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This article describes the synthesis, structures and systematic study of the spectroscopic and redox properties of a series of octahedral molybdenum metal cluster complexes with aromatic sulfonate ligands ( n Bu 4 N) 2 [{Mo 6 X 8 }(OTs) 6 ] and ( n Bu 4 N) 2 [{Mo 6 X 8 }(PhSO 3 ) 6 ] (where X - is Cl - , Br - or I - ; OTs - is p-toluenesulfonate and PhSO 3  - is benzenesulfonate). All the complexes demonstrated photoluminescence in the red region and an ability to generate singlet oxygen. Notably, the highest quantum yields (&gt;0.6) and narrowest emission bands were found for complexes with a {Mo 6 I 8 } 4+ cluster core. Moreover, cyclic voltammetric studies revealed that ( n Bu 4 N) 2 [{Mo 6 X 8 }(OTs) 6 ] and ( n Bu 4 N) 2 [{Mo 6 X 8 }(PhSO 3 ) 6 ] confer enhanced stability towards electrochemical oxidation relative to corresponding starting complexes ( n Bu 4 N) 2 [{Mo 6 X 8 }X 6 ].

Octahedral molybdenum cluster complexes with aromatic sulfonate ligands