Molecular Complexes of the Biphenylenes. π-Complexes with Tetracyanoethylene

Farnum, Donald G.; Atkinson, Edward R.; Lothrop, Warren C.

doi:10.1021/jo01067a041

Cited by 16 publications

(7 citation statements)

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“…It is immediately apparent that contrary to the initially proposed [12] and calculated [43,44] arrangement, the centers of the components are shifted relative to each other and are distant (5.316 Å), which leads to only a moderate overlap. Furthermore, the molecular planes of the two components are not parallel but tilted by an angle of 9.84°with respect to each other.…”

Section: Crystallographic Analysis Of the Bp-tcne Complexcontrasting

confidence: 69%

“…Following the first report on the BP-TCNE complex, [12] the system was reinvestigated by others [41,42] and the association constant was determined more accurately. The initially obtained value of 5.1 M À 1 (22 °C) was corrected, and new values of 0.71 � 0.007 [41] and 0.96 � 0.1 [42] (both at 25 °C) were reported (in CH 2 Cl 2 solution).…”

Section: Analysis Of the Equilibrium In Ch 2 CL 2 Solutionmentioning

confidence: 99%

“…Early experimental approaches to probe the nature of bonding in BP involved UV-Vis spectroscopic measurements, [2,3] reactivity studies in electrophilic aromatic substitution reactions, [4,5] X-ray crystallographic [6] and electron diffraction [7] analysis, NMR spectroscopy, [8 -10] photoelectron spectroscopy [11] and electron donor-acceptor complex formation. [12] More recently, biphenylene derivatives have been investigated in the context of organic functional materials and as organic semiconductors. [13][14][15][16][17] Synthetic approaches are available for the systematic Supporting information for this article is available on the WWW under https://doi.org/10.1002/hlca.202300079 investigation of structure-property relationships through the preparation of various BP derivatives.…”

Section: Introductionmentioning

confidence: 99%

“…[36] Donor-acceptor complexes of BP with several electron acceptor type molecules have been studied. [12,[37][38][39] Interestingly, the subject of the very first such study, the complex of BP with tetracyanoethylene (TCNE), [12] remained poorly characterized and less understood.…”

Section: Introductionmentioning

confidence: 99%

“…The BP-TCNE system was first investigated by Farnum and co-workers, who wanted to compare it with the fluorene-TCNE complex. [12] Based on experimentally obtained association constants they determined a comparably higher stability for the BP-TCNE complex and concluded that this demonstrated some degree of electronic delocalization between the sixmembered rings of BP. In their measurements TCNE was used in excess due to the low amount of BP that was available at the time, and their analysis was based on only four data points.…”

Section: Introductionmentioning

confidence: 99%

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The π‐Molecular Complex of Biphenylene and Tetracyanoethylene

Dobszay,

Mayer,

Holczbauer

et al. 2023

Helvetica Chimica Acta

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The investigation of the biphenylene (BP)‐tetracyanoethylene (TCNE) π‐molecular complex is reported. The first study on this complex appeared in 1961 and was considered as a charge transfer complex with a symmetric, co‐planar arrangement of the components. Moreover, it was assumed that this arrangement is not only dictated by the formation of a Mulliken‐type donor‐acceptor complex, but also by the electronic stabilization of the “cyclobutadieneoid” central ring of biphenylene through complex formation. Yet, crystal structure and associated computational analysis have not verified these predictions so far. We found that factors other than charge‐transfer interactions are most influential in the crystal formation. The low association constant in solution, and the weak interaction between the components in the 1:1 crystal structure point towards the low contribution of charge transfer interactions to their binding. Nevertheless, the presence of these interaction is hinted by the color of its solution and verified by theoretical calculations. Furthermore, Nucleus Independent Chemical Shift (NICS) calculations were carried out to characterize potential changes in the (anti)aromatic character of BP upon complex formation. The NICS(0) values of the rings of BP exhibit tiny changes both in the BP‐TCNE dimer and in the crystal, which also suggests weak electronic interactions between them.

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Section: Crystallographic Analysis Of the Bp-tcne Complexcontrasting

confidence: 69%

Section: Analysis Of the Equilibrium In Ch 2 CL 2 Solutionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

The π‐Molecular Complex of Biphenylene and Tetracyanoethylene

Dobszay,

Mayer,

Holczbauer

et al. 2023

Helvetica Chimica Acta

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Cyanocarbons

Webster

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Cyanocarbons are organic compounds in which a substantial portion of the total functionality consists of cyano groups. As a consequence of the large number of cyano groups, the cyanocarbons are highly reactive electrophilic molecules. The most important members of the cyanocarbon family are tetracyanomethane, hexacyanoethane, tetracyanoethylene (TCNE), tetracyanoquinodimethan (TCNQ), hexacyanobutadiene, dicyanoacetylene, hexacyanobenzene, tetracyanoquinone, tricyanomethanide, pentacyanopropenide, pentacyanocyclopentadienide, tetracyanoethylene oxide, tetracyanofuran, tetracyanothiophene, tetracyanodithiin, diaminomaleonitrile (DAMN), diiminosuccinonitrile, tetracyanopyrazine, diazotetracyanocyclopentadiene, diazodicyanoimidazole, tetracyanopyrole, tricyanoimidazole, and pentacyanopyridine. Examples of unusual reactivity are numerous. TCNE forms colored charge‐transfer complexes with aromatic hydrocarbons, tetracyanoethylene oxide adds to olefins by cleavage of its carbon‐carbon bond, and TCNE and TCNQ react with metals to produce anion radicals.

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Electronic Structure and Spectral Properties of Annulenes and Related Compounds

Figeys

1969

Topics in Carbocyclic Chemistry

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Molecular Complexes of the Biphenylenes. π-Complexes with Tetracyanoethylene

Cited by 16 publications

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The π‐Molecular Complex of Biphenylene and Tetracyanoethylene

The π‐Molecular Complex of Biphenylene and Tetracyanoethylene

Cyanocarbons

Electronic Structure and Spectral Properties of Annulenes and Related Compounds

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