Biphenylene

Biphenylene is an alternant, polycyclic hydrocarbon composed of two benzene rings joined together by a pair of mutual attachments (as opposed to a normal ring fusion), thus forming a 6-4-6 arene system. The resulting planar structure[2] was one of the first π-electronic hydrocarbon systems discovered to show evidence of antiaromaticity.

Biphenylene
Names
Preferred IUPAC name
Biphenylene[1]
Other names
Diphenylene
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.217.287
UNII
Properties
C12H8
Molar mass 152.196 g·mol−1
Appearance Solid
Melting point 109 to 111 °C (228 to 232 °F; 382 to 384 K)
Related compounds
benzene
cyclobutene
cyclobutadiene
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YN ?)
Infobox references

Preparation

The biphenylene structure can also be understood as a dimer of the reactive intermediate benzyne, which in fact serves as a major synthetic route, by heating the benzenediazonium-2-carboxylate zwitterion prepared from 2-aminobenzoic acid.[3] Another approach is by N-amination of 1H-benzotriazole with hydroxylamine-O-sulfonic acid. The major product, 1-aminobenzotriazole, forms benzyne in an almost quantitative yield by oxidation with lead(IV) acetate, which rapidly dimerises to biphenylene in good yields.[4]

Synthesis of Benzyne and Biphenylene from 1H-Benzotriazole

Properties

Biphenylene, a pale yellowish solid with a hay-like odor, was first synthesized by Lothrop in 1941.[5] The chemistry of biphenylene is extensive, and has been the subject of two major reviews.[6][7] Biphenylene is quite stable both chemically and thermally, and behaves in many ways like a traditional polycyclic aromatic hydrocarbon. However, both the spectral and chemical properties show the influence of the central [4n] ring, leading to considerable interest in the system in terms of its degree of lessened aromaticity.

Questions of bond alternation and ring currents have been investigated repeatedly. Both X-ray diffraction[8] and electron diffraction[9] studies show a considerable alternation of bond lengths, with the bridging bonds between the benzenoid rings having the unusually great length of 1.524 Å. The separation of the rings is also reflected by the absence of the transmission of NMR substituent effects through the central [4n] ring.[10] However, more sensitive NMR evidence, and particularly the shifting of proton resonances to high field, does indicate the existence of electron delocalization in the central [4n] ring.[11][12] This upfield shift has been interpreted in terms of diminished benzenoid ring currents, either with or without an accompanying paramagnetic ring current in the central [4n] ring. Magnetic susceptibility measurements also show a diminishing of both diamagnetic exaltation and diamagnetic anisotropy, relative to comparable pure [4n+2] systems, which is also consistent with a reduction of ring current diamagnetism.[13][14] The electronic structure of biphenylene in the gas phase has the HOMO at a binding energy of 7.8 eV.[15]

Higher biphenylenes

A fair number of higher polycycles containing the biphenylene nucleus have also been prepared, some having considerable antiaromatic character.[16][17][18][19][20] In general, additional 6-membered rings add further aromatic character, and additional 4-membered and 8-membered rings add antiaromatic character. However, the exact natures of the additions and fusions greatly affect the perturbations of the biphenylene system, with many fusions resulting in counter-intuitive stabilization by [4n] rings, or destabilization by 6-membered rings. This has led to significant interest in the systems by theoretical chemists and graph theoreticians. Even a complete 2-dimensional carbon sheet with biphenylene-like subunits has been proposed[21] and was in depth investigated by theoretical means finding a technologically relevant direct band gap of ca. 1 eV, excitonic binding energies of ca. 500 meV and potential as gas sensor. [22][23][24]

