In this work UVA and blue light have been used to study photo-isomerisation about the CvC double bond in complexes of the type [PtCl(-CHvCHAr)(tmeda)] [Ar = C 6 H 5 , (E)-2a; 4-CH 3 O-C 6 H 4 , (E)-2b; 3-NO 2 -C 6 H 4 , (E)-2c; and 3-CH 3 O-C 6 H 4 , (E)-2d]. The progress of the reaction has been monitored by NMR spectroscopy following irradiation of the NMR sample. The NMR data have been complemented with X-ray diffractometric analysis of compounds (E)-2a-c and (Z)-2a. The kinetic data clearly

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... indicate that a monomolecular mechanism is operating with the energy of the irradiating light influencing the rate of isomerisation but not the equilibrium composition, which is only slightly in favour of the Z isomer. DFT and TD-DFT theoretical investigations have been carried out to elucidate the nature of the main electronic transitions in the UV-Vis region and the mechanism of the photo-isomerisation reaction appears to proceed through a CvC bond twist process similar to that involved in purely organic molecules such as stilbene. In the Z isomer, one ortho proton of the phenyl group can come close to platinum (Pt⋯H ortho distance of 2.632 Å in (Z)-2a). In the case of 2c, the difference in chemical shift between the two ortho protons varies from 3.30 ppm in the Z isomer, where interaction with Pt is possible, to 0.60 ppm in the E isomer, where such interaction cannot take place. The analysis of the DFT orbitals indicates that the most shifted H ortho is that with a greater positive charge, pointing to an H-bond type of interaction. † Electronic supplementary information (ESI) available: Pdf file: Fig. S1-S8 and Tables S1-S5. CCDC 904374 [(E)-2a], 904375 [(Z)-2a], 904377 [(E)-2b] and 904378 [(E)-2c]. For ESI and crystallographic data in CIF or other electronic format see