Luminescent gold(I) complexes ([Au-6(Triphos)(4)Cl](PF6)(5)center dot 2(CH3C6H5), [Au-6(Triphos)(4)Cl](AsF6)(5)center dot 8(CH3C6H5), and [Au-6(Triphos)(4) Cl] (SbF6)(5)center dot 7(CH3C6H5) where Triphos = bis(2-diphenylphosphinoethyl)phenylphosphine) with a boxlike architecture have been prepared and crystallographically characterized. A chloride ion resides at the center of the box with two of the six gold(I) ions nearby. Mechanical grinding of blue luminescent crystals containing the cation, [Au-6(Triphos)(4)Cl](5+), results in their conversion into amorphous solids with green emission that contain the bridged helicate cation, [mu-Cl{Au-3(Triphos)(2)}(2)](5+). A mechanism of the mechanochromic transformation is proposed. The structures of the blue-emitting helicate, [Au-3(Triphos)(2)](CF3SO3)(3)center dot 4(CH3C6H5)center dot H2O, and the green-emitting bridged-helicate, [mu-Cl{Au-3(Triphos)(2)}(2)](PF6)(5)center dot 3CH(3)OH have been determined by single crystal X-ray diffraction.