The photoluminescent complex [Au~2(μ-PNP)~3](ClO~4)~2, PNP=2,6-bis (diphenylphophino) pyridine, which has an open cavity, can serve as a host-complex. When the size and character of the host match with those of the guest, the host and the guest may bind to each other. the changes in the photophysical properties of the complex caused by different guest molecules are explored by using electronic absorption, ^3^1P NMR and emission spectrometry.

Key words: PHOTOLUMINESCENCE, GOLD COMPLEX, SUPERMOLECULAR STRUCTURE, PYRIDINE P, PHOSPHORUS 31 MAGNETIC RESONANCE SPECTROMETRY