Synthesis and Crystal Structure of μ-oxo-bis[(octaethyloxoporphinato)iron(III)] Tetrafluoroborate

Exposure of dichloromethane solution of [OEOPFe(BF₄)], where OEOP is the monoanion of octaethyloxoporphyrin, to dioxygen results in its transformation into the μ-oxo bridged compound, [(OEOPFe)₂O)](BF₄)₂. The molecular structure of the title compound, [(OEOPFe)₂O](BF₄)₂, was determined by single-crystal X-ray diffraction. It contains a binuclear centrosymmetric [(OEOPFe)₂O]²⁺ cation (the bridging O atom lies on an inversion centre) and two tetrafluoroborate anions. The Fe atom is five-coordinate to four N atoms of the porphyrin ring and to one bridging O atom. The compound is characterized by an average Fe–N bond length of 2.064 Å. The Fe–O bond distance is 1.7665(11) Å and the Fe–O–Fe bond angle is 180.0° and the two porphyrin rings are parallel. Crystal data: crystal system, monoclinic, a = 8.867(3), b = 26.104(9), c = 15.748(6) Å, β = 105.40(3)°, space group, P2₁/c, V = 3514(2) Å³, Z = 2.     

Conjugation paths in monosubstituted 1,2- and 2,3-naphthoquinones

Optimization of monosubstituted (X = NO, NO(2), CN, CHO, Me, OMe, OH, NH(2), NHMe, and N(Me)(2)) derivatives of 1,2- and 2,3-naphthoquinone by use of B3LYP with the 6-311+G** basis set applying the GAUSSIAN03 program allowed us to analyze the character of interactions between the substituents and the carbonyl groups. It is shown that only one of two carbonyl groups exhibited substantial substituent effect evidenced by regression of the CO bond length and delocalization index, DI(CO) on the Hammett substituent constants, σ(p), with a very high correlation coefficient, whereas the other one did not depend in any substantial way on σ(p). Dependences of conjugation path built up of bonds between substituent and oxygen atoms of carbonyl groups on σ(p), give more acceptable correlations if the number of bonds in the path is even than in cases when they are odd.     

Evaluating Ecohydrological Model Sensitivity to Input Variability with an Information-Theory-Based Approach

Ecohydrological models vary in their sensitivity to forcing data and use available information to different extents. We focus on the impact of forcing precision on ecohydrological model behavior particularly by quantizing, or binning, time-series forcing variables. We use rate-distortion theory to quantize time-series forcing variables to different precisions. We evaluate the effect of different combinations of quantized shortwave radiation, air temperature, vapor pressure deficit, and wind speed on simulated heat and carbon fluxes for a multi-layer canopy model, which is forced and validated with eddy covariance flux tower observation data. We find that the model is more sensitive to radiation than meteorological forcing input, but model responses also vary with seasonal conditions and different combinations of quantized inputs. While any level of quantization impacts carbon flux similarly, specific levels of quantization influence heat fluxes to different degrees. This study introduces a method to optimally simplify forcing time series, often without significantly decreasing model performance, and could be applied within a sensitivity analysis framework to better understand how models use available information.