η2-SO2 Linkage Photoisomer of an Osmium Coordination Complex

Cole, Jacqueline M.; Velazquez-Garcia, Jose de J.; Gosztola, David J.; Wang, SuYin Grass; Chen, Yu -Sheng

doi:10.1021/acs.inorgchem.7b03032

Title: η²-SO₂ Linkage Photoisomer of an Osmium Coordination Complex

Journal Article · 20 February 2018 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.7b03032 · OSTI ID:1466363

^[1]; Velazquez-Garcia, Jose de J. ^[2];

^[3]; Wang, SuYin Grass ^[3]; Chen, Yu -Sheng ^[3]

Univ. of Cambridge, Cambridge (United Kingdom); STFC Rutherford Appleton Lab., Oxfordshire (United Kingdom); Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Cambridge, Cambridge (United Kingdom)
Argonne National Lab. (ANL), Argonne, IL (United States)

We report the discovery of an n²-SO₂ linkage photoisomer in the osmium pentaammine coordination complex, [Os(NH₃)₅(SO₂)][Os(NH₃)₅(SO₃)]Cl₄ (1). Its dark and light-induced crystal structures are determined via synchrotron X-ray crystallography, at 100K, where the photo-induced state is metastable in a single crystal that has been stimulated by 505 nm light for 2.5 hrs. The SO₂ photoisomer in the [Os(NH₃)₅(SO₂)]²⁺ cation contrasts starkly with the photo-inactivity of the SO₃ ligand in its companion [Os(NH₃)₅(SO₃)]²⁺ cation within the crystallographic asymmetric unit of this single crystal. Panchromatic optical absorption characteristics of this single crystal are revealed in both dark and light-induced states, using concerted absorption spectroscopy and optical microscopy. Its optical absorption halves across most of its visible spectrum, upon exposure to 505nm light. The SO₂ ligand seems to be responsible for this photo-induced bleaching effect, judging from a comparison of the dark and light-induced crystal structures of 1. The SO₂ linkage photo-isomerism is found to be thermally reversible and so this complex presents a rare example of an osmium-based solid-state optical switch. Such switching in an osmium-based complex is significant be-cause bottom-row transition metals stand to offer linkage photo-isomerism with the greatest photo-conversion levels and thermal stability. Furthermore, the demonstration of n²-SO₂ bonding in this complex also represents a fundamental contribution to osmium coordination chemistry

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1466363

Journal Information:: Inorganic Chemistry, Vol. 57, Issue 5; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 22 works

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References (17)

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Title: η2-SO2 Linkage Photoisomer of an Osmium Coordination Complex

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