Pt(II) bipyridyl complexes bearing substituted fluorenyl motif on the bipyridyl and acetylide ligands: Synthesis, photophysics, and reverse saturable absorption

A series of Pt(II) diimine complexes bearing benzothiazolylfluorenyl (BTZ-F₈), diphenylaminofluorenyl (NPh₂-F₈), or naphthalimidylfluorenyl (NI-F₈) motifs on the bipyridyl or acetylide ligands (Pt-4-Pt-8), (i.e., {4,4′-bis[7-R1-F₈-(≡)_n-]bpy}Pt(7-R₂-F₈- ≡ -)₂, where F₈ = 9,9′-di(2-ethylhexyl)fluorene, bpy = 2,2′-bipyridine, Pt-4: R₁ = R₂ = BTZ, n = 0; Pt-5: R₁ = BTZ, R₂ = NI, n = 0; Pt-6: R₁ = R₂ = BTZ, n = 1; Pt-7: R₁ = BTZ, R₂ = NPh₂, n = 1; Pt-8: R₁ = NPh₂, R₂ = BTZ, n = 1) were synthesized. Their ground-state and excited-state properties and reverse saturable absorption performances were systematically investigated. The influence of these motifs on the photophysics of the complexes was investigated by spectroscopic methods and simulated by time-dependent density functional theory (TDDFT). The intense absorption bands below 410 nm for these complexes is assigned to predominantly ¹π, π∗ transitions localized on either the bipyridine or the acetylide ligands; while the broad low-energy absorption bands between 420 and 575 nm are attributed to essentially ¹MLCT (metal-to-ligand charge transfer)/¹LLCT (ligand-to-ligand charge transfer) transitions, likely mixed with some ¹ILCT (intraligand charge transfer) transition for Pt-4-Pt-7, and predominantly ¹ILCT transition admixing with minor ¹MLCT/¹LLCT characters for Pt-8. The different substituents on the acetylide and bipyridyl ligands, and the degrees of π-conjugation in the bipyridyl ligand influence both the ¹π,π∗ and charge transfer transitions pronouncedly. All complexes are emissive at room temperature. Upon excitation at their respective absorption band maxima, Pt-4, Pt-6, and Pt-8 exhibit acetylide ligand localized ¹π,π∗ fluorescence and ³MLCT/³LLCT phosphorescence in CH₂Cl₂, while Pt-5 manifests ¹ILCT fluorescence and ³ILCT phosphorescence. However, only ¹LLCT fluorescence was observed for Pt-7 at room temperature. The nanosecond transient absorption study was carried out for Pt-4-Pt-8 in CH₃CN. Except for Pt-7 that contains NPh₂ at the acetylide ligands, Pt-4-Pt-6 and Pt-8 all exhibit weak to moderate excited-state absorption in the visible spectral region. Reverse saturable absorption (RSA) of these complexes was demonstrated at 532 nm using 4.1 ns laser pulses in a 2 mm cuvette. The strength of RSA follows this trend: Pt-4 > Pt-5 > Pt-7 > Pt-6 > Pt-8. Incorporation of electron-donating substituent NPh₂ on the bipyridyl ligand significantly decreases the RSA, while shorter π-conjugation in the bipyridyl ligand increases the RSA. Therefore, the substituent at either the acetylide ligands or the bipyridyl ligand could affect the singlet and triplet excited-state characteristics significantly, which strongly influences the RSA efficiency.