Mircea V. Diudea - Babeș-Bolyai Universitychem.ubbcluj.ro/~diudea/cursuri si...

11

Fullerenes Fullerenes 55

Mircea V. DiudeaMircea V. Diudea

Faculty of Chemistry and Chemical EngineeringFaculty of Chemistry and Chemical EngineeringBabesBabes--Bolyai UniversityBolyai University400028400028 Cluj, ROMANIACluj, ROMANIA

[email protected]@chem.ubbcluj.ro

22

ContentsContents

FullereneFullerene –– PhysicoPhysico--Chemical propertiesChemical properties

Addition ReactionAddition Reaction

StoneStone--Wales ReactionsWales Reactions

33

Fullerenes in NatureFullerenes in Nature

Fullerenes were found in the natural Fullerenes were found in the natural environment, but only in the environment, but only in the ppmppm--range. range. Some places are Shunga/Russia,Some places are Shunga/Russia,11 New New ZealandZealand22 and Sudbury/Canada.and Sudbury/Canada.33

1. P.R. 1. P.R. BusekBusek, S.J. , S.J. TsipurskyTsipursky, R. , R. HettichHettich, Science 257 (1992) 215 , Science 257 (1992) 215 2. D. 2. D. HeymannHeymann, L.P.F. , L.P.F. ChibanteChibante, R.R. Brooks, W.S. , R.R. Brooks, W.S. WolbachWolbach, R.E. Smalley,, R.E. Smalley,

Science 265 (1994) 645 Science 265 (1994) 645 3. L. Becker, J.L. 3. L. Becker, J.L. BadaBada, R.E. , R.E. WinansWinans, , J.E.HuntJ.E.Hunt, T.E. Bunch, B.M. French, , T.E. Bunch, B.M. French, Science 265 (1994) 642Science 265 (1994) 642

44

Isolated FullerenesIsolated Fullerenes

CC7070CC6060

55

Fullerenes Fullerenes –– physicophysico--chemical chemical propertiesproperties

Good solvents for fullerenes are CSGood solvents for fullerenes are CS22, toluene, , toluene, xylenexylene, and o, and o--dichlorobenzene while they are dichlorobenzene while they are insolubleinsoluble in water and stable at air. in water and stable at air. Thin layers of fullerenes and solutions are Thin layers of fullerenes and solutions are colouredcoloured, because of , because of ππππ**--electron transitions:electron transitions:11

-- CC6060 purple/purple/violetredvioletred-- CC7070 brickbrick--redred-- CC7676 light yellowlight yellow--green green -- CC2v2v--CC7878 maroon, Dmaroon, D33--CC7878 golden, golden, -- CC8484 brown andbrown and-- CC8686 oliveolive--green.green.

1. A.F. 1. A.F. HollemannHollemann, , LehrbuchLehrbuch der der anorganischenanorganischen ChemieChemie, 101. , 101. AuflageAuflage (1995),(1995),de de GruyterGruyter, 843., 843.

66

Chemical Reactions of FullerenesChemical Reactions of Fullerenes

Fullerenes are not “Fullerenes are not “aromaticaromatic” compounds.” compounds.11

No reactions with “No reactions with “reversion to typereversion to type” (preserving ” (preserving e.ge.g., the ., the ππ--electron distributionelectron distribution, as the substitution reactions of , as the substitution reactions of benzene benzene -- like molecules, like molecules, i.ei.e., aromatic species) occur.., aromatic species) occur.The general The general addition chemistryaddition chemistry of Cof C6060 is closer to “is closer to “super super alkenicalkenic” than “super aromatic”.” than “super aromatic”.22

1. J. 1. J. CastelsCastels, Some comments on fullerene terminology, nomenclature,, Some comments on fullerene terminology, nomenclature,and and aromaticityaromaticity. Fullerene Sci. Technol. 1994, 2, 367. Fullerene Sci. Technol. 1994, 2, 367--379. 379.

2.2. P. W. Fowler, D. J. Collins, and S. J. Austin, J. Chem. Soc., P. W. Fowler, D. J. Collins, and S. J. Austin, J. Chem. Soc., Perkin Perkin Trans., 1993, 2, 275Trans., 1993, 2, 275--277.277.

