Synthesis, conformational control, and photothermal application of helically twisted 3,6-carbazole-based porphyrinoids and mono-palladium complex.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 40781222.
- Also identified by DOI 10.1038/s41467-025-62763-1 and PMC identifier 12334570.
- No licence information is recorded for this record.
- Because redistribution is not established, this page shows the abstract only. Follow the links below for the full text.
Abstract
Synthetic control over multiple conformations of expanded porphyrinoids, which are intrinsically linked to their properties and functions, has long been a key objective in chemical research. Here, we present an N-substituent-controlled synthesis of 3,6-carbazole-based octaphyrins and dodecaphyrins via modified Rothemund-type condensation. The choice of pre-modified N-substituents (hydrogen, methyl, tert-butoxycarbonyl) on the 3,6-carbazolylene precursors critically dictates the assembly pathway, enabling access to porphyrinoids with distinct conformations. The octaphyrin scaffold comprises two figure-eight geometries and a half-twisted Möbius form, shaped by solvent-drived kinetic and thermodynamic control. The dodecaphyrins display two helically twisted topologies governed by thermodynamical control. Metalation with Pd(OAc)₂ stabilizes the dynamic twist of octaphyrin into a specific figure-eight geometry, yielding a mono-Pd<sup>II</sup> complex featuring an unconventional NNCC-Pd coordination mode. All these systems exhibit pronounced optical responses to near-infrared light and the mono-Pd<sup>II</sup> complex demonstrates efficient photothermal conversion after encapsulation within nanoparticles, allowing for tumor phototheranostics in the near-infrared bio-window.