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Title: η 2-SO 2 Linkage Photoisomer of an Osmium Coordination Complex

Abstract

We report the discovery of an n 2-SO 2 linkage photoisomer in the osmium pentaammine coordination complex, [Os(NH 3) 5(SO 2)][Os(NH 3) 5(SO 3)]Cl 4 (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 SO 2 photoisomer in the [Os(NH 3) 5(SO 2)] 2+ cation contrasts starkly with the photo-inactivity of the SO 3 ligand in its companion [Os(NH 3) 5(SO 3)] 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 SO 2 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 SO 2 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-rowmore » transition metals stand to offer linkage photo-isomerism with the greatest photo-conversion levels and thermal stability. Furthermore, the demonstration of n 2-SO 2 bonding in this complex also represents a fundamental contribution to osmium coordination chemistry« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [3];  [3]
  1. Univ. of Cambridge, Cambridge (United Kingdom); STFC Rutherford Appleton Lab., Oxfordshire (United Kingdom); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Univ. of Cambridge, Cambridge (United Kingdom)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1466363
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 5; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Cole, Jacqueline M., Velazquez-Garcia, Jose de J., Gosztola, David J., Wang, SuYin Grass, and Chen, Yu -Sheng. η2-SO2 Linkage Photoisomer of an Osmium Coordination Complex. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.7b03032.
Cole, Jacqueline M., Velazquez-Garcia, Jose de J., Gosztola, David J., Wang, SuYin Grass, & Chen, Yu -Sheng. η2-SO2 Linkage Photoisomer of an Osmium Coordination Complex. United States. doi:10.1021/acs.inorgchem.7b03032.
Cole, Jacqueline M., Velazquez-Garcia, Jose de J., Gosztola, David J., Wang, SuYin Grass, and Chen, Yu -Sheng. Tue . "η2-SO2 Linkage Photoisomer of an Osmium Coordination Complex". United States. doi:10.1021/acs.inorgchem.7b03032. https://www.osti.gov/servlets/purl/1466363.
@article{osti_1466363,
title = {η2-SO2 Linkage Photoisomer of an Osmium Coordination Complex},
author = {Cole, Jacqueline M. and Velazquez-Garcia, Jose de J. and Gosztola, David J. and Wang, SuYin Grass and Chen, Yu -Sheng},
abstractNote = {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},
doi = {10.1021/acs.inorgchem.7b03032},
journal = {Inorganic Chemistry},
number = 5,
volume = 57,
place = {United States},
year = {2018},
month = {2}
}

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Figures / Tables:

Figure 1 Figure 1: (a) Crystallographic asymmetric unit of 1 in its dark state (η1-SO2 isomer) at 100 K; (b) η2-SO2 photo-isomer in the lightinduced state of 1 (unshaded bonds), superimposed upon a dark state η1-SO2 configuration of 1 (shaded bonds). 9.3(3)% of the SO2 ligands in the light-induced crystal structure ofmore » 1 have been photo-converted into their η2-SO2 photo-isomer by irradiating a singlecrystal of 1 with 505 nm light for 2.5 hrs at 100 K. All atomic displacement parameters are shown at the 50% probability level.« less

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Works referencing / citing this record:

CCDC 1590580: Experimental Crystal Structure Determination: RESWUK : penta-ammine-(hydrogen sulfite)-osmium(iii) penta-ammine-(sulfur dioxide)-osmium(ii) tetrachloride
dataset, December 2017

  • Cole, Jacqueline M.; Velazquez-Garcia, Jose De J.; Gosztola, David J.
  • Cambridge Structural Database (CSD)
  • DOI: 10.5517/ccdc.csd.cc1qd419

CCDC 1821127: Experimental Crystal Structure Determination: RESYEW : penta-ammine-(hydrogen sulfite)-osmium(iii) bis(trifluoromethanesulfonate) monohydrate
dataset, January 2018

  • Cole, Jacqueline M.; Velazquez-Garcia, Jose De J.; Gosztola, David J.
  • Cambridge Structural Database (CSD)
  • DOI: 10.5517/ccdc.csd.cc1z4116

    Figures / Tables found in this record:

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.