77

Addition ReactionsAddition Reactions

Fullerenes are Fullerenes are electronelectron--defficientdefficient molecules.molecules.11

TheyThey form multipleform multiple--charged anions with electron charged anions with electron donating species, donating species, e.ge.g., the alkaline or alkaline., the alkaline or alkaline--earth earth metals.metals.EndohedralEndohedral complexescomplexes, like, like La@CLa@C8282 , are, are formed when the formed when the metal was metal was catalysedcatalysed the fullerene the fullerene growth.growth.ExohedralExohedral derivativesderivatives are synthesized by addition are synthesized by addition reactions.reactions.

1.1. P. J. Fagan, J. C. Calabrese, and B. Malone, Acc. Chem. Res.,P. J. Fagan, J. C. Calabrese, and B. Malone, Acc. Chem. Res.,1992, 25, 1992, 25, 134134--142142

88

Endohedral (a) and Endohedral (a) and exohedralexohedral (b) (b) derivativesderivatives

(b) (b) CC6060ClCl66(a) (a) LaLa@C@C8282

99

Addition ReactionsAddition ReactionsAlthough Although CC6060 has 12500 has 12500 KekuleKekule structures,structures,1 1 its its addition addition reactions, in which it reactions, in which it showsshows an an electronelectron--deficient deficient alkenicalkeniccharacter, are oriented by the character, are oriented by the Fries Fries KekuleKekule structure; structure; recallrecall that, in this unique structure, all that, in this unique structure, all pp (5,6) edges are (5,6) edges are formal single bonds while all formal single bonds while all hh (6,6) are formally double. (6,6) are formally double. The highest bond order (The highest bond order (i.ei.e., ., thethe 22--orderorder) is reached by the ) is reached by the StoneStone--WalesWales formal double bonds, located at the centre of formal double bonds, located at the centre of pyracylenepyracylene--like patches. like patches. AllAll 30 double bonds of C30 double bonds of C60 60 (among 90 edges) while in C(among 90 edges) while in C7070(among 105 edges) only 20 are of this type. The addition (among 105 edges) only 20 are of this type. The addition reaction will occur, most probably, at these electronreaction will occur, most probably, at these electron--rich rich bonds.bonds.

1. H. W. 1. H. W. KrotoKroto, J. R. Heath, S. C. O’Brian, R. F. , J. R. Heath, S. C. O’Brian, R. F. KurlKurl and R. E. Smalley,and R. E. Smalley,NatureNature, 1985,, 1985,318318, , 162.162.

1010

StoneStone--WalesWales isomerisationisomerisation11

pyracylenic patchpyracylenic patch

1. A. J. Stone and D. J. Wales, 1. A. J. Stone and D. J. Wales, Chem.PhysChem.Phys. Lett., 1986, 128, . Lett., 1986, 128, 501.501.

The bold edge shares two cycles The bold edge shares two cycles of size (of size (ssmm, , ssnn) to be reduced, ) to be reduced, after rotation, to (after rotation, to (ssmm--11, , ssnn--11).).

The two cycles joined by this edge The two cycles joined by this edge will increase their size from (will increase their size from (sspp, , ssrr) ) to (to (ssp+1p+1, , ssr+1r+1) )

1111

StoneStone--WalesWales isomerisationisomerisation11

pyracylenic patchpyracylenic patch

1. A. J. Stone and D. J. Wales, 1. A. J. Stone and D. J. Wales, Chem.PhysChem.Phys. Lett., 1986, 128, . Lett., 1986, 128, 501.501.

Most often, the edge flipping Most often, the edge flipping runs as a runs as a cascade SWcascade SWtransformationtransformation

1212

StoneStone--WalesWales isomerisationisomerisation

SWSW IIssomerizaomerization by ation by a concertconcertededmechanism, with a diradical transition mechanism, with a diradical transition statestate..

=

1313

StoneStone--WalesWales isomerisationisomerisation

SWSW IIssomerizaomerization tion iinvolving a carbenenvolving a carbene as as the the intermediaintermediatete..

