In situ synthesis, crystallisation, and thin-film processing of single crystals of trans-[Ru(SO2)(NH3)4(H2O)][p-TolSO3]2 bearing SO2 linkage photo-isomers: towards optical device applications

Cole, Jacqueline M.; Yeung, K. Y. M.; Pace, Giuseppina; Sylvester, Sven O.; Mersch, Dirk; Friend, Richard H.

doi:10.1039/c5ce00685f

Cited by 10 publications

(8 citation statements)

References 22 publications

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“…Photocrystallography has an important and notable history in the characterization of metastable linkage isomers of transition metal complexes containing NO, SO 2 , and NO 2 – , but its beginnings arise from irradiation of cinnamic acid to effect [2+2] cycloadditions, which continues today. , Coppens led the way in these studies on sodium nitroprusside. , Separately, Cole has uncovered synergistic motions inside crystals of [Ru(NH 3 ) 4 (X)SO 2 ] n + (X is typically an anionic or neutral ligand trans to SO 2 ), where the S-bonded SO 2 yields both η 2 -SO 2 - and O-bonded isomers upon irradiation of single crystals. ,− The relatively close packing of each Ru cation appears to cause other nearby cations to rotate. In this way, photonic energy is transduced to mechanical energy inside the crystal, reminiscent of a rotor .…”

Section: Correlating Electronic Structural Changes With Atomic Struct...mentioning

confidence: 99%

A Future Perspective on Phototriggered Isomerizations of Transition Metal Sulfoxides and Related Complexes

et al. 2021

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Photochromic molecules are examples of light-activated bistable molecules. We highlight the design criteria for a class of ruthenium and osmium sulfoxide complexes that undergo phototriggered isomerization of the bound sulfoxide. The mode of action in these complexes is an excited-state isomerization of the sulfoxide from S-bonded to O-bonded. We discuss the basic mechanism for this transformation and highlight specific examples that demonstrate the effectiveness and efficiency of the isomerization. We subsequently discuss future research directions within the field of phototriggered sulfoxide isomerizations on transition metal polypyridine complexes. These efforts involve new synthetic directions, including the choice of metal as well as new ambidentate ligands for isomerization.

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Section: Correlating Electronic Structural Changes With Atomic Struct...mentioning

confidence: 99%

A Future Perspective on Phototriggered Isomerizations of Transition Metal Sulfoxides and Related Complexes

et al. 2021

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“…1 Photo-switching between linkage isomers can be achieved in both solution and the solid-state, with irradiation of the solid leading to the production of a metastable state (MS) isomer below some critical temperature. 2 In situ photocrystallographic studies have to-date revealed the structures of various MS linkage isomers, including nitrosyl, 3,4 nitrite, [5][6][7][8] sulfur dioxide, [9][10][11] and di-nitrogen 12 systems.…”

Section: Introductionmentioning

confidence: 99%

The impact of hydrogen bonding on 100% photo-switching in solid-state nitro–nitrito linkage isomers

Hatcher

Raithby

2017

CrystEngComm

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-NO 2 ) isomer, which are previously shown to limit the achievable level of nitro → nitrito photoconversion. Irradiation at 100 K induces a mixture of endo-ONO and exo-ONO isomers in 1 and 2, with overall incomplete photo-activation. In contrast, irradiation at higher temperatures leads to much higher conversion, with 100% excitation in 1 at 150 K. The results show that the detrimental effects of hydrogen bonding on the photo-reaction are overcome at higher temperature, adding a new dimension of control to the isomerisation process.

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“…This was achieved by the in situ reaction of trans -[Ru(NH 3 ) 4 (SO 2 )Cl]Cl and p -toluenesulfonic acid in the PVA matrix and an in situ precipitating crystallization. Transmission electron microscopy, diffraction, and UV–vis spectroscopy indicated that the photoactivated linkage isomerization was uncompromised by inclusion in polymer thin films . The size of the crystallites was optimized within the polymer, having dimensions between 1 and 10 μm.…”

Section: Photocrystallographic Studies On Nitrosyl and Sulfur Dioxide...mentioning

confidence: 99%

“…Because of the relationship that we have established between temperature and lifetime in these linkage isomers, they should be useful benchmark materials as time-resolved diffraction methodology continues to develop. The successful incorporation of some of the nitrosyl and sulfur dioxide linkage isomers into polymers and xerogels without the loss of their switching function , suggests that these systems may have optical device applications. Schaniel et al have shown that it is possible to write short-lived phase gratings with identically and orthogonally polarized waves using nanosecond laser pulses in crystals of iron nitrosyl complexes.…”

Section: Concluding Remarksmentioning

confidence: 99%

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Photocrystallographic Studies on Transition Metal Nitrito Metastable Linkage Isomers: Manipulating the Metastable State

et al. 2019

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The design of solid-state materials whose properties and functions can be manipulated in a controlled manner by the application of light is an important objective in modern materials chemistry. When the material changes property or function, it is helpful if a simple measurable response, such as a change in color, can be detected. Potential applications for such materials are wide ranging, from data storage to smart windows. With the growing emphasis on solid-state materials that have two or more accessible energy states and which exhibit bistability, attention has turned to transition metal complexes that contain ambidentate ligands that can switch between linkage isomeric forms when activated by light. Suitable ligands that show promise in this area include nitrosyls, nitro groups, and coordinated sulfur dioxide molecules, each of which can coordinate to a metal center in more than one bonding mode. A nitrosyl normally coordinates through its N atom (η 1 -NO) but when photoactivated can undergo isomerism and coordinate through its O atom (η 1 -ON). At a molecular level, converting between these two configurations can act as an "on/off" switch. The analysis of such materials has been aided by the development of photocrystallographic techniques, which allow the full three-dimensional structure of a single crystal of a complex, under photoactivation, to be determined, when it is in either a metastable or short-lived excited state. The technique effectively brings the dimension of "time" to the crystallographic experiment and brings us closer to being able to watch solidstate processes occur in real time. In this Account, we highlight the advances made in photocrystallography for studying solid-state, photoactivated linkage isomerism and describe the factors that favor the switching process and which allow complete switching between isomers. We demonstrate that control of temperature is key to achieving either a metastable state or an excited state with a specific lifetime. We draw our conclusions from published work on the formation of photoactivated metastable states for nitrosyl and sulfur dioxide complexes and from our own work on photoactivated switching between nitro and nitrito groups. We show that efficient switching between isomers is dependent on the wavelength of light used, on the temperature at which the experiment is carried out, on the flexibility of the crystal lattice, and on both the electronic and steric environment of the ambidentate ligand undergoing isomerism. We have designed and prepared a number of nitro/nitrito isomeric metal complexes that undergo reversible 100% conversion between the two forms at temperatures close to room temperature. Through our fine control over the generation of the metastable states, it should be possible to effectively "dial up" a suitable temperature to give a metastable or an excited state with a desired lifetime.

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In situ synthesis, crystallisation, and thin-film processing of single crystals of trans-[Ru(SO₂)(NH₃)₄(H₂O)][p-TolSO₃]₂ bearing SO₂ linkage photo-isomers: towards optical device applications

Cited by 10 publications

References 22 publications

A Future Perspective on Phototriggered Isomerizations of Transition Metal Sulfoxides and Related Complexes

A Future Perspective on Phototriggered Isomerizations of Transition Metal Sulfoxides and Related Complexes

The impact of hydrogen bonding on 100% photo-switching in solid-state nitro–nitrito linkage isomers

Photocrystallographic Studies on Transition Metal Nitrito Metastable Linkage Isomers: Manipulating the Metastable State

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