Non-isothermal cold crystallization of liquid crystalline porphyrins.

A series of liquid crystalline porphyrins was synthesized, purified, and characterized. Differential scanning calorimetry (DSC) and hot-stage polarized optical microscopy (HS-POM) revealed that the porphyrins in the series with shorter alkyl arm lengths exhibit kinetic cold crystallization, wherein the molecules spontaneously organize into large, disc-like structures that remain stable upon cooling. Using DSC, the kinetic and thermodynamic parameters related to these materials were determined. Analysis of non-isothermal crystallization revealed the presence of multiple nucleation and growth processes related to cold crystallization.

Reduction of dioxygen to water by a Co(N2O2) complex with a 2,2'-bipyridine backbone.

We report a Co-based complex for the reduction of O2 to H2O utilizing decamethylferrocene as chemical reductant and acetic acid as a proton donor in methanol solution. Despite structural similarities to previously reported Co(N2O2) complexes capable of catalytic O2 reduction, this system shows selectivity for the four-electron/four-proton reduction product, H2O, instead of the two-electron/two-proton reduction product, H2O2. Mechanistic studies show that the overall rate law is analogous to previous examples, suggesting that the key selectivity difference arises in part from increased favorability of protonation at the distal O position of the key intermediate Co(iii)-hydroperoxide, instead of the proximal one. Interestingly, no product selectivity dependence is observed with respect to the presence of pyridine, which is proposed to bind trans to O2 during catalysis.

Electrocatalytic CO2 Reduction to Formate with Molecular Fe(III) Complexes Containing Pendent Proton Relays.

Previously, we reported an iron(III) complex with 6,6'-([2,2'-bipyridine]-6,6'-diyl)bis(2,4-ditertbutyl-phenol) as a ligand (Fe(tbudhbpy)Cl, 1) as catalytically competent for the electrochemical reduction of CO2 to formate (Faradaic efficiency FEHCO2- = 68 ± 4%). In mechanistic experiments, an essential component was found to be a pre-equilibrium reaction involving the association of the proton donor with the catalyst, which preceded proton transfer to the Fe-bound O atoms upon reduction of the Fe center. Here, we report the synthesis, structural characterization, and reactivity of two iron(III) compounds with 6,6'-([2,2'-bipyridine]-6,6'-diyl)bis(2-methoxy-4-methylphenol) (mecrebpy[H]2, Fe(mecrebpy)Cl, 2) and 6,6'-([2,2'-bipyridine]-6,6'-diyl)bis(4-(tert-butyl)benzene-1,2-diol) (tbucatbpy[H]4, Fe(tbucatbpy), 3) as ligands, where pendent -OMe and -OH groups are poised to modify the protonation reaction involving the Fe-bound O atoms. Differences in selectivity and activity for the electrocatalytic reduction of carbon dioxide (CO2) to formate (HCO2-) between complexes 1-3 were assessed via cyclic voltammetry and controlled potential electrolysis (CPE) experiments in N,N-dimethylformamide. Mechanistic studies suggest that the O atoms in the secondary coordination sphere are important for relaying the exogenous proton donor to the active site through a preconcentration effect, which leads to the JHCO2- (partial catalytic current density for formate) increasing by 3.3-fold for 2 and 1.2-fold for 3 in comparison to the JHCO2- of 1. These results also suggest that there is a difference in the strength of the interaction between the pendent functional groups and the sacrificial proton donor between 2 and 3, resulting in quantifiable differences in catalytic activity and efficiency. CPE experiments demonstrate an increased FEHCO2- = 85 ± 2% for 2, whereas 3 had a lower FEHCO2- = 71 ± 3%, with CO and H2 generated as co-products in each case to reach mass balance. These results indicate that using secondary sphere moieties to modulate metal-ligand interactions and multisite electron and proton transfer reactivity in the primary coordination sphere through reactant preconcentration can be a powerful strategy for enhancing electrocatalytic activity and selectivity.