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Revision as of 02:41, 11 September 2011 editCheMoBot (talk | contribs)Bots141,565 edits Updating {{chembox}} (no changed fields - added verified revid - updated 'DrugBank_Ref', 'UNII_Ref', 'ChEMBL_Ref') per Chem/Drugbox validation (report errors or bugs)← Previous edit		Latest revision as of 00:24, 9 November 2024 edit undo73.231.198.119 (talk) Added Buckybowl under other names.
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	{{chembox		{{chembox
			| Watchedfields = changed
	| verifiedrevid = 447509288		| verifiedrevid = 449660083
	| ImageFile = Corannulene.svg		| ImageFile = Corannulene.svg
	| ImageSize = 150px		| ImageSize = 150px
	| ImageFile1 = Corannulene3D.png		| ImageFile1 = Corannulene3D.png
	| ImageSize1 = 150px		| ImageSize1 = 150px
	| IUPACName = Dibenzofluoranthene		| IUPACName = Dibenzofluoranthene<ref>
			] is so named for its fluorescent property. It is not a fluorine compound.</ref>
	| OtherNames = circulene		| OtherNames = circulene; Buckybowl
	| Section1 = {{Chembox Identifiers		|Section1={{Chembox Identifiers
	| Abbreviations =		| Abbreviations =
	| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}		| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
	| ChemSpiderID = 10006487		| ChemSpiderID = 10006487
	| InChIKey = VXRUJZQPKRBJKH-UHFFFAOYAF		| InChIKey = VXRUJZQPKRBJKH-UHFFFAOYAF
	| SMILES1 = c1cc2ccc3ccc4ccc5ccc1c6c2c3c4c56		| SMILES1 = C1=CC2=CC=C3C=CC4=C5C6=C(C2=C35)C1=CC=C6C=C4
	| StdInChI_Ref = {{stdinchicite|correct|chemspider}}		| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
	| StdInChI = 1S/C20H10/c1-2-12-5-6-14-9-10-15-8-7-13-4-3-11(1)16-17(12)19(14)20(15)18(13)16/h1-10H		| StdInChI = 1S/C20H10/c1-2-12-5-6-14-9-10-15-8-7-13-4-3-11(1)16-17(12)19(14)20(15)18(13)16/h1-10H
	| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}		| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
	| StdInChIKey = VXRUJZQPKRBJKH-UHFFFAOYSA-N		| StdInChIKey = VXRUJZQPKRBJKH-UHFFFAOYSA-N
			| CASNo_Ref = {{cascite|correct|CAS}}
	| CASNo = 5821-51-2		| CASNo = 5821-51-2
			| UNII_Ref = {{fdacite|correct|FDA}}
			| UNII = KFD2X7NT86
	| EINECS =		| EINECS =
	| PubChem = 11831840		| PubChem = 11831840
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	| KEGG_Ref = {{keggcite|correct|kegg}}		| KEGG_Ref = {{keggcite|correct|kegg}}
	| KEGG =		| KEGG =
			}}
	| ATCCode_prefix =
		⚫	|Section2={{Chembox Properties
	| ATCCode_suffix =
	| ATC_Supplemental =}}
⚫	| Section2 = {{Chembox Properties
	| Formula = ]<sub>20</sub>]<sub>10</sub>		| Formula = ]<sub>20</sub>]<sub>10</sub>
	| MolarMass = 250.29 g/mol		| MolarMass = 250.29 g/mol
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	| Density =		| Density =
	| MeltingPt =		| MeltingPt =
	| Melting_notes =		| MeltingPt_notes =
	| BoilingPt =		| BoilingPt =
	| Boiling_notes =		| BoilingPt_notes =
	| Solubility =		| Solubility =
	| SolubleOther =		| SolubleOther =
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	| pKa =		| pKa =
	| pKb = }}		| pKb = }}
	| Section7 = {{Chembox Hazards		|Section7={{Chembox Hazards
	| EUClass =
	| EUIndex =
	| MainHazards =		| MainHazards =
	| NFPA-H =		| NFPA-H =
	| NFPA-F =		| NFPA-F =
	| NFPA-R =		| NFPA-R =
	| NFPA-O =		| NFPA-S =
	| RPhrases =
	| SPhrases =
	| RSPhrases =
	| FlashPt =		| FlashPt =
	| Autoignition =		| AutoignitionPt =
	| ExploLimits =		| ExploLimits =
	| PEL = }}		| PEL = }}
	}}		}}
