Photoluminescence and mechanoluminescence of solid-state zirconocene dichlorides

Spectral-luminescence properties of 23 samples of zirconium complexes were studied. Mechanoluminescence spectra of 10 complexes were obtained. The solid-state component of the mechanoluminescence spectrum, that is the luminescence of the crystal itself, coincided with the photoluminescence spectra of these complexes, which indicated identical emission from the same excited states in mechanoluminescence and photoluminescence, despite the different ways of excitation. The luminescence maximum was red shifted as substituents appeared in the ligand, in particular in the presence of a bridging group connecting π-ligands (ansa-complexes) and also for a substituted bis-indenyl complex rac-Me₂ Si(2-Me-4-Ph-5-OMe-6-Bu^t -Ind)₂ ZrCl₂ ). It was found that mechanical destruction of the rac-isomer of complex Mе₂ С(2-Me-4-Bu^t -C₅ H₂ )₂ ZrCl₂ , unlike that of the meso-isomer, was accompanied by a more than a 10-fold increase in intensity and by a shift in the mechanoluminescence spectrum to longer wavelengths.