620966-84-9Relevant academic research and scientific papers
Platinum complexes with the SC6F4H-4 ligand - Synthesis, structures and spectroscopy
Lingen, Verena,Lüning, Anna,Strau?, Christian,Pantenburg, Ingo,Deacon, Glen B.,Meyer, Gerd,Klein, Axel
, p. 152 - 162 (2014)
The reaction of HSC6F4H-4 and base with suitable platinum(II) chlorido precursor complexes leads to mononuclear complexes containing diimine ligands [(N^N)Pt(SC6F4H-4) 2], or [(N^N)Pt(Me)(SC6F4H-4)] (N^N = 2,2′-bipyridine (bpy), dipyrido[3,2-a:2′,3′-c]phenazine (dppz) or 11-trifluoromethyl-dipyrido[3,2-a:2′,3′-c]phenazine (CF 3dppz)), cycloocta-1,5-diene (COD) complexes [(COD)Pt(SC 6F4H-4)2] or [(COD)Pt(R)(SC6F 4H-4)] (R = Me, Bn (benzyl) or C6F5), or phosphine complexes cis-[(PPh3)2Pt(SC6F 4H-4)2], [(dppe)Pt(SC6F4H-4) 2] (dppe = 1,2-bis(diphenylphosphino)ethane) and [(dppb)Pt(C 6F5)(SC6F4H-4)] (dppb = 1,4-bis(diphenylphosphino)butane). Reaction of cis-[(DMSO)2PtCl 2] lead to the labile cis- and trans-[(DMSO)2Pt(SC 6F4H-4)2] which rapidly lose DMSO to yield polymeric [Pt(SC6F4H-4)2]m. Reaction of HSC6F4H-4 and KOtBu with K2PtCl4 gave K2[Pt(SC6F4H-4)4]. The new compounds were analysed and characterised by single crystal XRD, 1H, 19F and 195Pt NMR and IR spectroscopy. Both single crystal XRD (in the solid) and NMR (in solution) reveal that the ligand strength of the thiolate ligand -SC6F4H-4 strongly depends on the further ligands in the complexes. The crystal structures exhibit various inter- and intra molecular π stacking interactions of the SC 6F4H-4 coligands. The absorption spectroscopy and electrochemistry of the diimine complexes [(N^N)Pt(SC6F 4H-4)2] (N^N = bpy, dppz and CF3dppz) have been investigated and reveal that the Pt complexes are superior to the recently reported Pd derivatives in view of their application in photoactive materials.
PtII Diimine Chromophores with Perfluorinated Thiolate Ligands: Nature and Dynamics of the Charge-Transfer-to-Diimine Lowest Excited State
Weinstein, Julia A.,Blake, Alexander J.,Davies, E. Stephen,Davis, Adrienne L.,George, Michael W.,Grills, David C.,Lileev, Igor V.,Maksimov, Alexander M.,Matousek, Pavel,Mel'Nikov, Mikhail Ya.,Parker, Anthony W.,Platonov, Vyacheslav E.,Towrie, Michael,Wilson, Claire,Zheligovskaya, Natalia N.
, p. 7077 - 7085 (2008/10/08)
The synthesis of new PtII diimine complexes bearing perfluorinated thiolate ligands, PtII(NN)(4-X-C6F 4-S)2, where NN = 2,2′-bipyridine or 1,10-phenanthroline and X = F or CN, is reported, together with an investigation of the nature and dynamics of their lowest excited states. A combined UV-vis, (spectro)electrochemical, resonance Raman, and time-resolved infrared (TRIR) study has suggested that the HOMO is mainly composed of thiolate(φ)/S(p)/Pt(d) orbitals and that the LUMO is largely localized on the φ* (diimine) orbital, thus revealing the {charge-transfer-to-diimine} nature of the lowest excited state. An enhancement of the thiolate ring vibrations, C-F vibrations, and the vibration of the CN-substituent on the thiolate moiety was observed in the resonance Raman spectra, whereas no such enhancement was seen for the nonfluorinated analogues. Thus, the introduction of fluorine substituents on the thiolate moiety probably leads to a more pronounced contribution of the intrathiolate modes to the HOMO compared to the analogous complexes with nonfluorinated thiolates. Furthermore, the introduction of the p-CN group into the thiolate moiety has allowed the dynamics of the lowest excited state of Pt(bpy)(4-CN-C6F 4-S)2 to be monitored by picosecond TRIR spectroscopy. The dynamics of the lowest {charge-transfer-to-diimine} excited state are governed by ca. 2-ps vibrational cooling and 35-ps back electron transfer.
