A series of dibutyltin complexes, (Bu₂Sn)₂L, [(Bu₂Sn)₂L]₃ and H₂LSnBu₂, were synthesized by microwave-assisted methanolic solvothermal method, where H₄L is [2-(OH)-R-ArCH=NNH]₂CX, and X = O, R = 4-NEt₂ (T1), 5-Br (T2); X = S, R = H (T3); R = 5-Br (T4). Their structures were characterized by elemental analysis, IR and (¹H, ¹³C)-NMR spectra. The molecular structure of T2 was confirmed by X-ray diffraction. The crystal of T2 belongs to monoclinic system, space group Ia. Five-coordinated distorted triangular bipyramids and six-coordinated distorted octahedral configurations were formed by the coordination of oxygen and nitrogen atoms of ligand with two dibutyltins, thus forming a trimeric hexanuclear butyltin complex by the cross coordination of three units (Bu₂Sn)₂L with enol imines. The T2 and T4 exhibit fluorescence emission in DMF solvents and DMF-water mixture. The fluorescence intensity of T2-DMF-H₂O system decreases almost linearly with the increase of water volume fraction (WVF). The aggregation fluorescence enhancement effect of T4-DMF-H₂O solution system increases with the increase of WVF at the range of 0~20% WVF. When WVF is more than 20%, the fluorescence intensity decreases with the increase of WVF. In addition, T1~T4 have broad growth activities on target plants, such as Portulaca oleracea L., Amaranthus spinosus L., Cassia tora L., Brassica campestris L.ssp.chinensis var.utilis Tsen et Lee, and Amaranthus tricolor L., and can be used as a candidate herbicide for further research.