Correlation between Electron Delocalization and Ring Currents in All Metallic “Aromatic” Compounds

2010 ◽  
pp. 267-292
2018 ◽  
Vol 17 (01) ◽  
pp. 1850006
Author(s):  
Bi Xiao Yun ◽  
Ablikim Kerim

The global aromaticity of dithienopyridine and dithienobenzene isomers was investigated using the topological resonance energy (TRE) and percentage topological resonance energy (%TRE) methods. The effect of variations in the positions of sulfur and nitrogen atoms on [Formula: see text]-electron delocalization is analyzed. The local aromaticity of these isomers is described based on the bond resonance energy (BRE) and circuit resonance energy (CRE) methods. Our BRE and CRE results show that structure of the central six-membered rings has a strong effect on global aromaticity. The aromaticity of these dithienopyridine isomers is enhanced when a complete pyridine unit exists in their middle ring structure, while the aromaticity of the dithienobenzene isomers is enhanced when a complete benzene unit exists in their middle ring structure. For dithienopyridines, our results obtained using the TRE method correlate well with the Bird aromaticity index as reported in the literature. Our ring-current results show that all these compounds are diatropic systems.


2007 ◽  
Vol 79 (6) ◽  
pp. 969-979 ◽  
Author(s):  
Patrick W. Fowler ◽  
Mark Lillington ◽  
Leif P. Olson

The magnetic criterion of aromaticity is based on the ability of a cyclic system to support a ring current. If the ring current has the diatropic sense, the system is aromatic; if the sense is paratropic, the system is antiaromatic. Attribution of aromaticity ab initio therefore reduces to the calculation and visualization of induced current density. This can be achieved at modest computational cost within the ipsocentric approach, where current density at any point in space is calculated with that point as origin of vector potential. This choice leads to accurate maps of current density and a uniquely simple interpretation in terms of nonredundant orbital contributions governed by translational and rotational selection rules. For example, four-electron diatropicity and two-electron paratropicity are predicted for delocalized forms of [4n+2]- and [4n]-annulenes, respectively. A new application to homoaromatic systems is described. Two model tris-homoaromatics, both neutral molecules, are shown to exhibit a through-space, highest occupied molecular orbital (HOMO)-dominated, four-electron ring current, in a direct analogy with the conventional "aromatic" benzene π-current.


2008 ◽  
Vol 112 (26) ◽  
pp. 5960-5972 ◽  
Author(s):  
Ganga Periyasamy ◽  
Neil A. Burton ◽  
Ian H. Hillier ◽  
Jens M. H. Thomas

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