New sulfur-fullerite; its preparation, structure and spectral properties

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New sulfur-fullerite; its preparation, structure and spectral properties

N. Kushch, I. Majchrzak, W. Ciesielski, A. Graja, K. Woźniak, T. Krygowski

To cite this version:

N. Kushch, I. Majchrzak, W. Ciesielski, A. Graja, K. Woźniak, et al.. New sulfur-fullerite; its prepa-

ration, structure and spectral properties. Journal de Physique I, EDP Sciences, 1993, 3 (10), pp.1987-

1991. �10.1051/jp1:1993226�. �jpa-00246846�

Classification

Physics

Abstracts

61.50 61.10

Short Communication

New sulfur-filllerite; its preparation, structure and spectral properties

N-D- Kushch

(~,*),

I.

Majchrzak (~),

W. Ciesielski

(~),

A.

Graja (~),

^K.Wofniak

(~)

^and

T-M-

Krygowski (~)

(~) Institute of Molecular Physics, Polish Academy of Sciences, 60-179 Poznah, Poland

(~) Department of Chemisty, University of Warszawa, 02-093 Warszawa, Poland

(Received

8 July 1993, accepted in final form 3 August

1993)

Abstract. The preparation and unit cell parameters of _a novel fuflerene-containing _com- pound,

(C60)6S80.C2HC13,

is described. The compound is orthorhombic with _a

=

10.512(6) I,

b

=

21.072(26)

^I and _{c =}

38.985(50)I.

The UV-VIS-NIR-IR spectra ^{of the} compound _are analysed. It is concluded that the _new sulfur-fuflerite is true _van der Wafls solid without strong

interactions between the constituent molecules.

1 Introduction.

Fullerenes and

especially

their

derivatives,

so-called fullerites have attracted considerable atten- tion in many scientific

disciplines. Recently,

_{a new}

family

of C60

compounds,

which combine fullerene molecules with 58

rings

^{and have the}

general

formula

C2n(58)m

has been

synthe-

sized

[1-4].

^{Roth and Adelmann have}

reported

_a heteromolecular

compound, CmS48,

_com-

prising

^ordered

Cm

molecules and

crown-shaped

58

rings

in _a structure with

pronounced

two-

dimensional features

iii.

German [2] ^and

independently

Russian scientists [3] have

prepared

_a

new

fullerene-containing

_van der Walls

compound,

C60S16 in which the C60 molecules from _a three-dimensional framework with one-dimensional channels

containing crown-shaped

58

rings.

The solvent

containing compound, C60S6CS2

has been obtained

recently

_[4].

C60S8CS2

has

a framework _stucture with

58 rings

and

CS2

dumb-bells

filling

the channels.

Unfortunately, physical properties

of whichever _{ones are} not yet known.

(*)

Permanent address: Institute of Chemical Physics, Russian Academy of Sciences, 142432

Chernogolovka, Russia.

1988 JOURNAL DE PHYSIQUE I N°lo

Here,

_we describe the

preparation, preliminary X-Ray

measurements and basic

spectral properties

of

(C60)6S80.C2HC13,

_a new member of the sulfur-fullerites.

2

Experimental.

C60 _was

prepared

and

separated by

^{the usual method:} _an ^electric arc between

graphite

elec- trodes

burning

in _a helium

atmosphere,

fullerene extraction with hot

toluene, separation

of C60 and

Cm by liquid chromatography (n-hexane

+ 5~

toluene)

_on neutral

A1203

_IS,

6].

New sulfur-fullerite

(C60)6S80.C2HC13

_{was grown} ^from a solution of stoichiometric amounts of C60 and sulfur in

trichloroethylene,

at _room temperature. C60

(21.6

_mg, 2

x10~SM)

_was dis-

solved under _argon

atmosphere

in IS ml of

freshly

distilled

trichloroethylene.

Sulfur

(12.8

_mg,

4 _x

10~~M)

dissolved in 2 ml

trichloroethylene,

under _argon

atmosphere

_was added and mix- ture was heated about 4 h. The solution _was filtered and cooled down

slowly

in Dewar to

room temperature. Slow

evaporation

of the solvent gave

black, shining crystals

with

typical

dimensions _up to i _mm.

Elemental

analysis

of the sulfur-fullerite

(Found: C,

61.5;

S, 37.47; H,

< 0.01 and

Cl,

1.03. Calculated:

C,

61.95;

S,

36.51;

H,

o.oi and

Cl, 1.52.)

_suggests the

compound

formula

(C60)6S80'C2HC13.

X-Ray crystallographic

measurements on the

single crystal

_were

performed

at

R-T-,

with 4-circle diffractometer KUMA

using

CUK~ radiation. The

coumpound

is

orthorhombic,

_space

group C2 _mm with _a

=

10.512(6) I,

_b

=

21.072(26) I

and _c

=

38.985(50) ^I.

