To systematically explore the influence of the bulky aromatic ring skeleton with a large conjugated pi-system on the structures and properties of their complexes, six Cu-II, Co-II, and Ni-II complexes with the anthracene-based carboxylic ligand anthracene-9-carboxylic acid (HL1), were synthesized and characterized, sometimes incorporating different auxiliary ligands: [Cu-2(L-1)(4)(CH3OH)(2)](CH3OH) (1), [Cu-4(L-1)(6)(L-2)(4)](NO3)(2)(H2O)(2) (2), {[Cu-2(L-1)(4)(L-3)](CH3OH)(0.25)}(infinity) (3), [Co-2(L-1)(4)(L-4)(2)(mu-H2O)](CH3OH) (4), {[Co(L-1)(2)(L-5)(CH3OH)(2)]} (5), and {[Ni(L-1)(2)(L-5)(CH3OH)(2)]} (6) (L-2 = 2,2'-bipyridine, L-3 = 1,4-diazabicyclo[2.2.2]octane, L-4 = 1,10-phenanthroline, and L-5 = 4,4'-bipyridine). 1 has a dinuclear structure that is further assembled to form a one-dimensional (1D) chain and then a two-dimensional (2D)network by the C - H center dot center dot center dot O H-bonding and pi center dot center dot center dot pi stacking interactions jointly. 2 takes a tetranuclear structure due to the existence of the chelating L-2 ligand. 3 possesses a 1D chain structure by incorporating the related auxiliary ligand L-3, which is further interlinked via interchain pi center dot center dot center dot pi stacking, resulting in a three-dimensional (3D) network. 4 also has a dinuclear structure and then forms a higher-dimensional supramolecular network through intermolecular pi center dot center dot center dot pi stacking and/ or C - H center dot center dot center dot pi interactions. 5 and 6 are isostructural complexes, except they involve different metal ions, showing 1D chain structures, which are also assembled into 2D networks from the different crystallographic directions by interchain pi center dot center dot center dot pi stacking and C - H center dot center dot center dot pi interactions, respectively. The results reveal that the steric bulk of the anthracene ring in HL1 plays an important role in the formation of 1-6. The magnetic properties of the complexes were investigated, and the very long intermetallic distances result in weak magnetic coupling, with the exception of 1 and 3, which adopt the typical paddle-wheel structure of copper acetate and are thus strongly coupled.