MÖSSBAUER SPECTROSCOPIC STUDIES OF THE INTERMOLECULAR INTERACTION IN THE ORGANOMETALLIC MOLECULAR COMPOUNDS

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MÖSSBAUER SPECTROSCOPIC STUDIES OF THE INTERMOLECULAR INTERACTION IN THE ORGANOMETALLIC MOLECULAR COMPOUNDS

S. Matsubara, M. Katada, K. Sato, I. Motoyama, H. Sano

To cite this version:

S. Matsubara, M. Katada, K. Sato, I. Motoyama, H. Sano. MÖSSBAUER SPECTRO- SCOPIC STUDIES OF THE INTERMOLECULAR INTERACTION IN THE ORGANOMETALLIC MOLECULAR COMPOUNDS. Journal de Physique Colloques, 1979, 40 (C2), pp.C2-363-C2-366.

�10.1051/jphyscol:19792129�. �jpa-00218500�

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MOSSBAUER SPECTROSCO?IC S T U D I E S OF THE INTERMOLECULAR I N T E R A C T I O N I N THE O!?GANOMETALLIC MOLECULAR COMPOUNDS

S. Matsubara, M. Katada, K. Sato, I. Motoyama and H. Sano

Department o f Chemistry, Faculty o f Science, Metropolitan U n i v e r s i t y , Fukasawa, Tokyo 158, Japan

Rdsum6.- Le paramstre €I'M caractdristique de la constante de force intermoldculaire, a dtd estimd en appliquant l'approximation de Debye et Born von Karman pour calculer la variation en fonction de la tempdrature de la fraction d'effet sans recul dans quelques composds organiques dtain et de fer. On observe une distribution de ce paramstre qui depend de l'etat d'association moleculaire dans le so- lide.

Abstract.- As a parameter of intermolecular force constant, the value of

€12n

was estimated by apply- ing the Debye and Born von Karman's approximation to the temperature dependence of the recoil-free fraction of a number of organotin and some of organoiron compounds. The parameter is distributed de- pending upon the state of molecular association in solid.

The recoil-free fraction and its temperature €l is the Debye temperature, M is the molecular mass, dependence provide us with useful information of the and k is the Boltzmann constant. Although the abso- intermolecular interaction in a solid state. We have lute value of spatially averaged recoil-free frac- so far reported the recoil-free fraction for about tion is not always extrapolated to unity as tempera- thirty organotin compounds and found that the re- ture goes to 0 K,the relative value of the recoil- coil-free fraction and its temperature dependence free fraction shows almost the same slope of the are associated with the state of intermolecular absolute value in the temperature dependence. We association and of molecular packing in a solid / I - have applied the Debye approximation and the Born 9/. In the present work, the values of parameter of von Karman's one dimensional molecular solid appro- intermolecular force constant were evaluated from ximation to the slope in order to derive the para- the data obtained for several organotin and organoi- meter of intermolecular force constant,a, in a so- ron compounds and the data reported previously on lid by using the following relationship

organotin compounds.

-

k0

-

The compounds, C(c6~5) Z S6, ~( ~ 6 ~ 1 1 ) , ~ n , h - 'max ^a^(;)v2

( C ~ H S ) ~ S ~ ( C ~ F ~ ) , (C6Hs)zSn(C6Fs)2, (C5Hs)Fe(CO)zSn where vmax is the maximum lattice frequency which is (CsH5) 3 , (C5H5)Fe(C0)2SnC13, trans-Be C12(CNC6Hs assumed to be equal to the Debye cut-off frequency.

O C H ~ ) ~ , and cis and

~ ~ ~ ~ S - B ~ ( C N C ~ H ~ O C H ~ ) I ,

( ~ n ~ 1 3 a Combining ( I ) and (2) we can obtain the following were purchased or prepared according to the methods

described in references /10,11/. The purity was checked by melting point, elemental analysis and assbauer parameters. The samples were obtained in polycrystalline powders and the "absolute" value and

"celative" value of the recoil-free fraction were evaluated from the area of the Gssbauer spectrum for the compounds according to the method described in our previous works 161.

According to the Debye approximation in high temperature limit, the "relative" value of the recoil-free fraction, fa, is given by an expression

~ E ~ T fa = exp (

- -

1

blc2ke2

where E is the energy of the Gssbauer transition,

expression

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where 3 ~ ~ / k c ~ is 2.13 x

lo4

for "'~n and 7.76 x

lo3

for 5 7 ~ e .

