Biopyrrin pigments, which result from the degradation of heme in biological settings, feature three or two pyrrole rings and characteristic pyrrolin-2-one termini. These scaffolds serve as redox-active ligands and electron reservoirs in coordination compounds. Tripyrrin-1,14-dione coordinates divalent transition metals as a dianionic ligand hosting a delocalized radical. Herein, we report the synthesis and characterization of palladium(II) and platinum(II) tripyrrindione complexes featuring a primary amine (i.e., aniline, tert-butylamine, 1,2-ethylenediamine) at the fourth coordination site within square planar geometries. Interligand hydrogen-bonding interactions are observed between the coordinated amine and the carbonyl groups on the tripyrrindione scaffold. Notably, 1,2-ethylenediamine is employed to link two Pt(II) tripyrrindione complexes. As revealed by optical absorption and electron paramagnetic resonance (EPR) spectroscopy, all resulting complexes present ligand-based radicals that are stable at room temperature and when exposed to air. Spin pairing through multicenter interactions leads to [Formula: see text]-dimerization of the tripyrrindione radicals and a decrease in the EPR signal at low temperatures. Electrochemical measurements indicate that the ligand system undergoes quasi-reversible one-electron oxidation and reduction, thus confirming the ability of tripyrrindione to form square planar complexes in three different redox states.
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This content will become publicly available on December 21, 2024
Temperature-Dependent Spin-Driven Dimerization Determines the Ultrafast Dynamics of a Copper(II)-Bound Tripyrrindione Radical
Radicals and other open-shell molecules play a central role in chemical transformations and redox chemistry. While radicals are often highly reactive, stable radical systems are desirable for a range of potential applications, ranging from materials chemistry and catalysis to spintronics and quantum information. Here we investigate the ultrafast properties of a stable radical system with temperature-dependent spin-tunable properties. This radical complex, Cu(II) hexaethyl tripyrrin-1,14-dione, accommodates unpaired electrons localized on both the copper metal center and the tripyrrolic ligand. The unusual combination of two unpaired electrons and high stability in this radical molecule enable switchable temperature-dependent spin coupling. Two-dimensional electronic spectroscopy measurements of Cu(II) hexaethyl tripyrrin-1,14-dione were collected at room temperature and at 77 K. At room temperature, the molecules are present as monomers and have short picosecond lifetimes. At 77 K, the molecules are present in a dimer form mediated by ferromagnetic and antiferromagnetic coupling. This reversible spin-driven dimerization changes the optical properties of the system, generating long-lived excitonic states.
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- Award ID(s):
- 2236610
- NSF-PAR ID:
- 10487183
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- The Journal of Physical Chemistry Letters
- Volume:
- 14
- Issue:
- 50
- ISSN:
- 1948-7185
- Page Range / eLocation ID:
- 11268 to 11273
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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