	'''Corannulene''' is a ] with ] ]<sub>20</sub>]<sub>10</sub>.<ref>{{cite DOI|10.1351/pac199971020209}}</ref> The ] consists of a ] ring ] with 5 ] rings, so another name for it is circulene. It is of scientific interest because it is a ] and can be considered a fragment of ]. Due to this connection and also its bowl shape, corannulene is also known as a '''buckybowl'''. Corannulene exhibits a bowl-to-bowl inversion with an ] of 10.2 ]/] (42.7 ]/mol) at −64 °C.<ref name="cite DOI|10.1021/ja00031a079">{{cite DOI|10.1021/ja00031a079}}</ref>		'''Corannulene''' is a ] with ] ]<sub>20</sub>]<sub>10</sub>.<ref>{{Cite journal| doi = 10.1351/pac199971020209| title = Geodesic polyarenes with exposed concave surfaces| year = 1999| last1 = Scott | first1 = L. T.| last2 = Bronstein | first2 = H. E.| last3 = Preda | first3 = D. V.| last4 = Ansems | first4 = R. B. M.| last5 = Bratcher | first5 = M. S.| last6 = Hagen | first6 = S.| journal = Pure and Applied Chemistry| volume = 71| issue = 2| pages = 209 | s2cid = 37901191| doi-access = free}}</ref> The ] consists of a ] ring ] with 5 ] rings, so another name for it is ]. It is of scientific interest because it is a ] and can be considered a fragment of ]. Due to this connection and also its bowl shape, corannulene is also known as a '''buckybowl.''' Buckybowls are fragments of buckyballs. Corannulene exhibits a bowl-to-bowl inversion with an ] of 10.2 ]/] (42.7 ]/mol) at −64&nbsp;°C.<ref name="cite DOI|10.1021/ja00031a079">{{Cite journal| doi = 10.1021/ja00031a079| title = Corannulene bowl-to-bowl inversion is rapid at room temperature| year = 1992| last1 = Scott | first1 = L. T.| last2 = Hashemi | first2 = M. M.| last3 = Bratcher | first3 = M. S.| journal = Journal of the American Chemical Society| volume = 114| issue = 5| pages = 1920–1921 }}</ref>
	==Synthesis==		==Synthesis==
	Several synthetic routes exist to corannulene. ] techniques generally have lower ]s than solution-chemistry syntheses, but offer routes to more derivatives. Corannulane was first isolated in 1966 by multistep organic synthesis.<ref name="cite DOI|10.1021/ja00954a049">{{cite DOI|10.1021/ja00954a049}}</ref> A flash vacuum pyrolysis method followed in 1991.<ref>{{cite DOI|10.1021/ja00018a082}}</ref> One synthesis based on solution chemistry<ref>{{cite DOI|10.1021/ja0011461}}</ref> consists of a ]&ndash;] of an octabromide with ]:		Several synthetic routes exist to corannulene. ] techniques generally have lower ]s than solution-chemistry syntheses, but offer routes to more derivatives. Corannulene was first isolated in 1966 by multistep organic synthesis.<ref name="cite DOI|10.1021/ja00954a049">{{Cite journal| doi = 10.1021/ja00954a049| year = 1966| last1 = Barth | first1 = W. E.| title = Dibenzofluoranthene| last2 = Lawton | first2 = R. G.| journal = Journal of the American Chemical Society| volume = 88| issue = 2| pages = 380–381 }}</ref> In 1971, the synthesis and properties of corannulane were reported.<ref>{{cite journal|last1=Lawton|first1=Richard G.|last2=Barth|first2=Wayne E.|title=Synthesis of corannulene|journal=Journal of the American Chemical Society|date=April 1971|volume=93|issue=7|pages=1730–1745|doi=10.1021/ja00736a028|s2cid=94872875 }}</ref> A flash vacuum pyrolysis method followed in 1991.<ref>{{Cite journal| last4 = Warren | first3 = D. T. | first4 = H. B.| journal = Journal of the American Chemical Society| pages = 7082–7084| volume = 113| doi = 10.1021/ja00018a082| last3 = Meyer| year = 1991| title = Corannulene. A convenient new synthesis | first2 = M. M.| last1 = Scott | first1 = L. T.| last2 = Hashemi| issue = 18 }}</ref> One synthesis based on solution chemistry<ref>{{Cite journal| doi = 10.1021/ja0011461| title = A Practical, Large Scale Synthesis of the Corannulene System| year = 2000| last1 = Sygula | first1 = A.| last2 = Rabideau | first2 = P. W.| journal = Journal of the American Chemical Society| volume = 122| issue = 26| pages = 6323–6324 }}</ref> consists of a ]&ndash;] of an octabromide with ]:
	:]		:]
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	The bromine substituents are removed with an excess of ].		The bromine substituents are removed with an excess of ].
