Abstract
Molecular platinum fluorides PtF(n) , n=1-6, are prepared by two different routes, photo-initiated fluorine elimination from PtF(6) embedded in solid noble-gas matrices, and the reaction of elemental fluorine with laser-ablated platinum atoms. IR spectra of the reaction products isolated in rare-gas matrices under cryogenic conditions provide, for the first time, experimental vibrational frequencies of molecular PtF(3) , PtF(4) and PtF(5) . Photolysis of PtF(6) enabled a highly efficient and almost quantitative formation of molecular PtF(4) , whereas both PtF(5) and PtF(3) were formed simultaneously by subsequent UV irradiation of PtF(4) . The vibrational spectra of these molecular platinum fluorides were assigned with the help of one- and two-component quasirelativistic DFT computation to account for scalar relativistic and spin-orbit coupling effects. Competing Jahn-Teller and spin-orbit coupling effects result in a magnetic bistability of PtF(4) , for which a spin-triplet ((3) B(2g) , D(2h) ) coexists with an electronic singlet state ((1) A(1g) , D(4h) ) in solid neon matrices.