It is necessary to add that cell

filling

coefficient for

(C60)6S80.C2HC13 crystal

is

o.45,

I-e- somewhat smaller

than in the _case of similar

crystal

structures such _as

CmS48 (n

"

o.52), C60(CC14)2 (n

_"

0.59),

C60(n-C5H12)o.88.(C7H8)o.05 (n

_"

0.61),

C60S16

(n

"

0.62)

and

C60S8.CS2 (n

_"

0.65).

Infrared

powder

spectra ^{in the} _range ^of 4000-400 cm~~ _were recorded in KBr

pellets

with Perkin Elmer 1725 X FT IR spectrometer. ^UV-VIS-NIR spectra _were ^taken in KBr

pellets

and

C2HC13

solution with SPECORD apparatus. ESR _was measured in

polycrystal sample using SE/X

2544 X-band spectrometer ^made

by Radiopan.

The measurements _were

performed

at room temperature. Some IR spectra were taken after _a

sample heating

to

high

temperature in order to

investigate

_a

decomposition

of the

complex.

Thermal

stability

of the

crystals

_was evaluated

by microscope

observation and

supplementary

verified

by

IR spectroscopy. ^The

microscope

observations have been

performed

_on a 3 mg

sample

in the air

atmosphere using

5

K/min heating

rate in the temperature _range ^of 300- 650 K.

3.

Spectral properties.

Electronic and vibrational spectroscopy is _a

powerful

method for

studying

the interactions in the solid state between

C60,

sulfur and solvent molecules

holding

the

compound together.

Optical

spectra are sensitive indicators of

charge

distribution among the

complex

components.

In

particular,

it is

possible

to detect _a

charge

transfer and _a presence of C60 ions. On the other

hand,

the infrared spectroscopy ^{should be} sensitive to subtle deformations of the

complex

components. ^{It is}

important

for C60 derivatives because these deformations should reduce the

high

symmetry of the fullerene. IR spectroscopy ^should

give

_some information _on the sulfur

configuration

as well _{as on} the solvent content.

The VIS and NIR spectra ^of

(C60)6S80.C2HC13

in

trichloroethylene

solution _{are very} close to the spectra ^of pure

C60.

We detect neither the bands characteristic for

C(p

_{nor a} shift of

' '

2

~

~ l

J5

~

w o c

a ,

4

I~ b

4

~ i ,,"",,

," '~'"

i ," ',

' _,, ,

',-"

' O

30000 2sooo 20000 isooo

Frequency cm~~l

Fig. I. Electronic spectra of C60 in toluene

(a),

and

(C60)6S80.C2HC13

in KBr pellet

(b)

_{at room} temperature.

~

fW _f

~ _,., '... .-~ -'

~ ^~l

3 _b

c

U

#W

fl

©O

1800 1600 1400 1200 1000 800 600 400

Frequency (crrl)

Fig. 2. Infrared absorption spectra ^{of sulfur} (a), and

(C60)6580.C2HC13

complex(b) in KBr pellet,

at _room temperature.

the

absorption edge.

On the contrary, the spectra ^{recorded in KBr}

pellets (Fig. i)

reveal _an appearance of _{a new}

absorption

band in the

region

19000-23000 cm~~. _It suggests that C60 is

partly

ionized in the

complex

and the band centered at about 21000 cm~~ _{should be}

assigned

to a CT band. Thus it _seems that the sulfur-fullerite is _a very

weakly

bonded

complex.

On the other hand the electron

spin

_resonance measurements

performed

on

polycrystalline sample

reveal _a weak and _narrow ESR

line,

with g = 2.0016. The line with

g-factor

value lower than the free electron

value,

should be

assigned

to C60 anion. A similar line _was observed

by Greaney

and Gorun _{[7] at g}

= 2.0002. A

large g-value depression

_was

explained by

_a

spin-orbit coupling.

It is

interesting

to notice that in

(C60)6S80.C2HC13

the spins are localized _on the

C60,

contrary to the situation in the

(BEDT-TTF)2C60 complex

_[8] where the

spins

_are rather

on the

organic

cation.

The infrared spectrum of

(C60 )S80.C2HC13

^{shown in}

figure

2 is

essentially

_a

superposition

of

1990 JOURNAL DE PHYSIQUE I N°lo

Frequency (crr~)

Fig. 3. Infrared absorption spectra of C60

(a),

sulfur

(b)

and (C60)6S80-C2HC13 complex

(c)

in the

neighborhood of two C60 bands "feeling" ^the complex formation.

the spectra ^of

C60,

sulfur and

C2HC13.

The spectrum ^shows some small

frequency shifts,

about 2

cm~~

_or

less,

_as is

expected

of the

complex

with small

charge

transfer. The IR spectrum of pure C60 consists of four _narrow bands at

527, 576,

i183 and 1429 cm~~. Two last bands appear in the spectrum ^of

(C60)6S80.C2HC13

^without any

changes.

