A combination of density functional theory calculations, electronic absorption and resonance Raman spectroscopy has been applied to a series of beta-substituted zinc porphyrins to elucidate how the substituent affects the electronic structure of the metalloporphyrin and assign the nature of electronic transitions in the visible region. The use of conjugated beta substituents invokes a large per...

We report the results of density functional theory (DFT) calculations of the (57)Fe Mössbauer isomer shifts (delta(Fe)) for a series of 24 inorganic, organometallic, and metalloprotein/metalloporphyrin model systems in S = 0, (1)/(2), 1, (3)/(2), 2, and (5)/(2) spin states. We find an excellent correlation between calculation and experiment over the entire 2.34 mm s(-1) range of isomer shifts: ...

Box-like tetrakis(metalloporphyrin) supramolecular assemblies possessing Zn and Al metal sites can catalyze the methanolysis of phosphate triesters with a high rate enhancement, up to 430 times faster than the uncatalyzed reaction. Mechanistic studies suggest that the observed rate enhancement can be attributed to a high local concentration of methoxide ion that operates in concert with a solvo...

Continuous miniaturization of magnetic units in spintronics devices inspires efforts to search for novel 2D magnetic materials with giant magnetic anisotropy energy (MAE). Through systematic first-principles calculations, large MAE of 24 meV in W or Re embedded 2D polyporphyrin frameworks is found. Interestingly, the MAE can be enhanced up to 60 meV, through replacing the hydrogen atoms on the ...

The study of synthetic analogues of heme proteins has been thorough and successful.1 Despite many accomplishments, however, there remains a fundamental difference between the heme proteins themselves and the small molecules that mimic them; the analogues are generally not made from peptides, and the interactions between the heme and the protein remain largely unexplored.2 The few exceptions are...

The catalysis by S, 1 0, IS,20-tetrakis(pentafluorophenyl)-21H,23H-porphyrin iron(III) chloride (F20 TPPFeCl) of alkene epoxidation by H20 2 has been investigated. Extensive catalyst decomposition was observed during the reaction. A kinetics and product yield analysis has shown that this decomposition does not occur via either the oxoperferryl intermediate (F 20 TPP·+)F e =0 or the oxoferryl in...

We report a direct one-step method to chemically graft metalloporphyrins to a visible-light-absorbing gallium phosphide semiconductor with the aim of constructing an integrated photocathode for light activating chemical transformations that include capturing, converting, and storing solar energy as fuels. Structural characterization of the hybrid assemblies is achieved using surface-sensitive s...