			A kilogram scale synthesis of corannulene has been achieved.<ref>{{Cite journal| doi = 10.1021/op200387s| title = Kilogram-Scale Production of Corannulene| year = 2012| last1 = Butterfield | first1 = A.| last2 = Gilomen | first2 = B.| last3 = Siegel | first3 = J.| journal = Organic Process Research & Development| volume = 16| issue = 4| pages = 664–676 }}</ref>
	Much effort is directed at functionalization of the corannulene ring with novel functional groups such as ethynyl groups,<ref name="cite DOI|10.1021/ja00031a079"/><ref>{{cite DOI|10.1021/ja802334n}}</ref><ref name=Mack>{{cite DOI|10.1039/b705621d}}</ref> ether groups,<ref>{{cite DOI|10.1021/ol902352k}}</ref> thioether groups,<ref>{{cite DOI|10.1039/b919616a}}</ref> platinum function groups,<ref>{{cite DOI|10.1016/j.jorganchem.2009.07.015}}</ref> aryl groups,<ref name=pappo>{{cite DOI|10.1021/ol8028127}}</ref> phenalenyl fused <ref>{{cite DOI|10.1021/ja806708j}}</ref> and indeno extensions.<ref>{{cite DOI|10.1021/ja9031852}}</ref>
			Much effort is directed at functionalization of the corannulene ring with novel functional groups such as ethynyl groups,<ref name="cite DOI|10.1021/ja00031a079"/><ref>{{Cite journal| doi = 10.1021/ja802334n| pmid = 18642812| year = 2008| last1 = Wu | first1 = Y.| last2 = Bandera | first2 = D.| last3 = Maag | first3 = R.| last4 = Linden | first4 = A.| last5 = Baldridge | first5 = K.| last6 = Siegel | first6 = J.| title = Multiethynyl corannulenes: synthesis, structure, and properties| volume = 130| issue = 32| pages = 10729–10739| journal = Journal of the American Chemical Society }}</ref><ref name=Mack>{{Cite journal| doi = 10.1039/b705621d| pmid = 17637965| year = 2007| last1 = Mack | first1 = J.| last2 = Vogel | first2 = P.| last3 = Jones | first3 = D.| last4 = Kaval | first4 = N.| last5 = Sutton | first5 = A.| title = The development of corannulene-based blue emitters| volume = 5| issue = 15| pages = 2448–2452| journal = ]}}</ref> ether groups,<ref>{{Cite journal| doi = 10.1021/ol902352k| pmid = 19905024| year = 2009| last1 = Gershoni-Poranne | first1 = R.| last2 = Pappo | first2 = D.| last3 = Solel | first3 = E.| last4 = Keinan | first4 = E.| title = Corannulene ethers via Ullmann condensation| volume = 11| issue = 22| pages = 5146–5149| journal = Organic Letters }}</ref> thioether groups,<ref>{{Cite journal| doi = 10.1039/b919616a| pmid = 20024131| year = 2010| last1 = Baldridge | first1 = K.| last2 = Hardcastle | first2 = K.| last3 = Seiders | first3 = T.| last4 = Siegel | first4 = J.| title = Synthesis, structure and properties of decakis(phenylthio)corannulene| volume = 8| issue = 1| pages = 53–55| journal = Organic & Biomolecular Chemistry }}</ref> platinum functional groups,<ref>{{Cite journal| doi = 10.1016/j.jorganchem.2009.07.015| title = Synthesis and structure of penta-platinum σ-bonded derivatives of corannulene| year = 2009| last1 = Choi | first1 = H.| last2 = Kim | first2 = C.| last3 = Park | first3 = K. M.| last4 = Kim | first4 = J.| last5 = Kang | first5 = Y.| last6 = Ko | first6 = J.| journal = Journal of Organometallic Chemistry| volume = 694| issue = 22| pages = 3529–3532 }}</ref> aryl groups,<ref name=pappo>{{Cite journal| doi = 10.1021/ol8028127| pmid = 19193048| year = 2009| last1 = Pappo | first1 = D.| last2 = Mejuch | first2 = T.| last3 = Reany | first3 = O.| last4 = Solel | first4 = E.| last5 = Gurram | first5 = M.| last6 = Keinan | first6 = E.| title = Diverse Functionalization of Corannulene: Easy Access to Pentagonal Superstructure| journal = Organic Letters| volume = 11| issue = 5| pages = 1063–1066 }}</ref> phenalenyl fused <ref>{{Cite journal | first8 = T.| last9 = Nakasuji| last8 = Takui | first7 = K.| last7 = Sato | first9 = K.| title = Curve-structured phenalenyl chemistry: synthesis, electronic structure, and bowl-inversion barrier of a phenalenyl-fused corannulene anion| journal = Journal of the American Chemical Society| pages = 14954–14955| issue = 45| volume = 130 | first6 = K.| last6 = Ogasawara | first1 = S.| last2 = Morita| last1 = Nishida| year = 2008| pmid = 18937470 | first2 = Y.| last3 = Ueda| last5 = Fukui | first5 = K. | first4 = T.| last4 = Kobayashi | first3 = A.| doi = 10.1021/ja806708j }}</ref> and indeno extensions.<ref>{{Cite journal| doi = 10.1021/ja9031852| pmid = 19722628| year = 2009| last1 = Steinberg | first1 = B.| last2 = Jackson | first2 = E.| last3 = Filatov | first3 = A.| last4 = Wakamiya | first4 = A.| last5 = Petrukhina | first5 = M.| last6 = Scott | first6 = L.| title = Aromatic pi-systems more curved than C(60). The complete family of all indenocorannulenes synthesized by iterative microwave-assisted intramolecular arylations| volume = 131| issue = 30| pages = 10537–10545| journal = Journal of the American Chemical Society }}</ref> and ] groups.<ref name="Schmidt">{{cite journal | last1 = Topolinski | first1 = Berit | last2 = Schmidt | first2 = Bernd M. | last3 = Kathan | first3 = Michael | last4 = Troyanov | first4 = Sergej I. | last5 = Lentz | first5 = Dieter | year = 2012 | title = Corannulenylferrocenes: towards a 1D, non-covalent metal–organic nanowire | journal = Chem. Commun. | volume = 48 | issue = 50| pages = 6298–6300 | doi = 10.1039/C2CC32275G | pmid = 22595996 }}</ref>
	==Aromaticity==		==Aromaticity==
	The observed ] for this compound is explained with a so-called '''annulene-within-an-annulene model'''. According to this model corannulene is made up of an aromatic 6 electron ] surrounded by an aromatic 14 electron '''annulenyl''' ]. This model was suggested by Barth and Lawton in the first synthesis of corannulene in 1966.<ref name="cite DOI|10.1021/ja00954a049"/> They also suggested the trivial name 'corannulene', which is derived from the annulene-within-an-annulene model: core + annulene.		The observed ] for this compound is explained with a so-called '''annulene-within-an-annulene model'''. According to this model corannulene is made up of an aromatic 6 electron ] surrounded by an aromatic 14 electron '''{{chem name|annulenyl}}''' ]. This model was suggested by Barth and Lawton in the first synthesis of corannulene in 1966.<ref name="cite DOI|10.1021/ja00954a049"/> They also suggested the trivial name 'corannulene', which is derived from the annulene-within-an-annulene model: core + annulene.
