A Bis(dipyrrinato) Motif as a Building Block for Polynuclear Rhenium(I) Architectures

The coordination of a bis(dipyrrin) ligand ( L H 2 ) to Re(CO) 5 Cl delivers a dirhenium salt that serves as a precursor to a dinuclear phosphine compound or as a component of a metallacycle when combined with 4,4′‐bipyridine (bpy) to furnish a tetranuclear [{(CO) 3 Re} 4 L 2 (bpy) 2 ] complex. The distorted nature of the metallacycle was determined by single‐crystal X‐ray diffraction revealing that the Re‐bpy‐Re edges are twisted by approximately 119° and the Re‐ L ‐Re edges are twisted by approximately 88° from the idealized rectangular plane. The Re I metallacycle exhibits luminescence ( λ fluo. = 592 nm; λ phos. = 731 nm) in CH 2 Cl 2 at 77 K.