(en) 2 Cl] 2+ with paramagnetic anions based on chromium, cobalt, and manganese have been synthesized and characterized. , The light-induced transition of the ground state (GS) Ru-NO unit to its metastable isomer Ru-ON (MS1) was observed in all cases. MS1 is stable only at low temperature, although an increase in back-isomerization (MS1 to GS) temperature of 20–25 K was found, depending on the identity of the counteranion.…”

“…42 Another interest is the use of ruthenium nitrosyl complexes as building blocks for the assembly of systems combining a photoswitchable unit with a paramagnetic moiety in the same crystal. 40,43,44 Such systems may allow for light-induced linkage isomerization, which will trigger changes in magnetic behavior, leading potentially to novel functional materials. In particular, the ruthenium complexes [RuNO-(NH 3 ) 5 ] 3+ , [RuNO(NH 3 ) 4 OH] 2+ , and [RuNO(en) 2 Cl] 2+ with paramagnetic anions based on chromium, cobalt, and manganese have been synthesized and characterized.…”

Infrared Detection with Temperature Sweep for Stability Determination of Ru-ON Metastable States

“…Further near-infrared irradiation converts MS1 to MS2 with the crystal becoming black . Because of the highest thermal stability of MS among other metals, the ruthenium nitrosyl complexes are promising building blocks for the photochromic and photomagnetic materials . Further improvements are desirable because a few MS1 examples survive long enough at room temperature. − For most complexes, the O -coordinated nitrosyl has a lifetime of milliseconds before it converts back to the GS .…”