Herein, we report the synthesis of a novel heterohexanuclear complex (1) of a heteroaromatic cofactor, pyrroloquinolinequinone (PQQ). The crystal structure of 1 was determined to reveal that two PQQ-bridged RuIIAg I units were linked by two [AgI(OTf)2] - units (OTf = CF3SO3-). A solvent-bound RuIIAgI heterodinuclear complex (2) was formed from 1 in a coordinating solvent such as acetone to show an intense metal-to-ligand charge-transfer band at 709 nm.
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