Dual Metal Complex Functionalization of Black Phosphorus.

Black phosphorus (bP), a two-dimensional van der Waals material with a phosphine-like basal plane, offers a promising but underexplored platform for surface organometallic chemistry. Here we demonstrate the first dual organometallic functionalization of bP using two chemically orthogonal protocols applied sequentially: (i) direct coordination of Re(CO)3Cl to the bP surface and (ii) tethering Re or Ru complexes via ortho-quinone anchors. Together, these strategies establish bP as a versatile platform for programmable, molecularly precise, multimetal architectures.