Structural Capture of η 1 -OSO to η 2 -(OS)O Coordination Isomerism in a New Ruthenium-Based SO 2 -Linkage Photoisomer That Exhibits Single-Crystal Optical Actuation
[1];
[2];
- Cavendish Laboratory, Department of Physics, University of Cambridge, J. J. Thomson Avenue, Cambridge CB3 0HE, U.K., ISIS Neutron and Muon Source, STFC Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Didcot OX11 0QX, U.K., Center for Nanoscale Materials, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States
- Center for Nanoscale Materials, Argonne National Laboratory, 9700 S Cass Avenue, Lemont, Illinois 60439, United States
- Cavendish Laboratory, Department of Physics, University of Cambridge, J. J. Thomson Avenue, Cambridge CB3 0HE, U.K.
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(SO2)(NH3)4(3-fluoropyridine)]tosylate2 (1), which forms an η1-OSO photoisomer with 70% photoconversion upon the application of 505 nm light. The uncoordinated oxygen atom in this η1-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 η1-OSO to η2-(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 [RuSO2] complexes with functional applications.
- Research Organization:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; Consejo Nacional de Ciencia y Tecnologia (CONACYT); Science and Technologies Facilities Council (STFC-UK)
- Grant/Contract Number:
- AC02-06CH11357
- OSTI ID:
- 1867755
- Alternate ID(s):
- OSTI ID: 1869046
- Journal Information:
- Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Vol. 126 Journal Issue: 13; ISSN 1932-7447
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
Similar Records
Rapid build up of nanooptomechanical transduction in single crystals of a ruthenium-based SO 2 linkage photoisomer
η2-SO2 Linkage Photoisomer of an Osmium Coordination Complex