This work revealed that significant asymmetric nonlinear effects can be found in a coordination-directed conformational alteration through competing allosteric mechanisms. Toward this aim, we have prepared new chiral bridging ligands [(S,S)- and (R,R)-Im(2)An] containing an anthracene ring as a spacer with two ethynyl-linked chiral imidazole groups at the 9,10-positions. The (S,S)- and (R,R)-Im(2)An ligands (L) spontaneously form the assemblies with Zn2+ ions (M) in solution phase, giving L4M2-type assemblies with a general formula [(S,S)- or (R,R)-Im(2)An](4)(Zn-2(+))(2). NMR studies revealed that the [(S,S)-Im(2)An](4)(Zn2+)(2) assembly has an anthracene dimer structure with a parallel-displaced geometry, leading to relatively small circular dichroism (CD) signals, as expected for nonchiral objects. Conversely, subsequent addition of chiral coligands [(R)- or (S)-Ph-box] to [(S,S)-Im(2)An](4)(Zn2+)(2) afforded an alternative Zn2+ assembly with general formula [(R)- or (S)-Ph-box](2)[(S,S)-Im(2)An](2)(Zn2+)(2), where the chiral coligands expel two of the (S,S)-Im(2)An ligands that were singly bound to the Zn2+ ions in the original [(S,S)-Im(2)An](4)(Zn2+)(2) assembly. This ligand-exchange reaction causes conformational alteration from a parallel-displaced structure to a twisted stacking between the anthracene rings inside the Zn2+ assembly, which results in a significant enhancement of CD signals due to excitonic interactions of the chiral anthracene dimer. Dissymmetry factor (gCD) for CD due to chiral stacking structures shows a significant inverse sigmoidal response to the enantiomeric excess of the chiral coligands. The observed nonlinear phenomena are results of the two conflicting mechanisms, homochiral cooperative association (homochiral self-sorting) to form CD-active assemblies [(S)- or (R)-Ph-box](2)[(S,S)-Im(2)An](2)(Zn2+)(2) versus heterochiral cooperative dissociation of [(S,S)-Im(2)An](4)(Zn2+)(2) by sequestering of Zn2+ inside the assembly through formation of a heterochiral 2:1 Zn-2(+) complex ([(R)-Ph-box][(S)-Ph-box]Zn2+). The presented mechanisms provide a new strategy for generating switch-like OFF/ON states in chiral systems.