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References
  1. "Front Matter". Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. p. 209. doi:10.1039/9781849733069-FP001. ISBN 978-0-85404-182-4.
  2. Waser, Jurg; Lu, Chia-Si (1944). "The Crystal Structure of Biphenylene". J. Am. Chem. Soc. 66 (12): 2035–2042. doi:10.1021/ja01240a012.
  3. Logullo, Francis M.; Seitz, Arnold M.; Friedman, Lester (1968). "Benzenediazonium-2-Carboxylate and Biphenylene (Benzenediazonium, o-carboxy-, hydroxide, inner salt)". Organic Syntheses. 48: 12. doi:10.15227/orgsyn.048.0012.; Collective Volume, 5, p. 54
  4. Campbell, C.D.; Rees, C.W. (1969). "Reactive intermediates. Part I. Synthesis and oxidation of 1- and 2-aminobenzotriazole". J. Chem. Soc. C. 1969 (5): 742–747. doi:10.1039/J39690000742.
  5. Lothrop, W. C. (1941). "Biphenylene". J. Am. Chem. Soc. 63 (5): 1187–1191. doi:10.1021/ja01850a007.
  6. Cava, M. P.; Mitchell, M. J. (1967). "10". Cyclobutadiene and Related Compounds. Academic Press. pp. 255–316.
  7. Barton, J. W. (1969). "2". In J. P. Snyder (ed.). Nonbenzenoid Aromatics. 1. Academic Press. pp. 32–62.
  8. Fawcett, J. K.; Trotter, J. (1966). "A refinement of the structure of biphenylene". Acta Crystallogr. 20: 87–93. doi:10.1107/s0365110x66000161.
  9. Yokozeki, A.; Wilcox Jr., C. F.; Bauer, S. H. (1974). "Biphenylene. Internuclear distances and their root mean square amplitudes of vibration". J. Am. Chem. Soc. 96 (4): 1026–1032. doi:10.1021/ja00811a014.
  10. Sheffy, Forrest K. (1982). (Thesis). Cornell University. Missing or empty |title= (help)
  11. Katritzky, A. R.; Reavill, R. E. (1964). "Nuclear magnetic resonance evidence for partial bond fixation in biphenylene". Recl. Trav. Chim. Pays-Bas. 83 (12): 1230–1232. doi:10.1002/recl.19640831203.
  12. Fraenkel, G.; Asahi, Y.; Mitchell, M. J.; Cava, M. P. (1964). "NMR spectroscopy of benzocyclobutene and biphenylene". Tetrahedron. 20 (5): 1179–1184. doi:10.1016/s0040-4020(01)98985-9.
  13. Dauben Jr., Hyp. J.; Wilson, James D.; Laity, John L. (1969). "Diamagnetic susceptibility exaltation in hydrocarbons". J. Am. Chem. Soc. 91 (8): 1991–1998. doi:10.1021/ja01036a022.
  14. Anet, F. A. L.; Schenck, G. (1971). "Application of solvent effects to the study of diamagnetic and paramagnetic ring currents". J. Am. Chem. Soc. 93 (2): 556–557. doi:10.1021/ja00731a061.
  15. Lüder, Johann; de Simone, Monica; Totani, Roberta; et al. (2015). "The electronic characterization of biphenylene—Experimental and theoretical insights from core and valence level spectroscopy" (PDF). J. Chem. Phys. 142 (7): 074305. Bibcode:2015JChPh.142g4305L. doi:10.1063/1.4907723. hdl:11368/2842819. PMID 25702013.
  16. Wilcox Jr., Charles F.; Uetrecht, J. P.; Grohman, K. K. (1972). "Cycloocta[def]biphenylene". J. Am. Chem. Soc. 94 (7): 2532. doi:10.1021/ja00762a068.
  17. Wilcox Jr., Charles F.; Farley, Erik N. (1983). "Dicycloocta[1,2,3,4-def:1',2',3',4'-jkl]biphenylene. Benzenoid Atropism in a Highly Antiaromatic Polycycle". J. Am. Chem. Soc. 105 (24): 7191–7192. doi:10.1021/ja00362a040.
  18. Wilcox Jr., Charles F.; Farley, Erik N. (1984). "Dicyclooctabiphenylene. Synthesis and Properties". J. Am. Chem. Soc. 106 (23): 7195–7200. doi:10.1021/ja00335a055.
  19. Wilcox Jr., Charles F.; Farley, Erik N. (1985). "Cyclooctannelated Biphenylenes. Diagnosis of an Anomalous Bond Length by Analysis of Ring Current Geometric Factors". J. Org. Chem. 50 (3): 351–356. doi:10.1021/jo00203a013.
  20. Farley, Erik Neil (1984). Dicyclooctabiphenylenes (Thesis). Cornell University.
  21. Balaban, A. T. (1968). Revue Roumaine de Chimie. 13: 231. Missing or empty |title= (help)
  22. G. Brunetto, P. A. S. Autreto, L. D. Machado, B. I. Santos, R. P. B. dos Santos, and D. S. Galvao (2012). "Nonzero gap two-dimensional carbon allotrope from porous graphene". J. Phys. Chem. C . 116 (23): 12810–12813. arXiv:1205.6838. Bibcode:2012arXiv1205.6838B. doi:10.1021/jp211300n.CS1 maint: multiple names: authors list (link)
  23. Lüder J., Puglia C., Ottosson H., Eriksson O., Sanyal B., Brena B. (2016). "Many-body effects and excitonic features in 2D biphenylene carbon". J. Chem. Phys. . 144 (2): 024702. Bibcode:2016JChPh.144b4702L. doi:10.1063/1.4939273. PMID 26772582.CS1 maint: multiple names: authors list (link)
  24. Zhu L., Jin Y.,Xue Q., Li X., Zheng H., Wu T. Ling C. (2016). "Theoretical study of a tunable and strain-controlled nanoporous graphenylene membrane for multifunctional gas separation". J. Mater. Chem. A. 4 (39): 15015–15021. doi:10.1039/C6TA04456E.CS1 maint: multiple names: authors list (link)
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