		⚫	:]
			However, later theoretical calculations have disputed the validity of this approximation.<ref>{{Cite journal | doi = 10.1016/0166-1280(94)03961-J | title = Structure and inversion barriers of corannulene, its dianion and tetraanion. An ab initio study | first2 = P. W. | year = 1995 | last2 = Rabideau | last1 = Sygula | first1 = A. | journal = Journal of Molecular Structure: THEOCHEM | volume = 333 | issue = 3 | pages = 215–226 }}</ref><ref>{{Cite journal| doi = 10.1021/jp8038779| pmid = 18693706| year = 2008| last1 = Monaco | first1 = G.| last2 = Scott | first2 = L.| last3 = Zanasi | first3 = R.| title = Magnetic euripi in corannulene| volume = 112| issue = 35| pages = 8136–8147| journal = The Journal of Physical Chemistry A | bibcode = 2008JPCA..112.8136M}}</ref>
⚫	:]
			==Reactions==
	However, later theoretical calculations have disputed the validity of this approximation.<ref>{{cite doi|10.1016/0166-1280(94)03961-J}}</ref><ref>{{cite doi|10.1021/jp8038779}}</ref>
	== Corannulene anions ==		=== Reduction ===
	Corannulene can be reduced up to a tetraanion in a series of ]s. This has been performed with ], electrochemically and with bases. The corannulene dianion is ] and tetraanion is again ]. With ] as ] two tetraanions form a ] dimer with two bowls stacked into each other with 4 lithium ions in between and 2 pairs above and below the stack.<ref>{{cite DOI|10.1126/science.265.5175.1065}}</ref>. This self-assembly motif was applied in the organization of fullerenes. Penta-substituted fullerenes (with methyl or phenyl groups) charged with five electrons form supramolecular dimers with a complementary corannulene tetraanion bowl, 'stitched' by interstitial lithium cations.<ref>{{cite DOI|10.1021/ja0515102}}</ref> In a related system 5 lithium ions are sandwiched between two corannulene bowls <ref>''A Main Group Metal Sandwich: Five Lithium Cations Jammed Between Two Corannulene Tetraanion Decks'' Zabula, et al. Science 19 August 2011: 1008-1011. {{DOI|10.1126/science.1208686}} </ref>		Corannulene can be reduced up to a tetraanion in a series of ]s. This has been performed with ], electrochemically and with bases. The corannulene dianion is ] and tetraanion is again ]. With ] as ] two tetraanions form a ] dimer with two bowls stacked into each other with 4 lithium ions in between and 2 pairs above and below the stack.<ref>{{Cite journal| doi = 10.1126/science.265.5175.1065| pmid = 17832895| year = 1994| last1 = Ayalon | first1 = A.| last2 = Sygula | first2 = A.| last3 = Cheng | first3 = P.| last4 = Rabinovitz | first4 = M.| last5 = Rabideau | first5 = P.| last6 = Scott | first6 = L.| title = Stable High-Order Molecular Sandwiches: Hydrocarbon Polyanion Pairs with Multiple Lithium Ions Inside and out| volume = 265| issue = 5175| pages = 1065–1067| journal = Science |bibcode = 1994Sci...265.1065A | s2cid = 4979579}}</ref> This self-assembly motif was applied in the organization of fullerenes. Penta-substituted fullerenes (with methyl or phenyl groups) charged with five electrons form supramolecular dimers with a complementary corannulene tetraanion bowl, 'stitched' by interstitial lithium cations.<ref>{{Cite journal| doi = 10.1021/ja0515102| pmid = 15984885| year = 2005| last1 = Aprahamian | first1 = I.| last2 = Eisenberg | first2 = D.| last3 = Hoffman | first3 = R.| last4 = Sternfeld | first4 = T.| last5 = Matsuo | first5 = Y.| last6 = Jackson | first6 = E.| last7 = Nakamura | first7 = E.| last8 = Scott | first8 = L.| last9 = Sheradsky | first9 = T.| last10 = Rabinovitz | first10 = M.| title = Ball-and-socket stacking of supercharged geodesic polyarenes: bonding by interstitial lithium ions| volume = 127| issue = 26| pages = 9581–9587| journal = Journal of the American Chemical Society }}</ref> In a related system 5 lithium ions are sandwiched between two corannulene bowls <ref>{{cite journal | doi = 10.1126/science.1208686 | volume=333 | title=A Main Group Metal Sandwich: Five Lithium Cations Jammed Between Two Corannulene Tetraanion Decks | year=2011 | journal=Science | pages=1008–1011 | last1 = Zabula | first1 = A. V.| issue=6045 | pmid=21852497 | bibcode=2011Sci...333.1008Z | s2cid=1125747 }}</ref>
