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Thermal effects of coordination reaction of Cu(Ⅱ )-α,α’-bipyridyl-macrocyclic diox-otetraaming ternary complex compounds have been determined in aqueous solution at 25.0±0.1℃and I=0.1 mol.dm-3 KNO3 by means of model RD-1 automatic conduction calorimeter. Linearthermodynamic function relationships have been found to exist in this ternary system. Ther-modynamic properties of Cu(Ⅱ)biPy/phen-HRTADO ternary systems have been compared anddiscussed. The effects of substituents and stacking of aromatic ring to the thermodynamic prop-erties Cu(Ⅱ)-bipy/phen-HRTADO ternary systems also have been discussed.