The Electronegativity of Groups

Clifford, A. F.

doi:10.1021/j150578a003

Cited by 65 publications

(21 citation statements)

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“…25 The correlation is masked, however, by a strong dependence on some other variable. 25 The correlation is masked, however, by a strong dependence on some other variable.…”

Section: Of Ref 2 (C) Ourmentioning

confidence: 99%

Effects of Ring Geometry on Triplet and Singlet Energies of the Metal Mesoporphyrins

Fischer

Weiss

1970

The Journal of Chemical Physics

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Correlations were found between the hole size of 10 metalloporphyrins, determined by x-ray crystallography, and the ionic radius of the central metal atom, derived from a new compilation of ionic radii as a function of coordination number, spin state, and valence. These correlations were used to define representative porphyrin geometries for each of three different hole sizes. We recommend the use of these geometries for future molecular-orbital calculations. Molecular orbital calculations based on these porphyrin geometries predict a decrease in the phosphorescence energy as the hole size increases, a prediction in agreement with data in the literature on metal mesoporphyrins. Experimental excitation energy of the singlet Soret (but not the visible) band also decreases with increasing hole size, a result not given by calculations using either four-orbital or extensive configuration-interaction models. Electronegativity has a statistically significant eITect on the lowest excited singlet and, to a lesser extent, the lowest triplet ener!!:y. Changes in hole size produce little change in calculated bond order, indicating that structural changes induced by increased hole size are due to strain induced in sigma bonds. There is no correlation between either singlet or triplet energy and the charge density of the central metal atom as determined by previous molecular-orbital calculations. Thus, the primary effect of changing metals on the lowest triplet state of metal porphyrins is due to effects on the pi electrons of the geometric distortion of the porphyrin ring imposed by the steric requirements of the central metal atom. The effect of the central metal on the singlet energies remains to be fully explained.

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“…25 The correlation is masked, however, by a strong dependence on some other variable. 25 The correlation is masked, however, by a strong dependence on some other variable.…”

Section: Of Ref 2 (C) Ourmentioning

confidence: 99%

Effects of Ring Geometry on Triplet and Singlet Energies of the Metal Mesoporphyrins

Fischer

Weiss

1970

The Journal of Chemical Physics

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“…When the halogens are in the 5,5Ј positions, the change in the energy of the lowest energy MLCT transition correlates with the electronegativities (F, 4.0; Cl, 3.0; Br, 2.8) [22] of the halide substituent (R 2 = 0.99, Figure S7b). The second reduction potential correlates with the change in the lowest energy MLCT transition, thus the second reduction potential of the dye also correlates with the electronegativity of the halide substituent (R 2 = 0.99, Figure S7b).…”

Section: Resultsmentioning

confidence: 97%

Isomer Dependence of Efficiency and Charge Recombination in Dye‐Sensitized Solar Cells Using Ru Complex Dyes Bearing Halogen Substituents

et al. 2015

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“…If there is an electronegativity difference between M and the azido group in the formally covalent M(N 3 ) bond, then the molecule will be stabilized by ionic resonance. However the M(N 3 ) bond will be particularly weak where M is large and the electronegativities are similar 4. Neutral covalent azides can be stabilized by adduct formation with a Lewis base (e. g. pyridine), which results in surprisingly thermally stable compounds, as was successfully shown for azides of Group 133f and 14 13a.…”

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confidence: 95%

On the Way to “Solid Nitrogen” at Normal Temperature and Pressure? Binary Azides of Heavier Group 15 and 16 Elements

Knapp

Passmore

2004

Angew Chem Int Ed

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The Electronegativity of Groups

Cited by 65 publications

References 1 publication

Effects of Ring Geometry on Triplet and Singlet Energies of the Metal Mesoporphyrins

Effects of Ring Geometry on Triplet and Singlet Energies of the Metal Mesoporphyrins

Isomer Dependence of Efficiency and Charge Recombination in Dye‐Sensitized Solar Cells Using Ru Complex Dyes Bearing Halogen Substituents

On the Way to “Solid Nitrogen” at Normal Temperature and Pressure? Binary Azides of Heavier Group 15 and 16 Elements

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