	In one cyclopentacorannulene a concave - concave aggregate is observed by ] with 2 C–Li–C bonds connecting the tetraanions.<ref>{{cite DOI|10.1021/jo051949c}}</ref>		In one cyclopentacorannulene a concave - concave aggregate is observed by ] with 2 C–Li–C bonds connecting the tetraanions.<ref>{{Cite journal| doi = 10.1021/jo051949c| pmid = 16388648| year = 2006| last1 = Aprahamian | first1 = I.| last2 = Preda | first2 = D.| last3 = Bancu | first3 = M.| last4 = Belanger | first4 = A.| last5 = Sheradsky | first5 = T.| last6 = Scott | first6 = L.| last7 = Rabinovitz | first7 = M.| title = Reduction of bowl-shaped hydrocarbons: dianions and tetraanions of annelated corannulenes| volume = 71| issue = 1| pages = 290–298| journal = The Journal of Organic Chemistry }}</ref>
	:corannulene]]{{clear}}		:corannulene]]{{clear}}
	Metals tend to bind to the convex face of the annulene. Concave binding has been reported for a cesium / crown ether system <ref>Spisak, S. N., Zabula, A. V., Filatov, A. S., Rogachev, A. Y. and Petrukhina, M. A. (2011), ''Selective Endo and Exo Binding of Alkali Metals to Corannulene''. Angewandte Chemie International Edition, 50: 8090–8094. {{doi|10.1002/anie.201103028}}</ref>		Metals tend to bind to the convex face of the annulene. Concave binding has been reported for a cesium / crown ether system <ref>{{cite journal | last1 = Spisak | first1 = S. N. | last2 = Zabula | first2 = A. V. | last3 = Filatov | first3 = A. S. | last4 = Rogachev | first4 = A. Y. | last5 = Petrukhina | first5 = M. A. | year = 2011 | title = Selective Endo and Exo Binding of Alkali Metals to Corannulene | journal = Angewandte Chemie International Edition | volume = 50 | issue = 35| pages = 8090–8094 | doi = 10.1002/anie.201103028 | pmid=21748832 }}</ref>
			=== Oxidation===
⚫	==Corannulene radicals==
			UV 193-nm photoionization effectively removes a π-electron from the twofold degenerate E<sub>1</sub>-HOMO located in the aromatic network of electrons yielding a corannulene radical cation.<ref name="hag">{{cite journal|last=Galué|first=Héctor Alvaro|author2=Rice, Corey A. |author3=Steill, Jeffrey D. |author4=Oomens, Jos |title=Infrared spectroscopy of ionized corannulene in the gas phase|journal=The Journal of Chemical Physics|date=1 January 2011|volume=134|issue=5|pages=054310|doi=10.1063/1.3540661|pmid=21303123|bibcode = 2011JChPh.134e4310G |url=https://pure.uva.nl/ws/files/1233463/94290_345138.pdf}}</ref> Owing to the degeneracy in the HOMO orbital, the corannulene radical cation is unstable in its original C<sub>5v</sub> molecular arrangement, and therefore, subject to Jahn-Teller (JT) vibronic distortion.
⚫	Corannulene-based ]s have also been synthesised and studied.<ref>''The First Bowl-Shaped Stable Neutral Radical with a Corannulene System:  Synthesis and Characterization of the Electronic Structure'' Yasushi Morita, Shinsuke Nishida, Tadahiro Kobayashi, Kozo Fukui, Kazunobu Sato, Daisuke Shiomi, Takeji Takui, Kazuhiro Nakasuji Organic Letters 2004 6 (9), 1397-1400 {{doi| 10.1021/ol0497786}}</ref><ref>{{cite DOI|10.1002/anie.200704752}}</ref><ref>{{cite DOI|10.1002/anie.200906666}}</ref> A semiquinone radical anion obtained by reduction of the diketone by a ] (see below) has been reported stable in the solid state <ref>Ueda, A., Ogasawara, K., Nishida, S., Ise, T., Yoshino, T., Nakazawa, S., Sato, K., Takui, T., Nakasuji, K. and Morita, Y. (2010), ''A Bowl-Shaped ortho-Semiquinone Radical Anion: Quantitative Evaluation of the Dynamic Behavior of Structural and Electronic Features''. Angewandte Chemie International Edition, 49: 6333–6337. {{doi|10.1002/anie.201002626}}</ref>
⚫	:].
⚫	In this radical anion spin density is delocalized with a significant contribution from the central cyclopentadienyl radical.