1414

EnantiomerEnantiomerss byby SWSW: : CC2828:1:1

1515

A A SWSW FamilFamilyy -- CC3030

CC3030 : 1: 1 CC3030 : 2: 2 CC3030 : 3: 3

1616

CoalescenCoalescencece of of NanostructurNanostructureses

M. V. M. V. DiudeaDiudea, , CsCs. L. . L. NagyNagy, O. , O. UrsuUrsu, , andand T. S. Balaban, T. S. Balaban, FullerFuller. . NanotubNanotub. . CarbonCarbon NanostructNanostruct., ., 20032003, , 1111, 245, 245--255.255.

SW edgesSW edges

1717

tata--TubulenesTubulenes

1818

ta ta ––TubulenesTubulenes11

CC96(96(66 556677

66(5,6)(5,6)

66(6,5)(6,5)

6677

665 5

666)6) ((CC22))22CC24(24(66 55

6611

66-- A[12,0])A[12,0]) + + A[12,4]A[12,4]

CCN N ((kk 55kk

77kk

(56)(56)kk--A[2k,A[2k,nn])]) ; ; NN = 8= 8kk ++pp

1.1. M. V. Diudea, Stability of tubulenes, M. V. Diudea, Stability of tubulenes, Phys. Chem., Chem. Phys.Phys. Chem., Chem. Phys., , 2004, 6, 3322004, 6, 332--339339

1919

fa fa --TubulenesTubulenes

Geodesic ProjectionGeodesic ProjectionCC96(96(66 6666(5,6)(5,6)

66(6,6)(6,6)

66(6,5)(6,5)

6666

666) 6) ((DD66dd))

fa fa ––TubulenesTubulenes from from ta ta --TubulenesTubulenes byby SWSW isomerizationisomerization 11

1. A. J. Stone and D. J. Wales, 1. A. J. Stone and D. J. Wales, Chem. Phys. LettChem. Phys. Lett., ., 19861986, , 128128, 501, 501--503.503.

2020

kfzkfz--peanut Tubulenespeanut Tubulenes

2121

CC168(168(66 6666(5,6)(5,6)

66(6,5)(6,5)

6677

66(5,7)(5,7)

33(7,5)(7,5)

3377

66))CC168(168(66 66

66(5,6)(5,6)

66(6,5)(6,5)

6677

6666

6666

6677

66))

Peanut Peanut 11 kf kf ––TubulenesTubulenes CCNN’ NN’ ((kk--Z[2Z[2kk,,nn])])

1. D. L. Strout, R.L. Murry, C. Xu, W.C. Eckhoff, G. K. Odom, a1. D. L. Strout, R.L. Murry, C. Xu, W.C. Eckhoff, G. K. Odom, and G. E. Scuseria,nd G. E. Scuseria,Chem. Phys. LettChem. Phys. Lett. 1993, . 1993, 214214, 576, 576--582.582.

2222

PeanutPeanut kfkf--TubulenesTubulenes

Geodesic projectionGeodesic projectionCC72(772(76666

6666

6677

66))

Isomerization of the distancing nanotube by SW edge rotationsIsomerization of the distancing nanotube by SW edge rotations11

1. M. V. Diudea et al., Periodic Cages, Croat. Chem. Acta, 2004 (in press)

2323


Geodesic projectionGeodesic projectionCC72(772(76 6 5 65 6

4 4 7 77 7 66

4 4 55 77

66))



2424



2 2 7 5 77 5 7

2266

2 2 5 7 5 75 7 5 7

66))



2525



2 2 7 5 77 5 7

2266

2 2 5 7 5 75 7 5 7

66))



2626

Energetic and Spectral Properties ofEnergetic and Spectral Properties ofPeanut Peanut kfz kfz ––TubulenesTubulenes CCNN ((k…k…Z[2Z[2kk,,nn])])

PCPC0.200.20--0.0400.0400.1620.1625.435.4312.55312.553SS66CC168(168(66 ……7766(5,7)(5,7)

