Nitro–Nitrito Photoisomerization of Platinum(II) Complexes with Pt(NO2)42– and (FSO2)2N– Anions: Correlation between Isomerization Ratio and Reaction Cavity

Nakamura, Ibuki; Funasako, Yusuke; Mochida, Tomoyuki

doi:10.1021/acs.cgd.0c01294

Cited by 11 publications

(33 citation statements)

References 33 publications

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“…As reported in our previous study, 21 the nitro-nitrito photoisomerization reaction is governed by the reaction cavity surrounding the NO2 ligand. The reaction cavity also accounts for the observed difference in the photoreactions of the polymorphs of 1-PF6.…”

Section: Correlation Between Reaction Cavity Volume and Conversionsupporting

confidence: 59%

“…The conversion of cations A and B after 13 h of photoirradiation was 81% and 83%, respectively, which are within experimental error. The time course of the photoisomerization was almost the same as that of 1-FSA and 1-Pt(NO2)4, 21 reaching almost constant after 4 h. After photoirradiation, anion B exhibited a two-fold rotational disorder (0.72:0.28), whereas anion A remained ordered. This cation-anion distance is longer for anion B (Pt-PPF6(B) = 6.0 Å) than for anion A (Pt-PPF6(A) = 4.9 Å), which may cause less efficient electrostatic interactions, allowing disorder.…”

Section: Resultsmentioning

confidence: 71%

“…In the DTA trace of each salt, a large exothermic peak was observed around the decomposition temperatures, which is ascribed to the decomposition of the NO 2 ligand. α- 1-PF 6 exhibited a two-step weight loss similar to 1-FSA ; the first (∼10 wt %, 510–530 K) and the second step (∼40 wt %, 530–560 K) correspond to the losses of NO 2 (calculated value: 8 wt %) and chelate ligand (37 wt %), respectively. In contrast, 1-Tf 2 N exhibited a gradual weight loss.…”

Section: Resultsmentioning

confidence: 92%

“…The thermodynamic data are summarized in Table 1 along with those of 1-Pt(NO2)4 and 1-FSA reported previously. 21 The melting points of the crystals of -1-PF6 and 1-Tf2N were 462.5 and 363.5 K, respectively. No phase transitions were observed down to 150 K in either salt.…”

Section: Resultsmentioning

confidence: 95%

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Nitro–Nitrito Photoisomerization of Cationic Platinum(II) Complexes in the Solid State: Reactivity in Polymorphic Crystals and Glassy State

Nakamura

Sumitani

Mochida

2021

Crystal Growth & Design

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Nitro-nitrito isomerization is a well-known photoreaction exhibited by metal complexes in the solid state. We previously reported that the isomerization ratio in the salts of a cationic platinum(II) nitrito complex [Pt(L)(NO2)] + (L = N 1 -(2-(dimethylamino)ethyl)-N 2 ,N 2 -dimethyl-N 1pentyl-1,2-ethanediamine) is correlated to the reaction cavity surrounding the nitrito ligand. In this study, to further elucidate the effect of the packing structure on the reaction, we investigated the photoisomerization of the same cation in different packing environments. The salt of the cationic complex with the PF6 anion gave three polymorphs (-, -, and -forms) and a pseudopolymorph (form, acetonitrile solvate), of which the -form is formed from the -form upon desorption of acetonitrile. These polymorphs exhibited 36-100% conversions at 180 K depending on the reaction cavity. In addition, the -form exhibited a space group change upon photoirradiation. The salt with the (CF3SO2)2N − anion was an ionic liquid, taking both the crystalline and glassy states at low temperature.The crystalline state exhibited approximately 30% conversion at 100 K, whereas photoisomerization was not observed in its glassy state as investigated by IR spectroscopy. In these salts, less densely packed crystals deteriorated upon photoirradiation.Molecular structures, IR spectra, bond lengths and angles, and crystallographic parameters (PDF).

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Section: Correlation Between Reaction Cavity Volume and Conversionsupporting

confidence: 59%

Section: Resultsmentioning

confidence: 71%

Section: Resultsmentioning

confidence: 92%

Section: Resultsmentioning

confidence: 95%

See 2 more Smart Citations

Nitro–Nitrito Photoisomerization of Cationic Platinum(II) Complexes in the Solid State: Reactivity in Polymorphic Crystals and Glassy State

Nakamura

Sumitani

Mochida

2021

Crystal Growth & Design

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“…This allows examination of relatively shorterlived species, which would otherwise relax back to the ground state. Since these two methods do not require any specific and advanced experimental setups, they have been used extensively to study structural dynamics of a variety of systems, with particular emphasis on photo-switchable materials undergoing for example photoisomerization or reversible photolysis [28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46].…”

Section: Experimental Approachesmentioning

confidence: 99%

Advances in Diffraction Studies of Light-Induced Transient Species in Molecular Crystals and Selected Complementary Techniques

et al. 2021

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The review provides a summary of the current methods of tracing photoexcitation processes and structural dynamics in the solid state, putting major emphasis on the X-ray diffraction techniques (time-resolved Laue diffraction on synchrotron sources and time-resolved serial femtosecond crystallography on X-ray free-electron lasers). The recent developments and nowadays experimental possibilities in the field are discussed along with the data processing and analysis approaches, and illustrated with some striking literature examples of the respective successful studies. Selected complementary methods, such as ultrafast electron diffraction or time-resolved X-ray absorption spectroscopy, are briefly presented.

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Interrelations between Linkage Isomers of an Efficient Square‐planar Nickel(II) Nitrite Photoswitch in the Solid State

Potempa,

Deresz,

Jankowska

et al. 2023

Chemistry A European J

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An efficient nitrite nickel(II) photoswitch, with the 1‐phenyl‐2‐hydroxyimino‐3‐[(2’‐dimethylamino)ethyl]imino‐1‐propanone moiety used as the ancillary ligand, is reported. In the ground‐state (‘dark’) crystal structure, the studied compound exists predominantly as the nitro‐(η1‐N(O)2) isomer, however, traces of the exo‐ and endo‐nitrito‐(η1‐ONO) forms are detected both at 100 K (4−5% each) and under ambient conditions (~9% each). When excited with the 405−530 nm LED light, the nitro‐to‐nitrito isomerization takes place. The total conversion exceeds 90%. The exo‐nitrito linkage isomer constitutes the dominant photo‐generated form, whereas the relative population of both nitrito species depends on temperature. The reaction is fully reversible and reproducible. The photo‐products are stable up to 200 K. The system constitutes a good model case for the reaction mechanism studies. Thus, experimental and theoretical investigations on the photo‐isomerism were conducted and are presented in detail. Eventually, the nitro → exo‐nitrito → endo‐nitrito reaction pathway is proposed.

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Nitro–Nitrito Photoisomerization of Platinum(II) Complexes with Pt(NO₂)₄^2– and (FSO₂)₂N^– Anions: Correlation between Isomerization Ratio and Reaction Cavity

Cited by 11 publications

References 33 publications

Nitro–Nitrito Photoisomerization of Cationic Platinum(II) Complexes in the Solid State: Reactivity in Polymorphic Crystals and Glassy State

Nitro–Nitrito Photoisomerization of Cationic Platinum(II) Complexes in the Solid State: Reactivity in Polymorphic Crystals and Glassy State

Advances in Diffraction Studies of Light-Induced Transient Species in Molecular Crystals and Selected Complementary Techniques

Interrelations between Linkage Isomers of an Efficient Square‐planar Nickel(II) Nitrite Photoswitch in the Solid State

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