Dinuclear copper(I) complexes have been prepared starting from bis(diphenylphosphanyl)acetylene (dppa), [Cu(CH3CN)4](BF4) and various 1,10-phenanthroline ligands (NN), namely 1,10-phenanthroline (phen), neocuproine (dmp), bathophenanthroline (Bphen), bathocuproine (Bdmp) and 2-phenyl-1,10-phenanthroline (mpp). The resulting [Cu2(µ-dppa)2(NN)2](BF4)2 complexes have been thus obtained in excellent yields (88 to 94 %). X-ray crystal structure analysis of four complexes revealed that the 10-membered dimetallacycle adopts a chair-like conformation in the solid state. Detailed variable temperature NMR investigations have evidenced dynamic coordination/decoordination of the NN ligands as well as ligand exchange reactions. At high temperature (100 °C), entropic effects tend to destabilize the dinuclear heteroleptic complexes. As a result, homoleptic mononuclear complexes, i.e. [Cu(NN)2]+ and undefined dppa copper(I) complexes, start to appear in solution. In contrast, the heteroleptic coordination scenario is almost exclusively favored at lower temperatures. For most of the dinuclear complexes, the 10-membered dimetallacycle remains flexible and chair-to-chair interconversion occurs faster than the NMR timescale even at –70 °C. In the particular case of the mpp derivative, the bulky phenyl substituent prevents the isomerization of the metallacycle and thus contributes to rigidify the structure. This rigidification has a dramatic effect on the emission properties of this particular compound. The emission quantum yield of [Cu2(µ-dppa)2(mpp)2](BF4)2 is effectively one order of magnitude higher when compared to all the other complexes in this series (20 % vs. 0.3–1.7 % in the solid state).