Spiroconjugation involving sulfur 3p atomic orbitals

Baker, A. D.; Brisk, Marion A.; Venanzi, Thomas J.; Kwon, Young‐Tae; Sadka, S.; Liotta, Dennis

doi:10.1016/s0040-4039(00)93059-4

Cited by 6 publications

(2 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The PE spectrum of 33 indicated the dominant electronic interaction to be spiroconjugation involving sulfur 3p orbitals (122). The first three bands resulted from ionizations of a2, e, and b, orbitals, respectively.…”

Section: ^Rmentioning

confidence: 99%

Electron spectroscopy: ultraviolet and x-ray excitation

Baker¹,

Brisk²,

Liotta³

1978

Anal. Chem.

View full text Add to dashboard Cite

Section: ^Rmentioning

confidence: 99%

Electron spectroscopy: ultraviolet and x-ray excitation

Baker¹,

Brisk²,

Liotta³

1978

Anal. Chem.

View full text Add to dashboard Cite

“…The energy difference between spiro-antibonding and spiro-bonding MOs is referred to as spiro-splitting (ΔE s ) and it is explained in terms of matching and mismatching combinations of the p orbitals in space. [5] Several studies have provided theoretical [1,2,[6][7][8] and experimental evidence on spiroconjugation by π-facial selectivity in Diels-Alder reactions of spiro-linked dienes [9,10] or by employing spectroscopic tools including UV/Vis [11] and photoelectron spectroscopies, [3,5,[12][13][14] among others. [15] However, strategies for conscious tailoring and implementation of spiroconjugation into functional materi-als or even simple chromophoric systems are currently not available.…”

Section: Introductionmentioning

confidence: 99%

ON/OFF Spiroconjugation through Peripheral Functionalization: Impact on the Reactivity and Chiroptical Properties of Spirobifluorenes

et al. 2022

View full text Add to dashboard Cite

In memory of Prof. Dr. François Diederich Spirobifluorenes are an important class of spiro compounds frequently used in the field of organic electronics. However, harnessing spiroconjugation to obtain high-performance in such structural motifs remains unexplored. We herein propose that peripheral functionalization may serve as a useful tool to control spiroconjugation in an ON/OFF manner on both chemical reactivity and photophysical properties. In particular, the ratio of mono-and di-functionalized spirobifluorenes found experimentally during their synthesis were found to be 3/2, 7/2, and 12/2 for phenyl, nitro-phenyl and amino-phenyl analogues, respectively. These remarkable reactivity differences correlate with the spiroconjugation character evaluated theoretically at the CAM-B3LYP/6-31G(d,p) level of theory. Additionally, comparison of experimental and predicted optical and chiroptical responses shows that spiroconjugated molecular orbitals have a significant or negligible involvement on the main electronic transitions depending on the peripheral functionality of the spirobifluorene.

show abstract

Photoelectron spectroscopy of alcohols, phenols, ethers and peroxides

Eckert‐Maksić

1993

PATAI'S Chemistry of Functional Groups

View full text Add to dashboard Cite

Spiroconjugation involving sulfur 3p atomic orbitals

Cited by 6 publications

References 8 publications

Electron spectroscopy: ultraviolet and x-ray excitation

Electron spectroscopy: ultraviolet and x-ray excitation

ON/OFF Spiroconjugation through Peripheral Functionalization: Impact on the Reactivity and Chiroptical Properties of Spirobifluorenes

Photoelectron spectroscopy of alcohols, phenols, ethers and peroxides

Contact Info

Product

Resources

About