33(7,5)(7,5)

3377

66))66

PCPC0.050.05--0.0400.0400.0090.0095.195.1912.45212.452CC22CC168(168(66 … … 77665 65 6

227 5 77 5 7

2266

225 7 5 75 7 5 7

66))55

MCMC0.010.01--0.0230.023--0.0130.0135.165.1612.26112.261CC22CC168(168(66 ……77665 65 6

447 7 67 7 6

445 75 7

66))44

OPOP00--0.0230.023--0.0230.0235.115.1111.92711.927DD66ddCC168(168(66 6666(5,6)(5,6)

66(6,5)(6,5)

6677

6666

6666

6677

66))33

ShellShellGapGapλN/2+1λN/2HF/atHF/atSpectral DataSpectral DataPM3PM3

GapGapPM3PM3SymSymCageCage

2727

TubuleneTubulene (left) and peanut (left) and peanut z z --tubulenestubulenes (mean) (mean) corresponding to the corresponding to the multimulti--peanutpeanut (C(C6060))nn (right)(right)

2828

HOMO HOMO eigenvalueseigenvalues of multi peanut of multi peanut z z --tubulenestubulenes (C(C6060))44

-0.1

-0.05

0

0.05

0.1

0.15

0.2

0 0.5 1 1.5 2 2.5 3 3.5

no. necks

λ

2929

((5,7)3) ((5,7)3) kzkz--peanut peanut TubulenesTubulenes

3030

Rearrangement of (4, 6) pairs to (5, 5) onesRearrangement of (4, 6) pairs to (5, 5) onesby SW edge rotationby SW edge rotation11

CC84(84(77 557777

7755

141477

7755

777); 7); ((CCi i ))CC84(84(77 55

7777

77(4,6)(4,6)

7777

7755

777) 7)

1. A. J. Stone and D. J. Wales, 1. A. J. Stone and D. J. Wales, Chem. Phys. LettChem. Phys. Lett., 1986, ., 1986, 128128, 501, 501

3131

Rearrangement of all (5, 7) cages Rearrangement of all (5, 7) cages to the classical Cto the classical C12k12k fullerenes by SWfullerenes by SW11

CC60(60(55 6655(5,6)(5,6)

55(6,5)(6,5)

5566

555) 5) ((IIh h ))CC60(60(55 55

5577

5555

101077

5555

555) 5) ((CCi i ))

1. A. J. Stone and D. J. Wales, 1. A. J. Stone and D. J. Wales, Chem. Phys. LettChem. Phys. Lett., 1986, ., 1986, 128128, 501, 501

3232

2/Nλ 12/ +Nλ

PSC0.20440.01550.2199----196; 7; 196; 7; 3 3 66

OP00.22310.22315.11415.828CCii140;7; 140;7; 2 2 55

PSC0.01410.23110.24524.53816.249CCii84; 7; 84; 7; 1 1 44

PSCPSC0.29790.2979000.29790.2979------140; 5; 140; 5; 3 3 33

OPOP000.27850.27850.27850.27855.5925.59218.90618.906CCii100; 5; 100; 5; 2 2 22

PSCPSC0.15070.15070.22900.22900.37970.37975.6235.62321.15821.158CCii60 ; 5; 60 ; 5; 1 1 11

ShellShellGAPGAPΛΛΝ/2+1Ν/2+1ΛΛΝ/2Ν/2HF/atHF/at

Spectral DataSpectral DataPM3PM3GAPGAP

PM3PM3SymSym(5,7) Cage(5,7) CageCCN N ((kk 55

kk(7(7

kk55

22kk77

kk))rr55

kkkk))

Semiempirical and spectral data Semiempirical and spectral data for for ((5,7)3)((5,7)3) periodic cagesperiodic cages

3333

((5,7)3)((5,7)3) Periodic CagesPeriodic Cages

The The (((5,7)3)(5,7)3) periodic cages tend to periodic cages tend to isomerizeisomerize to the to the more stable more stable ffaa--tubulenestubulenes