			Using electrospray ionization, a protonated corannulene cation has been produced in which the protonation site was observed to be on a peripheral sp<sup>2</sup>-carbon atom.<ref name="hag" />
	==Corannulene carbocations==
⚫	Corannulene can react with ]s to form a corannulene ]. Reaction with ] and ] results in the formation of an AlCl<sub>4</sub><sup>-</sup> salt with a methyl group situated at the center with the cationic center at the rim. ] analysis shows the that the new carbon-carbon bond is elongated (157 pm) <ref>Zabula, A. V., Spisak, S. N., Filatov, A. S., Rogachev, A. Y. and Petrukhina, M. A. (2011),'' A Strain-Releasing Trap for Highly Reactive Electrophiles: Structural Characterization of Bowl-Shaped Arenium Carbocations.'' Angewandte Chemie International Edition, 50: 2971–2974. {{doi|10.1002/anie.201007762}}</ref>
			===Reaction with electrophiles===
⚫	==Bicorannulenyl==
		⚫	Corannulene can react with ]s to form a corannulene ]. Reaction with ] and ] results in the formation of an AlCl<sub>4</sub><sup>−</sup> salt with a methyl group situated at the center with the cationic center at the rim. ] analysis shows that the new carbon-carbon bond is elongated (157 pm) <ref>{{cite journal | last1 = Zabula | first1 = A. V. | last2 = Spisak | first2 = S. N. | last3 = Filatov | first3 = A. S. | last4 = Rogachev | first4 = A. Y. | last5 = Petrukhina | first5 = M. A. | year = 2011 | title = A Strain-Releasing Trap for Highly Reactive Electrophiles: Structural Characterization of Bowl-Shaped Arenium Carbocations | journal = Angewandte Chemie International Edition | volume = 50 | issue = 13 | pages = 2971–2974 | doi = 10.1002/anie.201007762 | pmid = 21404379 }}</ref>
⚫	'''Bicorannulenyl''' is the corannulene dimer, in which two corannulene units are connected through a single bond. The molecule's stereochemistry consists of two chiral elements: the asymmetry of a singly substituted corannulenyl, and the helical twist about the central bond. In the neutral state, bicorannulenyl exists as 12 conformers, which intercovert through multiple bowl-inversions and bond-rotations.<ref>{{cite DOI|10.1021/jo800359z}}</ref>
	When bicorannulenyl is reduced to a dianion with potassium metal, the central bond assumes significant double-bond character. This is due to its orbital structure, which has a LUMO orbital localized on the central bond.<ref>Eisenberg, D., Quimby, J. M., Jackson, E. A., Scott, L. T. and Shenhar, R. (2010), ''The Bicorannulenyl Dianion: A Charged Overcrowded Ethylene''. Angewandte Chemie International Edition, 49: 7538–7542. {{doi|10.1002/anie.201002515}}</ref>
	When bicorannulenyl is reduced to an octaanion with lithium metal, it self-assembles into supramolecular oligomers.<ref>Eisenberg, D., Quimby, J. M., Jackson, E. A., Scott, L. T. and Shenhar, R. (2010), ''Highly Charged Supramolecular Oligomers Based on the Dimerization of Corannulene Tetraanion''. Chemical Communications, 46: 9010–9012. {{doi|10.1039/c0cc03965a}}</ref>
	This is based on the "charged polyarene stacking" self-assembly motif.
		⚫	<!-- pretty tangential==Corannulene radicals==
	==Applications==
		⚫	Corannulene-based ]s have also been synthesised and studied.<ref>{{cite journal | doi = 10.1021/ol0497786 | volume=6 | title=The First Bowl-Shaped Stable Neutral Radical with a Corannulene System: Synthesis and Characterization of the Electronic Structure | year=2004 | journal=Organic Letters | pages=1397–1400 | last1 = Morita | first1 = Yasushi}}</ref><ref>{{cite journal|doi=10.1002/anie.200704752 | volume=47 | title=Curved Aromaticity of a Corannulene-Based Neutral Radical: Crystal Structure and 3 D Unbalanced Delocalization of Spin | year=2008 | journal=Angewandte Chemie International Edition | pages=2035–2038 | last1 = Morita | first1 = Yasushi | pmid=18256997}}</ref><ref>{{cite journal|doi=10.1002/anie.200906666 | volume=49 | title=Three-Dimensional Intramolecular Exchange Interaction in a Curved and Nonalternant π-Conjugated System: Corannulene with Two Phenoxyl Radicals | year=2010 | journal=Angewandte Chemie International Edition | pages=1678–1682 | last1 = Ueda | first1 = Akira | pmid=20108294}}</ref> A semiquinone radical anion obtained by reduction of the diketone by a ] (see below) has been reported stable in the solid state <ref>{{cite journal | last1 = Ueda | first1 = A. | last2 = Ogasawara | first2 = K. | last3 = Nishida | first3 = S. | last4 = Ise | first4 = T. | last5 = Yoshino | first5 = T. | last6 = Nakazawa | first6 = S. | last7 = Sato | first7 = K. | last8 = Takui | first8 = T. | last9 = Nakasuji | first9 = K. | last10 = Morita | first10 = Y. | year = 2010 | title = A Bowl-Shaped ortho-Semiquinone Radical Anion: Quantitative Evaluation of the Dynamic Behavior of Structural and Electronic Features | journal = Angewandte Chemie International Edition | volume = 49 | pages = 6333–6337 | doi = 10.1002/anie.201002626 | pmid=20661977}}</ref>
	]The corannulene group is used in ] with interactions based on ] , notably with ]s (the buckycatcher) <ref>{{cite DOI|10.1021/ja070616p}}</ref><ref>{{cite DOI|10.1002/jcc.21022 }}</ref> but also with ] <ref>{{cite DOI|10.1016/j.tetlet.2009.09.177}}</ref>
		⚫	:].
