Repozytorium

Perylene Diimide‐Derived Bis(Macrocyclic) Ligand Affords Chiral Multinuclear Pd(II) Complexes via Direct Bay‐Region Palladation

Autorzy

He-Ye Zhou

Shasha Yan

Huaxi He

Yuhua Wang

Jiaying Yan

Piotr J. Chmielewski

Frank Würthner

Bin Liu

Rok wydania

2026

Czasopismo

Angewandte Chemie - International Edition

Numer woluminu

65

Strony

e8176990/1-e8176990/9

DOI

10.1002/anie.8176990

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

Macrocyclic ligands provide powerful access to structurally defined multi-metallic architectures, yet direct π-core metalation of imide-functionalized polycyclic aromatic dyes remains difficult to control. Herein, we present the design and synthesis of a new nitrogen-rich bis(macrocyclic) ligand (1) based on a perylene diimide (PDI) scaffold. Coordination of Pd(II) to this ligand triggers direct C─H palladation at the bay region of the PDI, yielding two distinct complexes—a bis‑Pd and a tetra‑Pd species (1-Pd2 and 1-Pd4)—each featuring asymmetrically coordinated, bridged Pd centers within the macrocyclic cavities. Furthermore, palladation distorts the PDI core and induces conformational chirality in the macrocyclic framework. Ultrafast transient absorption measurements further reveal systematic changes in the excited-state response across the series. In addition, OTTLE spectroelectrochemical studies show that direct palladation creates strongly redox-responsive low-energy optical states, with markedly enhanced near-IR absorption in the reduced Pd complexes. This work provides a feasible synthetic route for the direct metalation of perylene diimide dyes, enabling strong dye-metal electronic coupling and establishing such chiral multinuclear complexes as functionally tunable multi-metallic π-systems.

Słowa kluczowe

chirality, macrocyclic ligands, multi-metallic complexes, palladium, perylene diimide

Adres publiczny

http://dx.doi.org/10.1002/anie.8176990

Strona internetowa wydawcy

onlinelibrary.wiley.com

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