Investigating the Photochemistry of Spiropyran Metal Complexes with Online LED-NMR

As one of the best studied photoswitches, spiropyrans (SPs) have attracted significant interest in the scientific community. Among the many stimuli to alter the isomerization into the merocyanine (MC) isomer, such as temperature, pH, solvent polarity, redox potential, or mechanical force, the ability of the MC form to act as a ligand site for metal complexation has recently raised new attention. We herein synthesize hitherto undescribed coordination compounds of 8-methoxy-1',3',3'-trimethyl-6-nitrospiro-[chromene-2,2'-indoline] with s-block ([Ca(MC) 4 ](ClO 4 ) 2 ), d-block ([Zn(MC) 2 (MeCN) 2 ](ClO 4 ) 2 , [Ni(MC) 2 (MeCN) 2 ](ClO 4 ) 2 ), as well as f-block ([La(NO 3 ) 3 (MC) 2 ]) metals. All complexes are structurally described by X-ray crystallography and systematically investigated in solution via Job's method of continuous variations (Job plots), as well as online NMR spectroscopic kinetic experiments with in situ irradiation of the analyte solution inside the NMR spectrometer (LED-NMR). We can unambiguously identify the photoresponsive nature of the complexes in solution, which is a crucial step toward the application of these promising molecules in material science.