Ultrafast dynamic processes and nonlinear optical properties of Platinum(II) fluoren-acetylides

Abstract

Two N-(4-ethylnylphenyl)-9H-fluoren-9-imine (EFT)arylacetylides (1, 2) and three EFT based Platinum(II) arylacetylides (3, 4, 5) were synthesized. The ultrafast dynamic processes after excitation and the nonlinear optical properties for picosecond lasers were investigatedusing femtosecond transient absorption and Z-scan techniques. The influence of conjugated length and Pt(II) content percentage on the properties ofthese moleculeswas discussed in detail. For compounds 1 and 2, two dynamic decay processes are observed after excitationby the pump laser beams. The first process is an ultrafast singlet (first singlet excited state, S1S*) → singlet state (ground state, GS), followed by a geometric twisting charge transfer state (CTS*) of the fluoren units relative to the central arylacetylide plane. For 3, 4, and 5, three dynamic decay processes are observed. The first process is the same as those of 1 and 2. However,the geometric twisting of 3, 4, and 5 is easier than 1 and 2 due to the presence of Pt atoms in the molecular skeleton of 3, 4, and 5, which makes a fast S1S* → geometric twisting state (TS*) occurred before the charge transfer occurring, and then a subsequent geometric twisting state (TS*) to geometric twisting charge transfer state (CTS*) occurs. The nonlinear optical properties of these compounds, studied using the open aperture Z-scan technique (λ = 532 nm, pulse width 23 ps), show that the values of the title compounds are around tens of cm/GW, which are comparable to newly reported porphyrin-based MOF materials and much better than Ru(II) terpyridine complexes..The mechanism of the nonlinear optical properties is attributed to the excited state absorption based on S1S*, TS*, and CTS* states, according to the femtosecond transient absorption and Z-scan results. The increase of Pt content percentage does not benefit the nonlinear absorption of Pt-containing compounds for the picosecond pulse laser. This is because the increase of the intersystem crossing rate weakly contributes to the nonlinear optical properties.