We report the synthesis, spectroscopic, structural, and ultrafast photophysical investigation of a series of homoleptic and heteroleptic Zn(II) complexes based on the donor-acceptor β-diketonate ligand 4,4,4-trifluoro-1-phenylbutane-1,3-dione. Mass spectrometry, infrared, and NMR analyses confirm complexation and indicate possible fragmentation pathways involving the sequential loss of β-diketonate ligands. Single-crystal X-ray diffraction revealed that all complexes adopt monomeric octahedral geometries, with the ancillary nitrogen-based ligands introducing variable distortions. Thermal analyses confirmed that the complexes are non-volatile and have an onset >250 °C, with thermal decomposition primarily to ZnO and ZnF₂. Complexes with aromatic Lewis base led to higher residue percentages, likely due to the final graphitic carbon content. UV-Vis absorption and femtosecond transient absorption spectroscopy demonstrate that the chelated β-diketonate ring serves as the main optically active chromophore, a property unaffected by the nitrogen ligands. The free ligand undergoes rapid internal conversion, whereas coordination to Zn stabilizes the triplet state via LMCT, producing long-lived and chemically reactive species relevant to dissociation processes. This study demonstrates how tailored ligand environments can be exploited to tune excited-state properties, offering a rational framework for the design of functional precursors suitable for nonlinear photolysis and advanced nanomaterial synthesis.

We report the synthesis, structural characterization, and ultrafast photophysical in-vestigation of a novel series of homoleptic and heteroleptic Zn(II) β-diketonates de-rived from donor–acceptor ligands. Single-crystal X-ray diffraction revealed that all complexes adopt monomeric octahedral geometries, with ancillary nitrogen-based ligands inducing variable distortions. UV–Vis absorption and femtosecond transient absorption spectroscopy established that the chelated β-diketonate ring constitutes the primary optically active chromophore, while Zn coordination markedly alters excit-ed-state dynamics. In contrast to the free ligand, which undergoes rapid internal con-version, Zn binding stabilizes the triplet state, generating a long-lived and chemically reactive species. Thermal and mass spectrometric analyses confirmed their stability and decomposition pathways, supporting their potential use as precursors for la-ser-induced three-dimensional ZnO growth. Such features underline the relevance of these complexes in photonic and electronic applications where controlled nanostruc-ture development is required. Overall, these findings provide fundamental insights into structure–photophysics relationships in Zn β-diketonates. They demonstrate how tailored ligand environments can be exploited to tune excited-state properties, offering a rational framework for the design of functional precursors suitable for nonlinear photolysis and advanced nanomaterial synthesis.