		⚫	In this radical anion spin density is delocalized with a significant contribution from the central cyclopentadienyl radical.-->
		⚫	==Bicorannulenyl==
	With long aliphatic side chains corannulenes are reported forming a thermotropic hexagonal columnar ].<ref>{{cite DOI|10.1021/ja808396b}}</ref> Corannulenes have also been used as the core group in a ] <ref name=pappo/> or as coordinating ] to metals.<ref>''Hexahapto Metal Coordination to Curved Polyaromatic Hydrocarbon Surfaces: The First Transition Metal Corannulene Complex'' T. Jon Seiders, Kim K. Baldridge, Joseph M. O'Connor, and Jay S. Siegel J. Am. Chem. Soc., 1997, 119 (20), pp 4781–4782 {{DOI|10.1021/ja964380t}}</ref><ref>''d8 Rhodium and Iridium Complexes of Corannulene'' Jay S. Siegel, Kim K. Baldridge, Anthony Linden, and Reto Dorta J. Am. Chem. Soc., 2006, 128 (33), pp 10644–10645 {{DOI|10.1021/ja062110x}}</ref><ref>{{cite DOI|10.1002/anie.200704783}}</ref><ref>{{cite DOI|10.1021/om0610795}}</ref><ref>{{cite DOI|10.1021/om060350f}}</ref><ref>{{cite DOI|10.1021/ja062110x}}</ref><ref>Bandera, D., Baldridge, K. K., Linden, A., Dorta, R. and Siegel, J. S. (2011),'' Stereoselective Coordination of C5-Symmetric Corannulene Derivatives with an Enantiomerically Pure Metal Complex.'' Angewandte Chemie International Edition, 50: 865–867. doi: 10.1002/anie.201006877</ref> Corannulenes with ethynyl groups are investigated for their potential use as blue emitters.<ref name=Mack/>
		⚫	'''Bicorannulenyl''' is the product of dehydrogenative coupling of corannulene. With the formula C<sub>20</sub>H<sub>9</sub>-C<sub>20</sub>H<sub>9</sub>, it consists of two corannulene units connected through a single C-C bond. The molecule's stereochemistry consists of two chiral elements: the asymmetry of a singly substituted corannulenyl, and the helical twist about the central bond. In the neutral state, bicorannulenyl exists as 12 conformers, which interconvert through multiple bowl-inversions and bond-rotations.<ref>{{Cite journal| doi = 10.1021/jo800359z| pmid = 18505292| year = 2008| last1 = Eisenberg | first1 = D.| last2 = Filatov | first2 = A.| last3 = Jackson | first3 = E.| last4 = Rabinovitz | first4 = M.| last5 = Petrukhina | first5 = M.| last6 = Scott | first6 = L.| last7 = Shenhar | first7 = R.| title = Bicorannulenyl: stereochemistry of a C40H18 biaryl composed of two chiral bowls| volume = 73| issue = 16| pages = 6073–6078| journal = The Journal of Organic Chemistry }}</ref>
			When bicorannulenyl is reduced to a dianion with potassium metal, the central bond assumes significant double-bond character. This change is attributed to the orbital structure, which has a LUMO orbital localized on the central bond.<ref>{{cite journal | last1 = Eisenberg | first1 = D. | last2 = Quimby | first2 = J. M. | last3 = Jackson | first3 = E. A. | last4 = Scott | first4 = L. T. | last5 = Shenhar | first5 = R. | year = 2010 | title = The Bicorannulenyl Dianion: A Charged Overcrowded Ethylene | journal = Angewandte Chemie International Edition | volume = 49 | issue = 41| pages = 7538–7542 | doi = 10.1002/anie.201002515 | pmid=20814993 }}</ref> When bicorannulenyl is reduced to an {{chem name|octaanion}} with lithium metal, it self-assembles into supramolecular oligomers.<ref>{{cite journal | last1 = Eisenberg | first1 = D. | last2 = Quimby | first2 = J. M. | last3 = Jackson | first3 = E. A. | last4 = Scott | first4 = L. T. | last5 = Shenhar | first5 = R. | year = 2010 | title = Highly Charged Supramolecular Oligomers Based on the Dimerization of Corannulene Tetraanion | journal = Chemical Communications | volume = 46 | issue = 47| pages = 9010–9012 | doi = 10.1039/c0cc03965a | pmid = 21057679 }}</ref> This motif illustrates "charged polyarene stacking".
