Switchable Closed-Shell and Open-Shell Biradical States in Bis-Palladium Complexes of Tetrathiadodecaphyrin via Coordination Rearrangement

Abstract

A figure-eight tetrathiadodecaphyrin (1), featuring two porphyrin-like sub-pockets separated by central carbazolylenes was synthesized. Metalation of the thiaporphyrinoid ligand with Pd(OAc)₂ produces two distinct bis-Pd(II) complexes with different coordination environments. Complex 2, adopting an {NNCS} metalation mode, exhibits a closed-shell electronic structure, whereas complex 3, with an {NNCC} coordination environment, exists as a ligand-centered organic biradicaloid with two magnetically independent spins (S = 1/2). Biradical formation is attributed to single-electron transfer from each ligand sub-pocket to the Pd(II) center accommodated in a d⁸ square-planner coordination geometry. Notably, the complexes are interconvertible through doubly one-electron redox processes, demonstrating a reversible metal coordination rearrangement via thiophene ring flipping within a porphyrinoid framework. This work establishes the first example of such tunable metal coordination, offering a precise strategy for modulating closed-shell and open-shell biradical states. In addition, while complex 2 displays intense absorption and photoacoustic responses to the first near-infrared (NIR-I) light in water after encapsulation within nanoparticles, the nanocomposites encapsulating biradicaloid 3 exhibits enhanced responsiveness in the second near-infrared (NIR-II) region.