^{The band} at 576 cm~~ _is shifted to 578 cm~~ and broadened from 4 to 6 cm~~

(Fig. 3). Insignificant broadening

and

shifting

is also observed for 527

cm~~

band. It is characteristic that _{no new} modes _emerge,

arguing

that C60 symmetry is retained. These results show that the nature of _our

complex

is

completely

^different from that of the A6C60

compounds (A

= K,

Rb).

Fu et al. [9] ^{observed that}

absorption

intensities, band positions ^{overall and} some modes

(e.g.

1429

cm~~)

in

particular,

are

strongly changed

in

A6C60 crystals.

The bands of the enhanced modes _are

significantly

broadened. These results

suggested

that the vibronic

dynamics

in A6C60 are

strongly

^modified

in contrast to our observation for

(C60)6S80.C2HC13.

A characteristic

absorption

band of

crown-shaped

58

rings

at 468 cm~~ in the _pure sulfur is somewhat shifted

(up

to 470

cm~~)

and broadened. Other bands of

58 (e.g.

667

cm~~) keep

their

frequency

and form.

The IR spectrum ^{of the}

complex

includes also _very weak bands

corresponding

to the strongest

absorption

bands of the solvent.

C2HC13

strongest ^bands at 927, 844 and 788 have their counterparts at

927,

839 and 774 cm~~. These results

testify

the solvent inclusion within the

crystal

and

specific

interactions between the chlorine _atoms of the

trichloroethylene

and

(C60)6S80

franiework.

All these observations suggest ^that

(C60)S80.C2HC13 complex

is

mostly molecular, perhaps

those of

C(p,

where _« 1. C60 is very little modified in the

complex

and testifies that the

charge

^transfer is small. Conclusions drawn from the

spectral investigation

of

(C60

)6S80

.C2HC13

are close _to that for other C60

compounds [8-1ii. Decomposition

of the

compound

_occurs in the range of about 380-490 K. An intensive liberation of the sulfur

begins

at about 460 K

resulting

in about 25 _{To mass} loss. It _means that after thermal

treating

^{the solvent and}

roughly

about 65 To of the sulfur is lost. Infrared spectrum of _a heated

sample (Fig. 4)

shows that except sulfur and solvent losses new components appear. It suggests that sulfur reacts with an oxygen and _a carbon. The main _new bands observed in the heated and

decomposed complex

_are:

iogg

cm~~

_(U

C=S,),

io32 cm~~

iv S=O)

and 712 cm~~

iv C-S).

3~ _b

<

~

g +

W

E

Iw

©

a

l100 1000 900 800 700

Frequency (crrl ₎

Fig. 4. Infrared spectra of freshly prepared

(C60)6S80.C2HC13 complex(a)

and after

heating (b).

4. Conclusion.

A _new

complex

ofC60 with

sulfur, containing

^{the solvent}

^molecules,

^{has been}

synthesized.

From the

spectral

observation _we think that the

crystals

of the _new

sulfur-fullerite,

_as fullerene

itself,

are true _van der Waals solid without

strong

interaction between the constituent molecules. An

X-Ray crystallographic analysis

and studies of

physical properties

of

(C60)6S80 .C2HC13 complex

are now in progress.

Acknowledgements.

We thank Dr. R.

§wietlik

_for discussions.

References

ii]

Roth G. and Adelmann P., J. Phys. I Hance 2

(1992)

1541.

[2] ^{Roth G. and Adelmann} P., App. Phys. A56

(1993)169.

[3] Buravov L-I-, Oyachenko O-A-, Konovalikhin S-V-, Kushch N-D-, Lavrentiev I-P-, Spitsyna N.G., Shilov G-V- and Yagubskii E.B., Mendeleev Commun.

(in press).

[4] ^Roth G., Adelmann P. and Knitter R., Mater. Lett.,

(in

press).

[5] ^Kritschmer W., Lamb L-D-, Festiropolous K. and Huflmann D-R-, Nature 347

(1990)

354.

[6] Ciesielski W. and Majchrzak I., Wiadomold Chemiczne

(in preparation).

[7] Greaney M.A. and Gorun S.M., J. Pl~ys. Cl~em. 95

(1991)

7142.

[8] Laukhina E.E., Majchrzak I., Ciesielski W. and Graja A., J. Chem. Soc., Chem. Commun.

(subnfitted).

[9] ^Fu K.-J., Karney W.L., Chapman O.L., Huang S.-M., Kaner R-B-, Diederich F., Holczer K. and Wl~etten RI., Phys. Rev. 846

(1992)1937.

[10] Pradeep T., Singh K.K., Sinha A.P.B. and Morris D-E-, J. Cl~em. Sac., Cl~em. Commun.

(1992)

1747.

Ii

II Kamar£s K., Breitscl~werdt A., Pekker S., Fader-Csorba K., Faigel G. and Tegze M., Appl. Pl~ys.

A56

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231.