			==Research==
			]The corannulene group is used in ] with interactions based on ], notably with ]s (the {{chem name|buckycatcher}}) <ref>{{Cite journal| doi = 10.1021/ja070616p| pmid = 17348661| year = 2007| last1 = Sygula | first1 = A.| last2 = Fronczek | first2 = F.| last3 = Sygula | first3 = R.| last4 = Rabideau | first4 = P.| last5 = Olmstead | first5 = M.| title = A double concave hydrocarbon buckycatcher| volume = 129| issue = 13| pages = 3842–3843| journal = Journal of the American Chemical Society | s2cid = 25154754}}</ref><ref>{{Cite journal| doi = 10.1002/jcc.21022| pmid = 18504779| year = 2009| last1 = Wong | first1 = B. M.| title = Noncovalent interactions in supramolecular complexes: a study on corannulene and the double concave buckycatcher| volume = 30| issue = 1| pages = 51–56| journal = Journal of Computational Chemistry | arxiv = 1004.4243| s2cid = 18247078}}</ref> but also with ]<ref>{{Cite journal| doi = 10.1016/j.tetlet.2009.09.177| title = Molecular clips and tweezers with corannulene pincers| year = 2009| last1 = Kobryn | first1 = L.| last2 = Henry | first2 = W. P.| last3 = Fronczek | first3 = F. R.| last4 = Sygula | first4 = R.| last5 = Sygula | first5 = A.| journal = Tetrahedron Letters| volume = 50| issue = 51| pages = 7124–7127 }}</ref>
			Alkyl-substituted corannulenes form a thermotropic hexagonal columnar ].<ref>{{Cite journal | first7 = M.| last8 = Aida| last7 = Takata | first6 = K.| last6 = Kato | first8 = T.| title = Liquid crystalline corannulene responsive to electric field| journal = Journal of the American Chemical Society| pages = 44–45| issue = 1| volume = 131 | first5 = J.| last5 = Kim | first1 = D.| last1 = Miyajima| year = 2009| pmid = 19128171| last2 = Tashiro | first2 = K. | first4 = H.| last4 = Takezoe | first3 = F.| last3 = Araoka| doi = 10.1021/ja808396b }}</ref> Corannulene has also been used as the core group in a ].<ref name=pappo/> Like other PAHs, corannulene ] metals.<ref>{{cite journal | last1 = Seiders | first1 = T. Jon | last2 = Baldridge | first2 = Kim K. | last3 = O'Connor | first3 = Joseph M. | last4 = Siegel | first4 = Jay S. | year = 1997 | title = Hexahapto Metal Coordination to Curved Polyaromatic Hydrocarbon Surfaces: The First Transition Metal Corannulene Complex | journal = J. Am. Chem. Soc. | volume = 119 | issue = 20| pages = 4781–4782 | doi = 10.1021/ja964380t }}</ref><ref>{{cite journal | last1 = Siegel | first1 = Jay S. | last2 = Baldridge | first2 = Kim K. | last3 = Linden | first3 = Anthony | last4 = Dorta | first4 = Reto | year = 2006 | title = d8 Rhodium and Iridium Complexes of Corannulene | journal = J. Am. Chem. Soc. | volume = 128 | issue = 33| pages = 10644–10645 | doi = 10.1021/ja062110x | pmid=16910635}}</ref><ref>{{Cite journal| doi = 10.1002/anie.200704783| pmid = 18214869| year = 2008| last1 = Petrukhina | first1 = M. A.| title = Coordination of buckybowls: the first concave-bound metal complex| volume = 47| issue = 9| pages = 1550–1552| journal = Angewandte Chemie International Edition in English }}</ref><ref>{{Cite journal| doi = 10.1021/om0610795| title = η6-Coordination of the Curved Carbon Surface of Corannulene (C20H10) to (η6-arene)M2+(M = Ru, Os)| year = 2007| last1 = Zhu | first1 = B.| last2 = Ellern | first2 = A.| last3 = Sygula | first3 = A.| last4 = Sygula | first4 = R.| last5 = Angelici | first5 = R. J.| journal = Organometallics| volume = 26| issue = 7| pages = 1721–1728 }}</ref><ref>{{Cite journal| doi = 10.1021/om060350f| title = Corannulene: A Preference forexo-Metal Binding. X-ray Structural Characterization of | year = 2006| last1 = Petrukhina | first1 = M. A.| last2 = Sevryugina | first2 = Y.| last3 = Rogachev | first3 = A. Y.| last4 = Jackson | first4 = E. A.| last5 = Scott | first5 = L. T.| journal = Organometallics| volume = 25| issue = 22| pages = 5492–5495 }}</ref><ref>{{Cite journal| doi = 10.1021/ja062110x| pmid = 16910635| year = 2006| last1 = Siegel | first1 = J.| last2 = Baldridge | first2 = K.| last3 = Linden | first3 = A.| last4 = Dorta | first4 = R.| title = D8 rhodium and iridium complexes of corannulene| volume = 128| issue = 33| pages = 10644–10645| journal = Journal of the American Chemical Society }}</ref><ref>{{cite journal | last1 = Bandera | first1 = D. | last2 = Baldridge | first2 = K. K. | last3 = Linden | first3 = A. | last4 = Dorta | first4 = R. | last5 = Siegel | first5 = J. S. | year = 2011 | title = Stereoselective Coordination of C5-Symmetric Corannulene Derivatives with an Enantiomerically Pure Metal Complex. | journal = Angewandte Chemie International Edition | volume = 50 | issue = 4 | pages = 865–867 | doi = 10.1002/anie.201006877 | pmid = 21246679 }}</ref> Corannulenes with ethynyl groups are investigated for their potential use as blue emitters.<ref name=Mack/> The structure was analyzed by infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy.<ref>{{Cite journal|last1=Diana|first1=Nooramalina|last2=Yamada|first2=Yasuhiro|last3=Gohda|first3=Syun|last4=Ono|first4=Hironobu|last5=Kubo|first5=Shingo|last6=Sato|first6=Satoshi|date=2021-02-01|title=Carbon materials with high pentagon density|url=https://doi.org/10.1007/s10853-020-05392-x|journal=Journal of Materials Science|language=en|volume=56|issue=4|pages=2912–2943|doi=10.1007/s10853-020-05392-x|bibcode=2021JMatS..56.2912D|s2cid=224784081|issn=1573-4803}}</ref>
	==In space==
			{{clear}}
	Efforts to detect corannulene in space have thus far failed.<ref>{{cite DOI|10.1111/j.1365-2966.2009.15067.x}}</ref><ref>{{cite DOI|10.1002/cphc.200800387}}</ref>
	==See also==		==See also==
			{{Commons category|Corannulene}}
			{{wiktionary}}
	* ]		* ]
	* ]		* ]
			* ]
	== References ==		== References ==
	{{Reflist|2}}		{{Reflist|2}}
	{{PAHs}}		{{PAHs}}
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