期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 24, 期 26, 页码 15718-15725出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2cp00632d
关键词
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资金
- UAREN program
- National Science Foundation [1454047]
- NSF Major Research Instrumentation Grant [0958790]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1454047] Funding Source: National Science Foundation
- Div Of Chem, Bioeng, Env, & Transp Sys
- Directorate For Engineering [0958790] Funding Source: National Science Foundation
The optical properties and time-resolved dynamics of stable open- and closed-shell Pd(ii) and Cu(ii) complexes were investigated using steady-state and ultrafast transient absorption measurements. The results showed that the overall spin state of the complexes can be tuned through their stable open-shell configurations and reversible redox activity.
Stable open- and closed-shell Pd(ii) and Cu(ii) complexes of hexaethyl tripyrrin-1,14-dione (TD1) produce triplet, doublet or singlet states depending on the metal center and the redox state of the ligand. Pd(ii) and Cu(ii) form neutral TD1 complexes featuring ligand-based radicals, thus resulting in doublet and triplet states, respectively. The reversible one-electron oxidation of the complexes removes an unpaired electron from the ligand, generating singlet and doublet states. The optical properties and time-resolved dynamics of these systems are studied here using steady-state and ultrafast transient absorption (pump-probe) measurements. Fast relaxation with recovery of the ground state in tens of picoseconds is observed for the copper neutral radical and oxidized complexes as well as for the palladium neutral radical complex. Significantly longer timescales are observed for the oxidized palladium complex. The ability to tune the overall spin state of the complexes through their stable open-shell configurations as well as the reversible redox activity of the tripyrrolic systems makes them particularly interesting for catalytic applications as well as exploring magnetism and conductivity properties.
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