3434

ISOMERIZATION OF (5, 7) PERIODICISOMERIZATION OF (5, 7) PERIODIC CAGESCAGES

to to fafa--TubulenesTubulenes

CC100(100(55 6655(5,6)(5,6)

55--A[10,2])A[10,2])CC100(100(kk 55

kk(7(7

kk55

22kk77

kk))rr55

kkkk);); kk = 5; = 5; rr = 2= 2

3535

ISOMERIZATION OF (5, 7) PERIODIC CAGESISOMERIZATION OF (5, 7) PERIODIC CAGES

CC100(100(kk 55kk77

kk(5,6)(5,6)

kk(6,6)(6,6)

kk(6,5)(6,5)

kk77

kk55

kkkk););

kk = 5= 5

CC100(100(kk 55kk77

kk55

22kk88

kk(5,6)(5,6)

kk(5,7)(5,7)

kk55

kkkk); );

kk = 5= 5

3636

ISOMERIZATION OF (5, 7) PERIODIC CAGESISOMERIZATION OF (5, 7) PERIODIC CAGES

CC100(100(kk66kk

((5,6)5,6)kk(5,8)(5,8)

kk(5,6)(5,6)

kk(6,5)(6,5)

kk66

kkkk); );

kk = 5= 5

CC100(100(kk 66kk

((5,6)5,6)kk(5,7)(5,7)

kk77

kk(5,6)(5,6)

kk(5,6)(5,6)

kkkk); );

kk = 5= 5

3737

2/Nλ12/ +Nλ

PCPC0.3500.350000.3500.3505.0455.04510.87610.876DD55ddCC100(100(55 6655(5,6)(5,6)

55--A[10,2])A[10,2])

66

PSC0.0080.2390.2473.84915.205D5dCC100(100(kk 55kk

77kk

(5,6)(5,6)kk

(6,6)(6,6)k k

(6,5)(6,5)kk

77k k

55kk

k)k)

5

PSC0.2670.1470.4145.40418.260C1CC100(100(kk 55kk

77kk

552k2k

88k k

(5,6)(5,6)k k

(5,7)(5,7)kk

55kk

k)k)

4

PSC0.3710.0200.3915.77013.966C5vCC100(100(kk66kk

(5,6)(5,6)kk

(5,8)(5,8)kk

(5,6)(5,6)kk

(6,5)(6,5)kk

66kk

k)k)

3

OP00.3110.3115.54615.146D5dCC100(100(kk 66kk

(5,6)(5,6)k k

(5,7)(5,7)kk

77k k

(5,6)(5,6)kk

(5,6)(5,6)kk

k)k)

2

OPOP000.2790.2790.2790.2795.5925.59218.90618.906CCiiCC100(100(kk 55kk

(7(7kk

552k2k

77kk

))rr55

kkk); k);

k = 5; r = 2k = 5; r = 2

11ShellShellGAPGAPHF/atHF/at

Spectral DataSpectral DataPM3PM3GAPGAP

PM3PM3SymSymCage Cage

Data for some ((5,7)3) peanut cages Data for some ((5,7)3) peanut cages and their isomerization to and their isomerization to fafa--tubulenestubulenes

3838

Functionalization Functionalization of of fullerenesfullerenes

3939

The study of 1,3The study of 1,3--bipolarbipolar nitriliminesnitrilimines andandfullerenefullerene CC6060 cycloadditioncycloaddition

During the study of 1,3During the study of 1,3--disubstituted nitriliminesdisubstituted nitrilimines andandfullerene cycloadditionfullerene cycloaddition reaction a model set ofreaction a model set offullerenepyrazolinesfullerenepyrazolines containing variouscontaining various substituentssubstituentsincludingincluding heterocyclicheterocyclic fragments and CFfragments and CF3 3 group was group was synthesized. Stable synthesized. Stable [6,6][6,6]--closedclosed adducts 1, 2, 3, 4, 5, 6, adducts 1, 2, 3, 4, 5, 6, and 7 were synthesized by and 7 were synthesized by 1,31,3--bipolarbipolar cycloadditioncycloaddition ofoffullerenefullerene andand nitriliminesnitrilimines, generated , generated in situ in situ from the from the correspondingcorresponding hydrazonoil halogenideshydrazonoil halogenides andandthreethylaminethreethylamine. .

