scholarly journals Challenges in studying steric interactions in highly strained perhalogenated alkanes and silanes

2021 ◽  
Author(s):  
Luís H. Simões ◽  
Rodrigo A. Cormanich
Keyword(s):  
Steric Interactions ◽  
Highly Strained

scholarly journals Challenges in Studying Steric Interactions in Highly Strained Perhalogenated Alkanes and Silanes.

2021 ◽  
Author(s):  
Luís Simões ◽  
RODRIGO CORMANICH
Keyword(s):  
Quantum Theory ◽  
Total Energy ◽  
Homologous Series ◽  
Nbo Analysis ◽  
Steric Effects ◽  
Electrostatic Effects ◽  
Steric Interactions ◽  
Stereoelectronic Effects ◽  
Helical Geometry ◽  
Highly Strained

The decomposition of the molecular total energy in their hyperconjugative, steric and electrostatic effects can lead to interesting interpretations about the stereoelectronic effects that govern their geometry and properties. In this work, we have studied homologous series of perfluoroalkanes, perchloroalkanes, perfluorosilanes and perchlorosilanes, and all molecules have preference for helical geometries. According to Natural Bond Orbitals (NBO) calculations, the silanes have their helical geometry stabilised by hyperconjugative interactions, as well as the perfluoroalkanes. However, it was surprisingly difficult to disclose that steric interactions are ruling the helical geometry preference in perchloroalkanes by comparing the NBO analysis and the Quantum Theory of Atoms ins Molecules (QTAIM). Although perchloroalkanes have extremely intense steric interactions between Cl lone pairs, some of them were underestimated by the NBO analysis, which showed the opposite behaviour compared with QTAIM that indicates steric effects as the leading forces to helical geometry preference.

Symmetry Breaking and the Turn-On Fluorescence of Small, Highly Strained Carbon Nanohoops

2019 ◽  
Author(s):  
Terri Lovell ◽  
Curtis Colwell ◽  
Lev N. Zakharov ◽  
Ramesh Jasti
Keyword(s):  
Symmetry Breaking ◽  
Theoretical Work ◽  
P Systems ◽  
Quantum Yields ◽  
Size Dependent ◽  
New Class ◽  
Carbon Carbon Bond ◽  
Conjugated Macrocycles ◽  
Structural Manipulation ◽  
Highly Strained

<p>[<i>n</i>]Cycloparaphenylenes, or “carbon nanohoops,” are unique conjugated macrocycles with radially oriented p-systems similar to those in carbon nanotubes. The centrosymmetric nature and conformational rigidity of these molecules lead to unusual size-dependent photophysical characteristics. To investigate these effects further and expand the family of possible structures, a new class of related carbon nanohoops with broken symmetry is disclosed. In these structures, referred to as <i>meta</i>[<i>n</i>]cycloparaphenylenes, a single carbon-carbon bond is shifted by one position in order to break the centrosymmetric nature of the parent [<i>n</i>]cycloparaphenylenes. Advantageously, the symmetry breaking leads to bright emission in the smaller nanohoops, which are typically non-fluorescent due to optical selection rules. Moreover, this simple structural manipulation retains one of the most unique features of the nanohoop structures-size dependent emissive properties with relatively large extinction coefficents and quantum yields. Inspired by earlier theoretical work by Tretiak and co-workers, this joint synthetic, photophysical, and theoretical study provides further design principles to manipulate the optical properties of this growing class of molecules with radially oriented p-systems.</p>

Symmetry Breaking and the Turn-On Fluorescence of Small, Highly Strained Carbon Nanohoops

2019 ◽  
Author(s):  
Terri Lovell ◽  
Curtis Colwell ◽  
Lev N. Zakharov ◽  
Ramesh Jasti
Keyword(s):  
Symmetry Breaking ◽  
Theoretical Work ◽  
P Systems ◽  
Quantum Yields ◽  
Size Dependent ◽  
New Class ◽  
Carbon Carbon Bond ◽  
Conjugated Macrocycles ◽  
Structural Manipulation ◽  
Highly Strained

