Normal coordinate analyses of ruthenium–sulfur dioxide complexes

Lauter, M.; Breitinger, Dietrich K.; Breiter, Roman; Mink, J.; Bencze, Éva

doi:10.1016/s0022-2860(00)00795-x

Cited by 7 publications

(11 citation statements)

References 3 publications

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“…On the other hand, a Ru−S peak assignment could stand to reason as a Raman shift at 360 cm −1 has previously been classified as a Ru−S stretching mode for 1, using the H/D isotope shift to aid assignment, as well as calculations. 48 A normal coordinate analysis was performed on 1 in the same study which revealed that both Ru−S and Ru−Cl stretching modes dominate the potential energy distributions for this Raman shift, with respective proportions of 24.9 and 56.0%; that is, this Raman shift exhibits a mixed contribution of vibrational modes.…”

Section: Characterizing Thementioning

confidence: 93%

Systems Approach of Photoisomerization Metrology for Single-Crystal Optical Actuators: A Case Study of [Ru(SO₂)(NH₃)₄Cl]Cl

et al. 2020

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Chemicals that undergo photoisomerization in their single-crystal form may act as optical actuators or sensors. It is important to determine the molecular-scale characteristics of this photoisomerization as they govern the macroscopic nature of the optical phenomenon. In situ single-crystal X-ray diffraction has led the way in this field of characterization, with photoinduced crystal structures being realized via technical developments that have become known as "photocrystallography". Single-crystal optical spectroscopy methods are less well developed in this research area, even though they provide synergistic information that is crucial for optimizing photoconversion levels in single-crystal optical actuators and enabling their comprehensive photoisomerization analysis. This paper demonstrates the importance of characterizing photoisomerism in crystalline media using a systems approach to photoisomerization metrology. Therefore, single-crystal optical spectroscopy, single-crystal Raman spectroscopy, and photocrystallography are concerted. The case study on [Ru(SO 2 )(NH 3 ) 4 Cl]Cl (1) shows how this approach optimizes its photoconversion levels, using key parameters that are established by single-crystal optical absorption spectroscopy. These parameters furnish the design of single-crystal Raman spectroscopy and photocrystallography experiments which are needed for a comprehensive photoisomerization analysis of 1. Raman shifts identify photostructural changes in isolated bonds as a function of temperature. One such shift leads to the realization of a previously unidentified photoisomer in 1, which is then confirmed by photocrystallography that renders its 3-D light-induced crystal structure. Both optical-spectroscopy methods are concerted with imaging to evidence photochromic changes in single crystals that occur upon photoisomerization and upon their thermal decay, whose characteristics are realized via single-crystal Raman spectroscopy. Overall, an end-to-end operational pipeline is showcased for more optimally characterizing the light-induced optical properties and structures of single-crystal optical actuators.

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Section: Characterizing Thementioning

confidence: 93%

Systems Approach of Photoisomerization Metrology for Single-Crystal Optical Actuators: A Case Study of [Ru(SO₂)(NH₃)₄Cl]Cl

et al. 2020

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“…The intense band at 989 cm −1 has both SO 2 units in a symmetric stretch but in an antisymmetric mode, that is, as one expands the other contracts, while that at 1119 cm −1 has the converse, that is, each SO 2 in an antisymmetric stretching vibration but coupled symmetrically. The assigned vibrations occur in the expected ranges. , …”

Section: Infrared Spectramentioning

confidence: 93%

“…The assigned vibrations occur in the expected ranges. 88,89 The isomeric disulfenate structure Ru(bpy) 2 (SO • SO) as an alternative formulation of species 1 was excluded above, but to be sure, the infrared spectrum of this isomer was calculated. It is shown in Figure 9C.…”

Section: Infrared Spectramentioning

confidence: 99%

Synthesis and Characterization of Ruthenium bis-Bipyridine Mono- and Disulfinato Complexes

Begum¹,

Farah²,

Hunter³

et al. 2009

Inorg. Chem.

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Reaction of cis-Ru(bpy)(2)Cl(2) with 1,2-benzenedithiol afforded a monosulfhydryl-monosulfinate complex, [Ru(bpy)(2)(S.SO(2))] (1). Complex 1 readily undergoes oxidation when treated with 30% H(2)O(2) and also upon exposure to atmospheric O(2) (rapidly in bright light) to afford the disulfinate complex, [Ru(bpy)(2)(SO(2.)SO(2))] (2). Complexes 1 and 2 were studied using various analytical techniques including elemental analysis, UV-vis, mass spectroscopy, NMR, IR spectroscopy, cyclic voltammetry, X-ray crystallography (for 2). Density functional theory computation was employed with extended charge decomposition and natural population analyses. The agreement between the observed electronic spectrum and that predicted by time dependent DFT, and between the observed infrared spectrum and that predicted by DFT, is truly exceptional. These molecules are relevant to the very unusual active site in the metalloenzyme nitrile hydratase.