4040

MethMethaanofullerenesnofullerenes

These These compoundscompounds representrepresent the most versatile and widely studied class of the most versatile and widely studied class of fullerene fullerene adducts. In theory, there exist four possible isomers: 6adducts. In theory, there exist four possible isomers: 6--55--open, open, 66--55--closed, 6closed, 6--66--open, 6open, 6--66--closed, depending on closed, depending on wherther wherther addition takes addition takes place at 6place at 6--6 or 66 or 6--5 bonds and whether the bridgehead C atoms are at 5 bonds and whether the bridgehead C atoms are at

nonbonding distance or are connected by a nonbonding distance or are connected by a transannular transannular bond.bond.

66--55--closedclosed 66--55--openopen 66--66--closedclosed 66--66--openopen

Functionalization of fullerenesFunctionalization of fullerenes

4141

Formation of the parent 6Formation of the parent 6--55--open (1) and open (1) and 66--66--closedclosed (2)(2)methanofullerenemethanofullerene (C(C6161HH22) isomers by ) isomers by 1,31,3--dipolardipolar cycloadditioncycloaddition ofofdiazomethanediazomethane to Cto C6060 to give a 6to give a 6--66--fusedfused pyrazolinepyrazoline intermediateintermediatefollowedfollowed by thermal or photochemical extrusion of Nby thermal or photochemical extrusion of N2.2.


4242


66--66--fused pyrazoline intermediatefused pyrazoline intermediate

4343

1,31,3--DipolarDipolar cycloadditioncycloaddition ofof tertbutyltertbutyl (t(t--Bu)Bu) diazoacetatediazoacetate yields a mixture of yields a mixture of twotwo diastereomericdiastereomeric 66--55--open (kinetic) and one 6open (kinetic) and one 6--66--closed (closed (thermodinamicthermodinamic) ) products.products.


4444

The optically activeThe optically active fullerenefullerene--sugar conjugate 4 is obtained by the sugar conjugate 4 is obtained by the attack of aattack of a nucleophilicnucleophilic glycosylideneglycosylidene carbenecarbene (formed(formed from the from the correspondingcorresponding diazirine)diazirine) to to CC6060..


4545

In theIn the BingelBingel reaction, reaction, ∝∝--bromobromo--malonatesmalonates areare deprotonateddeprotonated by a baseby a baseand and react asreact as nucleophilesnucleophiles withwith CC6060 to give an intermediate anion, which, to give an intermediate anion, which, by displacement of the halide, closes theby displacement of the halide, closes the methanomethano bridgebridge toto diestersdiesterssuch as 5.such as 5.


4646

TrimethylsilylTrimethylsilyl--protected 3protected 3--bromopentabromopenta-- 1,41,4-- diynediyne reacts in the reacts in the presence of presence of basesbases withwith trimethylsilylethynetrimethylsilylethyne affords 7, which, upon affords 7, which, upon electrolysis, yields a electrolysis, yields a conducting polymeric filmconducting polymeric film at the cathode at the cathode (TMEDA, N,N,N’,N’(TMEDA, N,N,N’,N’--tetramethylethylenediaminetetramethylethylenediamine;; PhPh, phenyl; and Me, , phenyl; and Me, methyl).methyl).


4747

FormationFormation ofof methanofullerenesmethanofullerenes byby nucleophilicnucleophilic additionadditionof aof a phosphonium ylidephosphonium ylide, a, a WittigWittig reagent.reagent.


4848A A fullerenefullerene--dendrimerdendrimer


4949


5050


5151

CyclopropanationCyclopropanation ReactionsReactions11

11. J. J--. Y. . Y. ZhengZheng, , ShSh. Noguchi, K. . Noguchi, K. MiyauchiMiyauchi, M. Hamada, K. , M. Hamada, K. KinbaraKinbara, and, andK. K. SaigoSaigo, Tether, Tether--linked [60]fullerenelinked [60]fullerene--donor dyads. Fullerene Sci. donor dyads. Fullerene Sci. Technol. 2001, 9, 467Technol. 2001, 9, 467--475.475.

