Using End Groups to Tune the Linear and Nonlinear Optical Properties of Bis(dioxaborine)‐Terminated Polymethine Dyes

Six anionic pentamethine dyes with different 2,2‐difluoro‐4‐aryl‐1,3,2(2 H)‐dioxaborin‐6‐yl termini were synthesized and isolated as tetra‐n‐octylammonium salts with a variety of aryl groups appended to increase conjugation beyond the dioxaborine termini. The increased conjugation was expected to decrease the energy of the lowest‐lying excited state, and increase the transition dipole moment linking this state to the ground state, which would be anticipated to result in an increase in the real part of the third‐order polarizability, Re(γ). UV/Vis‐NIR absorption spectroscopy indicates that the absorption maxima in DMSO vary from 691 to 761 nm, with the longest wavelength transitions observed for a derivative where the aryl group is 4‐nitrophenyl. Closed‐aperture Z‐scan measurements at 1.3 μm in DMSO indicate that Re(γ) varies from ?2.9×10^?33 to ?5.4×10^?33 esu in these systems. The largest magnitude of Re(γ) was observed for a dye with E‐4‐styrylphenyl aryl groups. This result can be rationalized using a two‐state expression which relates Re(γ) to the energy and transition dipole moment of the transition from the ground state to the lowest‐lying excited state. A nonamethine analogue of this compound was also synthesized and exhibits a slightly larger Re(γ) with respect to a previously reported bis(dioxaborine)‐terminated nonamethine. The extension of conjugation beyond the dioxaborine termini seems to result in an overall increase in Re(γ). However, the effects are smaller than those found by increasing conjugation in the polymethine bridge due to reduced participation of terminal groups in the HOMO.