Sterically Increased C-H Stretching Frequencies in Fused Bicycloheptane and Half-cage Structures<sup>1,2</sup>

Kivelson, Daniel; Winstein, S.; Bruck, P.; Hansen, Robert L.

doi:10.1021/ja01474a034

Cited by 46 publications

(5 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Furthermore, from various vibrational normal modes those mainly originating from C-H vibrations involved in the ultrashort H…H contacts have been selected and considered; this engages the symmetric and anti-symmetric stretching vibrations of the two target C-H bonds. These high frequency C-H stretching modes were previously observed experimentally and their origin has been attributed to H…H steric effects [71,72].…”

Section: Resultssupporting

confidence: 64%

Seeking for ultrashort “non-bonded” hydrogen–hydrogen contacts in some rigid hydrocarbons and their chlorinated derivatives

Firouzi

Shahbazian

2014

Struct Chem

View full text Add to dashboard Cite

In this communication a systematic computational survey on some rigid hydrocarbon skeletons, e.g. half-cage pentacyclododecanes and tetracyclododecanes, and their chlorinated derivatives in order to seek for the so-called ultrashort "non-bonded" hydrogen-hydrogen contacts is done. It is demonstrated that upon a proper choice and modifications of the main hydrocarbon backbones, and addition of some chlorine atoms instead of the original hydrogen atoms in parts of the employed hydrocarbons, the resulting strain triggers structural changes yielding ultrashort hydrogen-hydrogen contacts with inter-nuclear distances as small as 1.

show abstract

Section: Resultssupporting

confidence: 64%

Seeking for ultrashort “non-bonded” hydrogen–hydrogen contacts in some rigid hydrocarbons and their chlorinated derivatives

Firouzi

Shahbazian

2014

Struct Chem

View full text Add to dashboard Cite

show abstract

“…No mention has been made of any experimental evidence for this kind of tautomeric ring formation in these ketones or in the more highly strained bicyclo [2.1.1] 1,6,6-trimethyl-5-hexanone (238). OH Since it has recently been shown that opposing hydrogens in fused bicycloheptanes are extremely close (163), it is attractive to predict the likelihood of ring tautomer formation in ketones with this structure. Some of them, together with their corresponding, hypothetical ring tautomers, are listed below.…”

Section: Ohmentioning

confidence: 99%

“…Although only partial information on the spectral properties of these ketones has been published, there was no suggestion that the carbonyl group is abnormal (163).…”

Section: Ohmentioning

confidence: 99%

Ring-Chain Tautomerism.

Jones¹

1963

Chem. Rev.

108

View full text Add to dashboard Cite

“…TCD is rigid and has only sigma bond cycloalkanes, which can be considered a nanometer-sized H-terminated 2D material. , More than five decades ago, Winstein et al prepared several polycyclic hydrocarbons . Ermerhas reported crystal structure analysis on the derivatives of exo-exo-tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodecanols .…”

Section: Introductionmentioning

confidence: 99%

“… 43 , 44 More than five decades ago, Winstein et al prepared several polycyclic hydrocarbons. 45 Ermerhas reported crystal structure analysis on the derivatives of exo-exo-tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodecanols. 46 Fused[ n ]polynorbornane-based frameworks appear to be one of the most useful and well-organized macromolecular scaffolds that may be customized for specific applications.…”

Section: Introductionmentioning

confidence: 99%

Designing Excess Electron Compounds by Substituting Alkali Metals to a Small and Versatile Tetracyclic Framework: A Theoretical Perspective

et al. 2023

View full text Add to dashboard Cite

Organic compound-based nonlinear optical (NLO) materials have sparked a lot of attention due to their multitude of applications and shorter optical response times than those of inorganic NLO materials. In the present investigation, we designed exo-exo-tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodecane (TCD) derivatives, which were obtained by replacing H atoms of methylene bridge carbon with alkali metals (Li, Na, and K). It was observed that upon the substitution of alkali metals at bridging CH 2 carbon, absorption within the visible region occurred. Moving from 1 to 7 derivatives, the maximum absorption wavelength of the complexes exhibited a red shift. The designed molecules showed a high degree of intramolecular charge transfer (ICT) and excess electrons in nature, which were responsible for rapid optical response time and significant large molecular (hyper)polarizability. Calculated trends also inferred that the crucial transition energy decreased in order that also played a key role in the higher nonlinear optical response. Furthermore, to examine the effect of the structure/property relationship on the nonlinear optical properties of these investigated compounds (1−7), we calculated the density of state (DOS), transition density matrix (TDM), and frontier molecular orbitals (FMOs). The largest first static hyperpolarizability (β tot ) of TCD derivative 7 was 72059 au, which was 43 times greater than that of the prototype p-nitroaniline (β tot = 1675 au).

show abstract

Sterically Increased C-H Stretching Frequencies in Fused Bicycloheptane and Half-cage Structures^1,2

Cited by 46 publications

References 1 publication

Seeking for ultrashort “non-bonded” hydrogen–hydrogen contacts in some rigid hydrocarbons and their chlorinated derivatives

Seeking for ultrashort “non-bonded” hydrogen–hydrogen contacts in some rigid hydrocarbons and their chlorinated derivatives

Ring-Chain Tautomerism.

Designing Excess Electron Compounds by Substituting Alkali Metals to a Small and Versatile Tetracyclic Framework: A Theoretical Perspective

Contact Info

Product

Resources

About

Sterically Increased C-H Stretching Frequencies in Fused Bicycloheptane and Half-cage Structures1,2

Cited by 46 publications

References 1 publication

Seeking for ultrashort “non-bonded” hydrogen–hydrogen contacts in some rigid hydrocarbons and their chlorinated derivatives

Seeking for ultrashort “non-bonded” hydrogen–hydrogen contacts in some rigid hydrocarbons and their chlorinated derivatives

Ring-Chain Tautomerism.

Designing Excess Electron Compounds by Substituting Alkali Metals to a Small and Versatile Tetracyclic Framework: A Theoretical Perspective

Contact Info

Product

Resources

About

Sterically Increased C-H Stretching Frequencies in Fused Bicycloheptane and Half-cage Structures^1,2