We report the microwave-assisted synthesis of two symmetrical tetrathiafulvalene (TTF) derivatives via trialkyl phosphite-promoted coupling of a DMIT precursor. The microwave irradiation led to an increase in the reaction yield and significantly reduced the reaction time, affording the 2,3,6,7-tetrakis(2'-methy lacetatethio) tetrathiafulvalene (4) in 74% isolated yield. Hydrolysis of 4 yielded the tetraacid 5 in excellent yield. The nonlinear optical properties of both TTF compounds at 532 nm were studied by using the Z-scan technique in the picosecond regime exhibiting large third-order refractive index and saturated nonlinear absorption with promising applications in optical limiting devices. (C) 2018 Elsevier B.V. All rights reserved.