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

Kushch, L.A.; Kurochkina, L. S.; Yagubskii, Eduard B.; Шилов, Г. В.; Алдошин, С. М.; Emel’yanov, V. A.; Shvachko, Yuri N.; Mironov, V. S.; Schaniel, Dominik; Woike, Theo; Carbonera, Chiara; Mathonière, Corine

doi:10.1002/ejic.200600271

Cited by 31 publications

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References 42 publications

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“…2, а) 6 ] complex. 13 A qualitative comparison of the intensities of these peaks for complexes 1 and 2 shows that the concentration of the metastable states generated by irradiation in 1 is high er than that in 2.…”

Section: Resultsmentioning

confidence: 97%

Synthesis, structure, and properties of the [RuNO(NH3)5][Co(CN)6] complex containing a photochromic cation

et al. 2008

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The salt of cobalt hexacyanide with the photochromic mononitrosyl cation [RuNO(NH 3 ) 5 ] 3+ with the composition [RuNO(NH 3 ) 5 ][Co(CN) 6 ] was synthesized. Single crystals of the salt were grown, and the crystal structure was solved. The photochromic properties were studied by differential scanning calorimetry (DSC).Key words: synthesis, cobalt hexacyanide, photochromic ruthenium mononitrosyl complex cation, crystal structure, long lived metastable state.In the last decade, the new line of investigation in materials chemistry and physics associated with the de sign of molecular multifunctional compounds based on transition metal coordination complexes has been exten sively developed. The coexistence of various functional building blocks in one and the same crystal lattice allows the control of one of the properties by exposing another property to external factors, such as the temperature, light, or magnetic and electric fields, depending on the combination of the properties of the material. A com bination of these properties in one and the same crystal lattice and their synergism can give rise to the previously unknown properties and new applications in molecular electronics.In this area of investigation, the design of molecular photomagnetic materials (compounds containing light sensitive and magnetic molecular blocks) has attract ed great interest. The low temperature photomagnetic effect was discovered for the first time in the Prussian blue analogue {K 0.2 Co 1.4 [Fe(CN) 6 ]}•6.9H 2 O. 1 Photo magnets based on various classes of transition metal com pounds, in which the light induced electronic structural changes lead to substantial changes in the magnetic prop erties, were synthesized. 2 Among these compounds, most attention has been given to complexes, in which the fol lowing light induced electronic structural changes are ob served: 1) charge transfer from one metal to another (Prus sian blue analogues 1 ); 2) isomerization of the ligand ac companied by changes in the spin state; 3 3) thermal spin transition, such as the transition from one spin state in Fe II complexes; 4 4) metal to ligand charge transfer (nick el nitroprusside 5 ).Recently, it has been found that, like the photo chromic anionic octahedral mononitrosyl complexes [MNOX 5 ] 2-(M = Fe, Ru, or Os; X = CN, Cl, or Br), the cationic ruthenium mononitrosyl complexes [RuNOL 4 X] n+ (L = NH 3 or ethylenediamine; X = NH 3 , Cl, or OH; n = 2 or 3) can form long lived metastable states under light irradiation. 6,7 As opposed to the anionic complexes, only one metastable state (MS1) is formed in the cationic ruthenium mononitrosyl complexes under irradiation at a wavelength of 350-550 nm. The second metastable state (MS2) in these complexes is generated by successive irradiation at 435 and 1064 nm. 8 It is note worthy that the transition temperatures (260-293 K) 8-11 from the metastable state (MS1) to the ground state in the cationic ruthenium mononitrosyl complexes are sub stantially higher than those in the anionic complexes (203-223 K). 8 In t...

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Section: Resultsmentioning

confidence: 97%

Synthesis, structure, and properties of the [RuNO(NH3)5][Co(CN)6] complex containing a photochromic cation

et al. 2008

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“…This high energetic position leads to a rather high saddle point of about 3 eV, which must be overcome during population of the metastable state by illumination with light in the energy range 2.48-3.35 eV. In case of the Cr-and Cocompound this influence might be due to the pecularities of their crystal structure, which are characterized by the presence of a three-dimensional network of hydrogen bonds and van der Waals contacts between the CN-ligands of the anions and NH 3 -as well as NO-ligands of the cations [18,19]. It seems therefore plausible that for both compounds the energetic position of state SI is lifted by 2.1 eV with respect to GS since the presence of rigid hydrogen bonds shifts the energetic position of the potential minimum.…”

Section: Discussionmentioning

confidence: 98%

“…[13]. Furthermore populations of 30% for SI and SII in the paramagnetic compound enable us to investigate the influence of photoinduced linkage isomers on the magnetic properties of the compound [18].…”

Section: Discussionmentioning

confidence: 99%

“…Furthermore the generation of the metastable linkage isomers can lead to a ferromagnetic ordering of the counter ions, as was shown for the Ni 2+ with S = 1 in Ni[Fe(CN) 5 NO] [17]. In a recent article it was reported that the paramagnetic signal in [RuNO(NH 3 ) 5 ][Cr(CN) 6 ] is influenced by the excitation of the metastable linkage isomers [18]. The higher the achievable population of the metastable states the higher the chances to influence significantly the magnetic properties of these compounds by light.…”

Section: Introductionmentioning

confidence: 89%

“…[RuNO(NH 3 ) 5 ]X with X = Cl 3 AE H 2 O, Cr(CN) 6 , Co(CN) 6 , and ZrF 6 was prepared as described elsewhere [12,18,19].…”

Section: Methodsmentioning

confidence: 99%

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Photoinduced nitrosyl linkage isomers in complexes based on the photochromic cation [RuNO(NH3)5]3+ with the paramagnetic anion [Cr(CN)6]3− and the diamagnetic anions [Co(CN)6]3− and [ZrF6]2−

et al. 2007

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

Kushch¹,

al.²

2006

ChemInform

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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.

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

Abstract: (5) is reported. The crystal structures of the salts 1 and 3 are discussed. In contrast to 1 and 3 which exhibit reversible photochromic properties, illumination of 2 and 4 results in an

Cited by 31 publications

References 42 publications

Synthesis, structure, and properties of the [RuNO(NH3)5][Co(CN)6] complex containing a photochromic cation

Synthesis, structure, and properties of the [RuNO(NH3)5][Co(CN)6] complex containing a photochromic cation

Photoinduced nitrosyl linkage isomers in complexes based on the photochromic cation [RuNO(NH3)5]3+ with the paramagnetic anion [Cr(CN)6]3− and the diamagnetic anions [Co(CN)6]3− and [ZrF6]2−

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

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

Abstract: (5) is reported. The crystal structures of the salts 1 and 3 are discussed. In contrast to 1 and 3 which exhibit reversible photochromic properties, illumination of 2 and 4 results in an

Cited by 31 publications

References 42 publications

Synthesis, structure, and properties of the [RuNO(NH3)5][Co(CN)6] complex containing a photochromic cation

Synthesis, structure, and properties of the [RuNO(NH3)5][Co(CN)6] complex containing a photochromic cation

Photoinduced nitrosyl linkage isomers in complexes based on the photochromic cation [RuNO(NH3)5]3+ with the paramagnetic anion [Cr(CN)6]3− and the diamagnetic anions [Co(CN)6]3− and [ZrF6]2−