The values of €I'M estimated from the data of the temperature dependence of the recoil-free fraction of the organotin and organoiron compounds were summarized in table I together with the values obtained for the data reported previously on a number of organotin compounds. It was found that there is the distribution of the parameters of the intermolecular force constant with respect to the state of molecular associationinsolid state as shown in figure 1.

The values of parameter are distributed around unity for non-associated compounds.

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:19792129

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JOURNAL DE PHYSIQUE

Table I :Debye temperatures and parameters of intermolecular force constant for organometallic compounds.

Molecular Debye Parameter of State of 1) weight temperature intermolecular molecular

Compound force constant association

0

M (K) x

mono.

h.p.

1-p.

2-p.

3-p.

--

1) mono. = monomer; h.p. = helical chain polymer; 1-p. = one-dimensional polymer; 2-p.

-

two-dimensional polymer: 3-p. = three-dimensional polymer.

2) ArNC = p-CH30C6H4NC.

3) TDT = 3.4 toluene dithiol.

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quadrupole split spectrum is observed in most of

Parameter.

6%

110~amu

Fig. 1 : The distribution of parameters of the intermolecular force constant with respect to the state of molecular association in solid state.

_ - .

^monomer;

--- - .

one-dimensional polymer;

---

^:two-dimensional polymer.

It may be worth mentioning both the values of

e2n

obtained for "'~n a n d ' 5 7 ~ e atoms are essentially the same. The similarity of the values of 0 ' ~ found for the compounds which have iron and tin atoms in a given molecule may prove the consistency of the parameter. Those of one-dimensional polymer compounds and of two-dimensional polymer compounds are distributed around 1.3 and 1.7, respectively. The distribution of the values of parameter for three- dimensional polymer compounds is not shown since there are few organometallic compounds which are known as three-dimensional polymer. It is expected, however, that the parameter may lie above the values for two-dimensional polymer compounds, because the values of the parameter of tin bis-3, 4-toluenedi- thiolate, Sn(TDT)2, and of dimethyltin molybdate,

(CH3)nSnMoOr, known as three-dimensional polymer compounds are 2.08 and 3.24,respectively.

As the value of parameter is evaluated from the spatially averaged recoil-free fraction, a lar- ge portion of overlapping is observed between the non-associated compounds and one-dimensional polymers and between the one-dimensional and two-dimensional polymers, but the parameter still seems to reflect statistically the difference in the intermolecular association. Harrison and his co-workers 1121 have recently reported the temperature dependence of the area of Mijssbauer spectrum for 17 tin compounds and pointed out that the temperature dependence was a useful guide to the nature of the

those one- and two-dimensional polymer compounds.

This line asynnwtry, the Gol'danskii-~aryagin effect, arises from the anisotropy of the recoil-free fraction due to the difference in the intermolecular bonding in molecular solid compounds. The parameters evaluated for each component in the direction parallel to and perpendicular to the polymer bonding in (CsH5)2SnO, ( C ~ H S ) ~ S ~ O C ~ H ~ O and (CH3)3 SnOH are summarized in table 11.

Table I1 : The parameters of the intermolecular force constant for one- and two-dimensional polymer compounds.

-

Temperature Parameter of ^I

region intermolecular

Compound force constant

( K ) o2n x 1 0 - ~ parallel to the I 70-160 1.80 polymer plane

'

^160-280 ^3.56

(c6n,,) 2Sn0 perpendicular to

70-160 1.06 the polymer plane

I

^160-280 0.76

parallel to the 1 70-160 3.12 polymer plane

160-240 1.26 (C6H5) 2SnOC6H40

perpendicular to 70-160 0.52 the polymer plane

{

^160-240 ^0.94

parallel to the 70-170 1.52 polymer axis

(CHj) .,SnOH

perpendicular to 70-170 0.93

the ~olnser axis

As can be seen from the table, the parameter of intermolecular force constant for the direction parallel to polymer bonding is larger than that for the non-polymeric direction. The anisotropy of the parameter may be used for the determination of the molecular association in solid together with the over- all value of the parameter.

lattice structure of tin compounds. Using their data, we evaluated the values of parameter of intermolecular force constant for those tin compounds.

The parameters thus obtained are distributed in the same region of the corresponding lattice structure as that shown in figure I .

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JOURNAL DE PHYSIQUE

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