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To lessen the greenhouse effect, measures such as improving the recovery of crude oil and converting carbon dioxide (CO 2 ) into valuable chemicals are necessary to create a sustainable low-carbon future. To this end, the development of efficient new oil-displacing agents and CO 2 conversion has aroused great interest in both academia and industry. The Knoevenagel condensation and CO 2 cycloaddition are the key reactions to solve the above problems. Four Cu- or Zn-based molecular complexes built from different ligands possessing hydrophilic-hydrophobic layers and different dimensionalities were chosen as solid catalysts for this study. Structural analysis revealed the presence of hydrophilic-hydrophobic layers and open metal sites in the low-dimensional complexes. To obtain deep insight into the reaction mechanism, first-principles density functional theory (DFT) calculations were carried out. These calculations confirmed that in the Knoevenagel condensation reaction, the final formation of benzylidenemalononitrile is the rate-determining step (an energy barrier (Δ E ) value of 73.2 kJ mol -1 ). The zero-dimensional (0D) Cu molecular complex with unsaturated metal centers, hydrophilic and hydrophobic layers, exhibited higher catalytic activity (yield: 100%, temperature: room temperature, and time: 2 h) compared with one- and two-dimensional Cu complexes. In the presence of a 0D Zn complex co-catalyzed with Br - in the CO 2 cycloaddition reaction, the Δ E value reduces to 35.5 kJ mol -1 for the ring opening of styrene oxide (SO), which is significantly lower than Br - catalyzed (80.9 kJ mol -1 ) reactions. The roles of unsaturated metal centers, hydrophilic-hydrophobic layers and dimensionality in the Knoevenagel condensation and CO 2 cycloaddition were explained in the results of structure-activity relationships.