<p>[<i>n</i>]Cycloparaphenylenes, or “carbon nanohoops,” are unique conjugated macrocycles with radially oriented p-systems similar to those in carbon nanotubes. The centrosymmetric nature and conformational rigidity of these molecules lead to unusual size-dependent photophysical characteristics. To investigate these effects further and expand the family of possible structures, a new class of related carbon nanohoops with broken symmetry is disclosed. In these structures, referred to as <i>meta</i>[<i>n</i>]cycloparaphenylenes, a single carbon-carbon bond is shifted by one position in order to break the centrosymmetric nature of the parent [<i>n</i>]cycloparaphenylenes. Advantageously, the symmetry breaking leads to bright emission in the smaller nanohoops, which are typically non-fluorescent due to optical selection rules. Moreover, this simple structural manipulation retains one of the most unique features of the nanohoop structures-size dependent emissive properties with relatively large extinction coefficents and quantum yields. Inspired by earlier theoretical work by Tretiak and co-workers, this joint synthetic, photophysical, and theoretical study provides further design principles to manipulate the optical properties of this growing class of molecules with radially oriented p-systems.</p>

Sterically Crowded Heterocycles. X. A New Mechanistic Approach to the Ferricyanide Oxidation of 4,6'-Disubstituted 1-(Pyridin-2'-yl)-2,6-diphenylpyridinium Salts

1999 ◽  
Vol 64 (8) ◽  
pp. 1274-1294 ◽  
Author(s):  
Radek Pohl ◽  
Stanislav Böhm ◽  
Josef Kuthan
Keyword(s):  
Transition States ◽  
Oxidative Transformation ◽  
Steric Interactions ◽  
Radical Intermediates ◽  
Mechanistic Approach

The oxidations of the title perchlorates, bearing the sterically diverse 6'-substituents (H, Me, Et, i-Pr, n-Bu, t-Bu and Ph) in two series with the same 4-substituents (Ph and t-Bu) lead to pairs of isomeric 3',5-disubstituted (Z)-1'-phenyl-3'-(2-phenylimidazo[1,2-a]pyridin-3-yl)prop-2'- en-1'-ones and 3,6'-disubstituted [5-phenyl-1-(6'-pyridin-2'-yl)-1H-pyrrol-2-yl](phenyl)methanones except where the both variable substituents are t-Bu and then only pyrrolic product is formed. Considering steric interactions of the substituents in some intermediate and/or transition states a multistep mechanism for the oxidative transformation is proposed and supported by model PM3-PECI calculations of some radical intermediates.

scholarly journals Indirect light absorption model for highly strained silicon infrared sensors

2021 ◽  
Vol 130 (5) ◽  
pp. 055105
Author(s):  
Nicolas Roisin ◽  
Guillaume Brunin ◽  
Gian-Marco Rignanese ◽  
Denis Flandre ◽  
Jean-Pierre Raskin
Keyword(s):  
Light Absorption ◽  
Strained Silicon ◽  
Absorption Model ◽  
Infrared Sensors ◽  
Highly Strained

Void-Enriched and Highly Strained Porous Au–Ag Nanoalloy as a Bifunctional Electro-Catalyst in Alkaline Direct Alcohol Fuel Cell

2021 ◽  
Author(s):  
Sandip Kumar De ◽  
Arpita Nandy ◽  
Subrata Mondal ◽  
Anuradha Roy ◽  
Sourav Mondal ◽  
...  
Keyword(s):  
Fuel Cell ◽  
Direct Alcohol Fuel Cell ◽  
Alcohol Fuel ◽  
Highly Strained

Electrical resistivity of a highly strained sample of potassium

Physica B+C ◽  
1981 ◽  
Vol 108 (1-3) ◽  
pp. 907-908 ◽  
Author(s):  
Meir Danino ◽  
Moshe Kaveh ◽  
Nathan Wiser
Keyword(s):  
Electrical Resistivity ◽  
Highly Strained
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