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“…An increase in the intensity of several weak peaks that are characteristic of Ru-N amine bending modes (480–490 cm –1 ) 53 and amine rocking modes (815 cm –1 ) 52 also becomes more apparent by ca. 230 K (see Figure 6 ), while vibrational modes that are associated with amine stretching modes are also present at 3200–3350 cm –1 (for details, see the Supporting Information ).…”

Section: Resultsmentioning

confidence: 98%

“…Thereby, three peaks are significant at 90 K: the largest peak at 340 cm –1 , which represents a Ru–OSO vibrational stretch; 44 the more modest peak at 540 cm –1 , which is indicative of an SO 2 deformation mode of the η 1 -OSO isomer; 44 , 53 and the weakest peak at 1130 cm –1 , which is reminiscent of an η 1 -SO 2 symmetric stretching mode. 43 , 44 , 53 …”

Section: Resultsmentioning

confidence: 99%

Structural Capture of η¹-OSO to η²-(OS)O Coordination Isomerism in a New Ruthenium-Based SO₂-Linkage Photoisomer That Exhibits Single-Crystal Optical Actuation

2022

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Recent discoveries of a range of single-crystal optical actuators are feeding a new form of materials chemistry, given their broad range of potential applications, from light-induced molecular motors to light sensors and optical-memory media. A series of ruthenium-based coordination complexes that exhibit sulfur dioxide linkage photoisomerization is of particular interest because they exhibit single-crystal optical actuation via either optical switching or nano-optomechanical transduction processes. We report the discovery of a new complex in this series of chemicals, [Ru(SO 2 )(NH 3 ) 4 (3-fluoropyridine)]tosylate 2 ( 1 ), which forms an η 1 -OSO photoisomer with 70% photoconversion upon the application of 505 nm light. The uncoordinated oxygen atom in this η 1 -OSO photoisomer impinges on one of the arene rings in a neighboring tosylate counter ion of 1 just enough that incipient nano-optomechanical transduction is observed. The structure and optical properties of this actuator are characterized via in situ light-induced single-crystal X-ray diffraction (photocrystallography), single-crystal optical absorption spectroscopy and microscopy, as well as single-crystal Raman spectroscopy. These materials-characterization methods were also used to track thermally induced reverse isomerization processes in 1 . One of these processes involves an η 1 -OSO to η 2 -(OS)O transition, which was found to proceed sufficiently slowly at 110 K that its structural mechanism could be determined via a time sequence of photocrystallography experiments. The resulting data allowed us to structurally capture the transition, which was shown to occur via a form of coordination isomerism. Our newfound knowledge about this structural mechanism will aid the molecular design of new [RuSO 2 ] complexes with functional applications.

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Normal coordinate analyses of ruthenium–sulfur dioxide complexes

Cited by 7 publications

References 3 publications

Systems Approach of Photoisomerization Metrology for Single-Crystal Optical Actuators: A Case Study of [Ru(SO₂)(NH₃)₄Cl]Cl

Systems Approach of Photoisomerization Metrology for Single-Crystal Optical Actuators: A Case Study of [Ru(SO₂)(NH₃)₄Cl]Cl

Synthesis and Characterization of Ruthenium bis-Bipyridine Mono- and Disulfinato Complexes

Structural Capture of η¹-OSO to η²-(OS)O Coordination Isomerism in a New Ruthenium-Based SO₂-Linkage Photoisomer That Exhibits Single-Crystal Optical Actuation

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Normal coordinate analyses of ruthenium–sulfur dioxide complexes

Cited by 7 publications

References 3 publications

Systems Approach of Photoisomerization Metrology for Single-Crystal Optical Actuators: A Case Study of [Ru(SO2)(NH3)4Cl]Cl

Systems Approach of Photoisomerization Metrology for Single-Crystal Optical Actuators: A Case Study of [Ru(SO2)(NH3)4Cl]Cl

Synthesis and Characterization of Ruthenium bis-Bipyridine Mono- and Disulfinato Complexes

Structural Capture of η1-OSO to η2-(OS)O Coordination Isomerism in a New Ruthenium-Based SO2-Linkage Photoisomer That Exhibits Single-Crystal Optical Actuation

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Systems Approach of Photoisomerization Metrology for Single-Crystal Optical Actuators: A Case Study of [Ru(SO₂)(NH₃)₄Cl]Cl

Systems Approach of Photoisomerization Metrology for Single-Crystal Optical Actuators: A Case Study of [Ru(SO₂)(NH₃)₄Cl]Cl

Structural Capture of η¹-OSO to η²-(OS)O Coordination Isomerism in a New Ruthenium-Based SO₂-Linkage Photoisomer That Exhibits Single-Crystal Optical Actuation