Light‐Induced Spin‐State Switching of the MoIV Centre in Trinuclear [CuII(diamine)2]2[MoIV(CN)8] Molecules

Korzeniak, Tomasz; Sasmal, Sujit; Pinkowicz, Dawid; Stefańczyk, Olaf; Sieklucka, Barbara

doi:10.1002/ejic.201800138

Eur J Inorg Chem

2018

DOI: 10.1002/ejic.201800138

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Light‐Induced Spin‐State Switching of the Mo^IV Centre in Trinuclear [Cu^II(diamine)₂]₂[Mo^IV(CN)₈] Molecules

Tomasz Korzeniak

Sujit Sasmal

Dawid Pinkowicz

et al.

Abstract: New trinuclear molecules [Cu(meen) 2 ] 2 [Mo IV (CN) 8 ]· 5H 2 O (1) and [Cu(eten) 2 ] 2 [Mo(CN) 8 ]·7H 2 O (2) (meen = N -methylethylenediamine; eten = N-ethyl-ethylenediamine) have been prepared and characterised by X-ray diffraction and dc magnetometry. The crystal structure of 1 and 2 consists of trinuclear Cu 2 Mo molecules interacting through weak semicoordination bonds and resulting in the formation of 2D and 3D supramolec- [a]

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Cited by 7 publications

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Spectroscopic Detection and Theoretical Description of Spin‐Crossover Effect in Co(II)‐terpyridine System

Stefanczyk,

Li,

Kumar

et al. 2024

Eur J Inorg Chem

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Spin‐crossover (SCO) effect on octahedral Co(II) centers is much rarer and less known than in the case of Fe(II) complexes, although it is no less promising for the development of fundamental research, sophisticated memories, and sensors. The representative compound [Co(terpy)2]I2·2H2O (terpy = 2,2′:6′,2′′‐terpyridine) was synthesized, and its physicochemical properties were studied both experimentally and theoretically. Magnetic experiments revealed a very gradual SCO between a low‐spin state (SCo(II)‐LS = 1/2) and a high‐spin state (SCo(II)‐HS = 3/2) for the pristine sample and an abrupt SCO with a narrow thermal hysteresis around 130 K for the desolvated sample. Moreover, temperature‐dependent vibrational and electronic spectroscopy were employed to track the evolution of spectroscopic features related to SCO and desolvation processes. Additionally, quantum chemical calculations were utilized to determine the electronic structure, molecular orbitals, and vibrations for different spin states at various temperatures, offering a more comprehensive understanding of the compound's spectroscopic and magnetic behaviors. These extensive investigations provide valuable insights into Co(II)‐based SCO materials and their theoretical underpinnings, paving the way for the application of their thermometric properties.

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Spectroscopic Detection and Theoretical Description of Spin‐Crossover Effect in Co(II)‐terpyridine System

Stefanczyk,

Li,

Kumar

et al. 2024

Eur J Inorg Chem

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Irradiation Temperature Dependence of the Photomagnetic Mechanisms in a Cyanido-Bridged Cu^II₂Mo^IV Trinuclear Molecule

et al. 2018

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We report a new bimetallic cyanido-bridged trinuclear complex [Cu(enpnen)][Mo(CN)]·6.75HO (1) (enpnen = N,N'-bis(2-aminoethyl)-1,3-propanediamine) that shows reversible photomagnetic effect. The photo-induced increase of magnetization is characterized by the irradiation temperature-dependent shapes of the χ T( T) plots and different magnetization values at low temperature in high magnetic field, suggesting multiple photoexcited states. The photomagnetic effect in 1 is explained through two possible processes simultaneously: the light-induced metal-to-metal charge transfer (MMCT) in the Cu-NC-Mo pair and the light-induced excited spin-state trapping (LIESST) effect in Mo center. A numerical model assuming the simultaneous existence of three possible states after irradiation: the MMCT Cu-NC-Mo-CN-Cu state, the LIESST Cu-NC-Mo-CN-Cu state, and the ground-state Cu-NC-Mo-CN-Cu was applied to the data and resulted in Cu-Mo exchange coupling constants J = 11 cm and J = 109 cm for the MMCT and LIESST mechanisms induced states, respectively. Fractions of respective states after irradiations at different temperatures were also calculated, shedding light on the influence of irradiation temperature on the photomagnetic mechanism. The proposed model can provide the interpretative framework for testing and refinement of the mechanism of photomagnetic effect in other coordination networks with cyanido-bridged Cu-[Mo(CN)] linkages.

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Synthesis of Two-Dimensional Photomagnetic K₄{[Cu^II(ida)]₂[M^IV(CN)₈]}·4H₂O (M^IV = Mo, W) Materials

Stefańczyk

Ohkoshi

2020

Inorg. Chem.

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Self-assembly of two complex salts [Cu(ida)(H2O)2] n (ida2– = iminodiacetate) and K4[M(CN)8]·2H2O (M = Mo, W) resulted in the unique examples of 2-D layer K4{[Cu(ida)]2[M(CN)8]}·4H2O coordination polymers, where M = Mo (1) and W (2). These two assemblies are rare instances of d-block metal complexes with imino or amino acids and polycyanidometallates. Furthermore, both complexes in their ground states are paramagnetic materials with weak antiferromagnetic interactions at low temperature. Interestingly, photoirradiation of both systems at 10 K with a 407 nm light for 24 h results in the photomagnetic effect observed as a 30% and 3% increase of magnetization for 1 and 2, respectively, which relax to the initial ground state after heating above 200 K. To the best of our knowledge, this is the first report of the photomagnetic effect for a Cu(II)–W(IV) system.

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Light‐Induced Spin‐State Switching of the Mo^IV Centre in Trinuclear [Cu^II(diamine)₂]₂[Mo^IV(CN)₈] Molecules

Cited by 7 publications

References 31 publications

Spectroscopic Detection and Theoretical Description of Spin‐Crossover Effect in Co(II)‐terpyridine System

Spectroscopic Detection and Theoretical Description of Spin‐Crossover Effect in Co(II)‐terpyridine System

Irradiation Temperature Dependence of the Photomagnetic Mechanisms in a Cyanido-Bridged Cu^II₂Mo^IV Trinuclear Molecule

Synthesis of Two-Dimensional Photomagnetic K₄{[Cu^II(ida)]₂[M^IV(CN)₈]}·4H₂O (M^IV = Mo, W) Materials

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Light‐Induced Spin‐State Switching of the MoIV Centre in Trinuclear [CuII(diamine)2]2[MoIV(CN)8] Molecules

Cited by 7 publications

References 31 publications

Spectroscopic Detection and Theoretical Description of Spin‐Crossover Effect in Co(II)‐terpyridine System

Spectroscopic Detection and Theoretical Description of Spin‐Crossover Effect in Co(II)‐terpyridine System

Irradiation Temperature Dependence of the Photomagnetic Mechanisms in a Cyanido-Bridged CuII2MoIV Trinuclear Molecule

Synthesis of Two-Dimensional Photomagnetic K4{[CuII(ida)]2[MIV(CN)8]}·4H2O (MIV = Mo, W) Materials

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Product

Resources

About

Light‐Induced Spin‐State Switching of the Mo^IV Centre in Trinuclear [Cu^II(diamine)₂]₂[Mo^IV(CN)₈] Molecules

Irradiation Temperature Dependence of the Photomagnetic Mechanisms in a Cyanido-Bridged Cu^II₂Mo^IV Trinuclear Molecule

Synthesis of Two-Dimensional Photomagnetic K₄{[Cu^II(ida)]₂[M^IV(CN)₈]}·4H₂O (M^IV = Mo, W) Materials