Luminescence from open-shell, first-row transition metal dipyrrin complexes.

Several first-row transition metal complexes of the 1,9-bis(2',4',6'-triphenylphenyl)-5-mesityl dipyrrinato ligand and its tetrahalogenated analogues have been synthesized and their luminescence spectra obtained. The protonated ligands, as well as the Li(i), Mn(ii), Cu(i), Cu(ii), and Zn(ii) chelates show appreciable luminescence, despite the paramagnetism of the Mn(ii) and Cu(ii) ions. Fluorescence quantum yields (ΦF) as high as 0.67 were observed for the zinc complex. Luminescence was partially quenched by the introduction of heavy halogens to the backbone of the ligand, as well as by the introduction of paramagnetic metal ions. Room-temperature, solution state phosphorescence was observed from the halogenated dipyrrinato lithium salts, as well as from the non-halogenated Mn(ii) complex.

Reactivity of a stable copper-dioxygen complex.

We report the isolation of a room temperature stable dipyrromethene Cu(O2) complex featuring a side-on O2 coordination. Reactivity studies highlight the unique ability of the dioxygen adduct for both hydrogen-atom abstraction and acid/base chemistry towards phenols, demonstrating that side-on superoxide species can be reactive entities.

Electronic perturbations of iron dipyrrinato complexes via ligand ß-halogenation and meso-fluoroarylation.

Systematic electronic variations were introduced into the monoanionic dipyrrinato ligand scaffold via halogenation of the pyrrolic ß-positions and/or via the use of fluorinated aryl substituents in the ligand bridgehead position in order to synthesize proligands of the type 1,9-dimesityl-ß-R(4)-5-Ar-dipyrrin [R = H, Cl, Br, I; Ar = mesityl, 3,5-(F(3)C)(2)C(6)H(3), C(6)F(5) in ligand 5-position; ß = 2,3,7,8 ligand substitution; abbreviated ((ß,Ar)L)H]. The electronic perturbations were probed using standard electronic absorption and electrochemical techniques on the different ligand variations and their divalent iron complexes. The free-ligand variations cause modest shifts in the electronic absorption maxima (λ(max): 464-499 nm) and more pronounced shifts in the electrochemical redox potentials for one-electron proligand reductions (E(1/2): -1.25 to -1.99 V) and oxidations (E(1/2): +0.52 to +1.14 V vs [Cp(2)Fe](+/0)). Installation of iron into the dipyrrinato scaffolds was effected via deprotonation of the proligands followed by treatment with FeCl(2) and excess pyridine in tetrahydrofuran to afford complexes of the type ((ß,Ar)L)FeCl(py) (py = pyridine). The electrochemical and spectroscopic behavior of these complexes varies significantly across the series: the redox potential of the fully reversible Fe(III/II) couple spans more than 400 mV (E(1/2): -0.34 to +0.50 V vs [Cp(2)Fe](+/0)); λ(max) spans more than 40 nm (506-548 nm); and the (57)Fe Mössbauer quadrupole splitting (|ΔE(Q)|) spans nearly 2.0 mm/s while the isomer shift (δ) remains essentially constant (0.86-0.89 mm/s) across the series. These effects demonstrate how peripheral variation of the dipyrrinato ligand scaffold can allow systematic variation of the chemical and physical properties of iron dipyrrinato complexes.