TransTrans--44--[60]fullerene [60]fullerene bisbis--adducts adducts ––fluorescence studiesfluorescence studies

5252

Dimeric Dimeric CC6060;; a [2 +2] a [2 +2] cicloadductcicloadduct

CC120120-- ((pppp--cc))CC120 120 -- ((hhhh))

S. Lebedkin, A. S. Lebedkin, A. GromovGromov, S. , S. GiesaGiesa, R. , R. GleiterGleiter, B. , B. RenkerRenkerH. H. RietschelRietschel and W. and W. KrätschmerKrätschmer, Raman scattering study of, Raman scattering study ofC120, a C60 C120, a C60 dimerdimer. Chem. Phys. Lett, 1998, 285, 210. Chem. Phys. Lett, 1998, 285, 210--215.215.

C5C5--c2c2--2_7(all sp2); 120;2_7(all sp2); 120; DD5d5d; HF = 10.625 kcal/mol; HF = 10.625 kcal/mol

5353

Cycloaddition [2 +3] = Cycloaddition [2 +3] = CC120120OOCC120 120 -- O (O (hhhh))EpoxiEpoxi--[60]fullerene[60]fullerene

AA. . GromovGromov, S. Lebedkin, S. , S. Lebedkin, S. BallenwegBallenweg, A. G. , A. G. AventAvent, R. Taylor and, R. Taylor andW. W. KrätschmerKrätschmer, C, C120120OO22: The first [60]fullerene : The first [60]fullerene dimerdimer with cages with cages bisbis--linked by linked by furanoidfuranoid bridges, Chem. Commun. 1997, 209bridges, Chem. Commun. 1997, 209--210. 210.

5454

Fullerenes Fullerenes –– physical propertiesphysical properties

The discovery of The discovery of superconductivitysuperconductivity in alkali doped fullerides at in alkali doped fullerides at moderately high temperatures (1991). moderately high temperatures (1991).

The chemistry of fullerenes also includes the synthesis of The chemistry of fullerenes also includes the synthesis of endohedral fullerenesendohedral fullerenes having the formula having the formula M@CM@Cn n , where M stands , where M stands for a metal atom inside the fullerene cage. for a metal atom inside the fullerene cage. These studies have suggested enormous potential and a wide rangeThese studies have suggested enormous potential and a wide rangeof applications for carbonof applications for carbon--based materials, thanks to the based materials, thanks to the possibility possibility of tailoring their physical propertiesof tailoring their physical properties and performances. and performances. It was suggested that the It was suggested that the superconducting criticalsuperconducting critical temperaturetemperature of of doped fulleritedoped fullerite increasesincreases with the with the curvaturecurvature of fullerene cages, of fullerene cages, namely with the reduction of the cluster size from Cnamely with the reduction of the cluster size from C6060 down to Cdown to C3636,,and perhaps Cand perhaps C2828 and Cand C2020. . Moreover, an unexpected Moreover, an unexpected ferromagneticferromagnetic behavior has been recently behavior has been recently described in fullerenic materials.described in fullerenic materials.

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Utilizations of FullerenesUtilizations of Fullerenes

Soft Soft ferromagneticsferromagnetics, , Organic conductors, Organic conductors, Lubricant materials,Lubricant materials,Superconductivity, discovered in fullerene films Superconductivity, discovered in fullerene films doppeddopped with alkaline metals. The temperature of with alkaline metals. The temperature of transition into this state, at 45 K is exceeded transition into this state, at 45 K is exceeded only by ceramic superconductors, but fullerene only by ceramic superconductors, but fullerene films have higher criticalfilms have higher critical-- current values.current values.Applications in catalysis is also of interest.Applications in catalysis is also of interest.

