Synthesis and Structures of Polyphenylphenanthrenes

Xiao, Yonglong; Mague, Joel T.; Donahue, James P.; Wilson, Laura J.; Kraml, Christina M.; Pascal, Robert A.

doi:10.1002/chem.202001563

Cited by 8 publications

(16 citation statements)

References 29 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…There are various ways that one may estimate the strain in a molecule, but most involve a dissection of the structure and a comparison of the energies of the components via isodesmic, or better, homodesmotic reactions. In the present cases, we chose to ask, “How unfavorable is the formation of the central bond of the crowded biaryl when compared with the formation of the central bond in unsubstituted biphenyl?” As we have done previously, [9] three rather different DFT methods were used for these calculations: B3PW91, M052X‐D3, and PW6B95‐D3(BJ), [10–14] as implemented in Gaussian 16 [15] . We previously observed that B3PW91 gives particularly good molecular geometries for organic compounds, [16] and it also was the best common functional for the estimation of the relative energies of hydrocarbon isomers [17] .…”

Section: Resultsmentioning

confidence: 99%

Extremely Crowded Biaryls

Mague

Pascal

2021

Eur J Org Chem

Self Cite

View full text Add to dashboard Cite

Highly congested derivatives of biphenyl were prepared by double Diels-Alder reactions of cyclopentadienones with substituted butadiynes. The reaction of 2,3,5-tri(tert-butyl) cyclopentadienone (5) and diphenylbutadiyne (3) gave only the single adduct, 1-(phenylethynyl)-2-phenyl-3,5,6-tri-tert-butylbenzene (6), and even extreme conditions gave no second addition. When tetracyclone (4) was added to bis(trimethylsilyl) butadiyne ( 8), two additions were achieved, but one silyl group was lost either during, or immediately following, the second addition to give 2-(trimethylsilyl)-2 ',3,3',4,4',5,5',6-octaphenylbiphenyl (11). However, when 3,4-diphenyl-2,5-dimeth-ylcyclopentadienone (12) was added to 8, the fully substituted 2,2'-bis(trimethylsilyl)-4,4 ',5,5'-tetraphenyl-3,3',6,6'-tetramethylbiphenyl (14) was formed. The X-ray structures of compounds 11 and 14 show them to be quite crowded, but the central biphenyl rings do not exhibit the distortions previously observed in decaphenylbiphenyl. In an alternative approach, arynes were added to 5,5'-bis(4-chlorophenyl)-3,3',4,4'-tetraphenyl-2,2'-bis(cyclopentadienone) (18). Simple benzyne added twice to give 4,4'-bis(4-chlorophenyl)-2,2',3,3'-tetraphenyl-1,1'binaphthyl ( 19) in low yield, but tetraphenylbenzyne, generated from tetraphenylanthranilic acid, added only once.

show abstract

Section: Resultsmentioning

confidence: 99%

Extremely Crowded Biaryls

Mague

Pascal

2021

Eur J Org Chem

Self Cite

View full text Add to dashboard Cite

show abstract

“…In 2020, Xiao’s research group reported DA cycloaddition between 1,1-dioxo-2,3,4,5-tertrabromothiophene and diphenylacetylene (with SO 2 extrusion) employed in the syntheses of decaphenylphenanthrene (DPhA) ( Scheme 266 ) [ 320 ].…”

Section: 11- Dioxothiophene For the Benzene And Naphthalene Ring Formationmentioning

confidence: 99%

“… DA of diphenylacetylene and tetrabromothiophene as an initial step in the syntheses of DPhA [ 320 ]. Reagents and conditions: a = xylene, rfx, Y = 35%; b = next two steps.…”

Section: Figure and Schemesmentioning

confidence: 99%

Diels–Alder Cycloaddition with CO, CO2, SO2, or N2 Extrusion: A Powerful Tool for Material Chemistry

et al. 2021

View full text Add to dashboard Cite

Phenyl, naphthyl, polyarylphenyl, coronene, and other aromatic and polyaromatic moieties primarily influence the final materials’ properties. One of the synthetic tools used to implement (hetero)aromatic moieties into final structures is Diels–Alder cycloaddition (DAC), typically combined with Scholl dehydrocondensation. Substituted 2-pyranones, 1,1-dioxothiophenes, and, especially, 1,3-cyclopentadienones are valuable substrates for [4 + 2] cycloaddition, leading to multisubstituted derivatives of benzene, naphthalene, and other aromatics. Cycloadditions of dienes can be carried out with extrusion of carbon dioxide, carbon oxide, or sulphur dioxide. When pyranones, dioxothiophenes, or cyclopentadienones and DA cycloaddition are aided with acetylenes including masked ones, conjugated or isolated diynes, or polyynes and arynes, aromatic systems are obtained. This review covers the development and the current state of knowledge regarding thermal DA cycloaddition of dienes mentioned above and dienophiles leading to (hetero)aromatics via CO, CO2, or SO2 extrusion. Particular attention was paid to the role that introduced aromatic moieties play in designing molecular structures with expected properties. Undoubtedly, the DAC variants described in this review, combined with other modern synthetic tools, constitute a convenient and efficient way of obtaining functionalized nanomaterials, continually showing the potential to impact materials sciences and new technologies in the nearest future.

show abstract

“…However, only a few substances possessing conjugated substituents linked at these positions have been studied [33–35] . Importantly, the numbers of phenanthrenes in which π‐units are present at both 1,8‐ and 3,6‐positions are quite limited [36] …”

Section: Introductionmentioning

confidence: 99%

Synthesis, Photophysical and Electrochemical Study of 1,3,6,8‐Tetraarylsubstituted X‐Shaped Phenanthrene Derivatives

2022

View full text Add to dashboard Cite

X‐shaped phenanthrene derivatives containing aryl substituents at the 1,3,6,8‐positions were synthesized through Suzuki coupling reactions of two types of phenanthrenes possessing bromine and chlorine substituents. X‐shaped phenanthrenes, with four t‐butylphenyl, 9,9‐dimethyl‐9H‐fluoren‐2‐yl or 4‐diphenylaminophenyl (DPAP) groups, are highly emissive in the blue region and their fluorescence efficiencies increase as the extent of aryl π‐conjugation increases. To assess the effects of donor (D) and acceptor (A) groups at the 1,8‐ and 3,6‐positions on intramolecular charge‐transfer emission, two D−A compounds with two DPAP D‐groups and two 4‐pyridyl (Py) A‐groups were synthesized. Results of electrochemical studies reveal that the phenanthrene with four DPAP groups does not undergo oxidative polymerization in dichloromethane, but the two D−A analogs possessing both DPAP and Py groups do undergo oxidative polymerization, producing films which have electrochromic properties.

show abstract

Synthesis and Structures of Polyphenylphenanthrenes

Abstract: This is the author manuscript accepted for publication and has undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record.

Cited by 8 publications

References 29 publications

Extremely Crowded Biaryls

Extremely Crowded Biaryls

Diels–Alder Cycloaddition with CO, CO2, SO2, or N2 Extrusion: A Powerful Tool for Material Chemistry

Synthesis, Photophysical and Electrochemical Study of 1,3,6,8‐Tetraarylsubstituted X‐Shaped Phenanthrene Derivatives

Contact Info

Product

Resources

About