1,5-bis(R)-3,7-bis[2-(pyridine-2′-yl)ethyl)-1,5-diaza-3,7-diphosphacyclooctanes 1 and 2 and their copper(I) complexes 3 and 4 were developed. The butterfly-shaped copper-iodide core and unusual P,N-chelate and P,P-bridged coordination mode of the heterocyclic ligand in the dinuclear complexes 3 and 4 were revealed. Complexes 3 and 4 display emission in green range of spectra, with lifetimes in a microsecond domain and quantum yields of luminescence in solid-state up to 38 %. Thermochromic effects found for the phosphorescence of 4 in solutions are ascribed to rigidochromism.