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ReferencesReferences

1. Diudea, M. V.; Graovac, A.; 1. Diudea, M. V.; Graovac, A.; Generation and GraphGeneration and Graph--Theoretical Theoretical Properties of C4Properties of C4--Tori. Tori. Commun. Math. Comput. Chem. Commun. Math. Comput. Chem. ((MATCHMATCH)), , 2001, 2001, 4444, 93, 93--102102

2. Diudea, M. V.; Silaghi2. Diudea, M. V.; Silaghi--Dumitrescu, I.; Parv, B. Dumitrescu, I.; Parv, B. ToranesToranes versus versus TorenesTorenes..Commun. Math. Comput. ChemCommun. Math. Comput. Chem. (. (MATCHMATCH), 2001, ), 2001, 4444, 117, 117--133133

3. Diudea, M. V.; John, P. E. Covering Polyhedral Tori. 3. Diudea, M. V.; John, P. E. Covering Polyhedral Tori. Commun. Math. Commun. Math. Comput. Comput. Chem. (Chem. (MATCHMATCH), 2001, ), 2001, 4444, 103, 103--116116

4. Diudea, M. V.; Kirby, E. C. The Energetic Stability of Tori 4. Diudea, M. V.; Kirby, E. C. The Energetic Stability of Tori and and SingleSingle--wall Tubes. wall Tubes. Fullerene Sci. Technol.Fullerene Sci. Technol. 2001, 2001, 99, 445, 445--465.465.

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ReferencesReferences

5. 5. Diudea, M. V. Diudea, M. V. GraphenesGraphenes from 4from 4--Valent Tori. Valent Tori. Bull. Chem. Soc. Bull. Chem. Soc. JapanJapan, 2002,, 2002, 7575, 487, 487-- 492. 492.

6. Diudea, M. V.; Silaghi6. Diudea, M. V.; Silaghi--Dumitrescu, I.; Dumitrescu, I.; PârvPârv, Toroidal Fullerenes. , Toroidal Fullerenes. Ann. Ann. West Univ.West Univ.TimisoaraTimisoara, 2001, , 2001, 1010, 21, 21--4040

7. Diudea, M. V.; Silaghi7. Diudea, M. V.; Silaghi--Dumitrescu, I.; Dumitrescu, I.; PârvPârv, B. Toroidal Fullerenes , B. Toroidal Fullerenes from Square Tiled Tori. from Square Tiled Tori. Internet Electronic Journal of Molecular Internet Electronic Journal of Molecular DesignDesign. . 2002, 2002, 11, 10, 10--22.22.

8. Diudea, M. V. Hosoya Polynomial in Tori. 8. Diudea, M. V. Hosoya Polynomial in Tori. Commun. Math. Comput. Commun. Math. Comput. ChemChem. (. (MATCHMATCH), 2002,), 2002, 4545, 109, 109--122.122.

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ReferencesReferences9.9. Diudea, M. V. Phenylenic and Diudea, M. V. Phenylenic and NaphthylenicNaphthylenic Tori. Tori. Fullerenes, Fullerenes,

Nanotubes Carbon Nanostruct.Nanotubes Carbon Nanostruct.,, 2002, 2002, 1010, 273, 273--292.292.

10. Diudea, M. V.; Parv, B.; Kirby, E. C. Azulenic Tori. 10. Diudea, M. V.; Parv, B.; Kirby, E. C. Azulenic Tori. Commun. Math. Commun. Math. Comput. ChemComput. Chem. (. (MATCHMATCH), ( in press).), ( in press).

11. Diudea M. V., Periodic 4,7 cages. 11. Diudea M. V., Periodic 4,7 cages. Bul. Stiint. Univ. Baia Mare Ser. B Bul. Stiint. Univ. Baia Mare Ser. B 2002, 2002, 1818, 000, 000--000. 000.

12. Diudea M. V. Topology of 12. Diudea M. V. Topology of NaphthylenicNaphthylenic Tori. Tori. PCCPPCCP 2002, 2002, 44, 4740, 4740--4746.4746.

13. Diudea, M. V., Ed., 13. Diudea, M. V., Ed., Nanostructures Nanostructures –– Novel ArchitectureNovel Architecture, , Nova Science, Huntington, New York, (in preparation).Nova Science, Huntington, New York, (in preparation).

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