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.

Abstract

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 (<b>1</b>), 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 <b>1</b> just enough that incipient nano-optomechanical transduction is observed. The structure and optical properties of this actuator are characterized via <i>in situ</i> 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 <b>1</b>. 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.