Ultrafast Intermolecular Interaction Dynamics between NIR-Absorbing Unsymmetrical Squaraines and PCBM: Effects of Halogen Substitution.

Among near-infrared (NIR) dyes, squaraine derivatives are applied as efficient sensitizers in optoelectronic and biomedical devices due to their simple synthesis, intense absorption, and emission and exceptional photochemical stability. The fundamental understanding of the structure-property relationships of sensitizers provides the insight to increase the efficiency of such devices. Here, unsymmetrical squaraine derivatives (ABSQs) with donor-acceptor-donor (D-A-D') architectures having N,N-dimethyl amino anthracene and benzothiazole (ABSQ-H) halogenated with fluoride (ABSQ-F), chloride (ABSQ-Cl), and bromide (ABSQ-Br) were synthesized to understand the effect of halogen on the photophysical properties and intermolecular interaction dynamics with phenyl-C61-butyric acid methyl ester (PCBM), which is used widely as an electron acceptor in bulk heterojunction-based devices. Interestingly, ABSQ-H exhibited intense absorption (ε ∼ 6.72 × 104 M-1 cm-1) spectra centered at ∼660 nm. Upon halogen substitution, a bathochromic shift in the absorption spectra with an increase of molar absorptivity was observed (ε ∼ 8.59 × 104 M-1 cm-1), which is beneficial for NIR light harvesting. The femtosecond transient absorption spectra of ABSQs revealed that the polarity of the solvent controlled the excited-state relaxation dynamics. Upon addition of PCBM, the fluorescence intensity and dynamics of halogenated ABSQs were quenched, and the formation of a squaraine radical cation was observed, reflecting the occurrence of intermolecular charge-transfer dynamics between ABSQs and PCBM. Thus, the observation of a bathochromic shift with intense absorption and an efficient intermolecular interaction with PCBM upon halogenation of ABSQs provide a design strategy for the development of unsymmetrical squaraine derivatives for bulk heterojunction-based optoelectronic devices.