Synthesis and Properties of Some New Organic Intercalation

3 Synthesis and Properties of Some N e w

Organic

Intercalation Complexes of Tantalum Sulfide R. L .

HARTLESS

and A . M .

TROZZOLO

Downloaded by COLUMBIA UNIV on April 5, 2013 | http://pubs.acs.org Publication Date: June 1, 1974 | doi: 10.1021/bk-1974-0005.ch003

B e l l Laboratories, M u r r a y Hill, N.J. 07974

Intercalation of layered compounds by metals has been p r e v i o u s l y r e p o r t e d ( 1 - 5 ) . A number o f i n o r g a n i c and biological m o l e c u l e s have been found to i n t e r c a l a t e c l a y s and g r a p h i t e ( 6 , 7 ) . The first intercalation of layered transition m e t a l c h a l c o g e n i d e s by o r g a n i c m o l e c u l e s was r e p o r t e d by Weiss and Rudhardt ( 8 ) . They intercalated TiS w i t h h y d r a z i n e and aliphatic amides and o b s e r v e d i n c r e a s e s o f s e v e r a l angstroms in the interlayer s p a c i n g o f the c h a l c o g e n i d e . More r e c e n t s t u d i e s show t h a t a v a r i e t y o f o r g a n i c m o l e c u l e s intercalate layered transition m e t a l c h a l c o g e n i d e s (9-11). The o r g a n i c m o l e c u l e s p e n e t r a t e the i n t e r l a y e r p l a n e s and form a p e r i o d i c crystalline structure. In a d d i t i o n to i n c r e a s e d i n t e r p l a n a r s p a c i n g , the i n t e r c a l a t e d complexes showed enhancement o f the critical superconducting temperature ( Tc) above t h a t o b s e r v e d f o r the unintercalated chalcogenide. Tantalum sulfide crystallizes i n several polytypes which are c h a r a c t e r i z e d by layer-like structures i n which the m e t a l atoms are l o c a t e d between a l t e r n a t e sulfur layers. The bonds forming the i n t r a p l a n a r l a y e r s are s t r o n g ( p r i m a r i l y c o v a l e n t ) bonds. Each s u l f u r - t a n t a l u m - s u l f u r l a y e r ( i n t e r p l a n a r ) i s bonded to a d j a c e n t l a y e r s by weak van der Waals attraction. Intercalation ( i n s e r t i o n ) o f atoms o r m o l e c u l e s between the l a y e r s o c c u r s by c l e a v a g e a l o n g the p l a n e s which have the low energy i n t e r a c t i o n . F i g u r e 1 g i v e s a schematic d e s c r i p t i o n o f the s t r u c t u r e o f the l a y e r e d transition metal chalcogenide prior to intercalation where M i s the transition m e t a l atom and X i s the c h a l c o g e n atom. Shown are t h r e e i n t r a p l a n a r l a y e r s s e p a r a t e d by the van der Waals gap. The intraplanar l a y e r s are a p p r o x i m a t e l y 6 Å t h i c k and the i n t e r l a y e r distance between transition m e t a l atoms i s a p p r o x i mately 6Å. Upon intercalation of the organic molecule, 2

o

23

In Extended Interactions between Metal Ions; Interrante, L.; ACS Symposium Series; American Chemical Society: Washington, DC, 1974.

24

EXTENDED

INTERACTIONS B E T W E E N

METAL

IONS

the van der Waals gap expands as s c h e m a t i c a l l y r e p r e sented i n F i g u r e 2. T a b l e 1 shows the s y n t h e s i s con d i t i o n s and parameters f o r some p r e v i o u s l y i n t e r c a l a t e d complexes ( 9 ) . The i n t e r l a y e r d i s t a n c e f o r the p y r i d i n e - T a S g c o m p l e x i n c r e a s e s ~Joh t o g i v e a m e t a l m e t a l d i s t a n c e o f ^12A. In the case o f the o c t a decylamine-TaS^ complex, the enhanced i n t e r l a y e r d i s t a n c e was Λ,^ΟΑ which was a t t r i b u t e d t o two l a y e r s o f the amine o r i e n t e d end-to-end and p e r p e n d i c u l a r to the TaS2 p l a n e s ( F i g u r e 3 ) . In g e n e r a l , o r g a n i c m o l e c u l e s capable o f i n t e r c a l a t i n g T a S a r e Lewis bases c o n t a i n i n g an sp3 o r s p h y b r i d i z e d n i t r o g e n . T h i s study i n v o l v e s i n t e r c a l a t i o n o f the 2Hp o l y t y p e o f tantalum s u l f i d e ( T a S ) w i t h o r g a n i c m o l e c u l e s o f v a r i o u s s t r u c t u r e s t o form complexes w i t h i n c r e a s e d i n t e r l a y e r s p a c i n g and enhanced c r i t i c a l s u p e r c o n d u c t i n g temperatures. The e x t e n t o f i n t e r p l a n a r l a y e r expansion and T enhancement v a r i e s w i t h the p a r t i c u l a r i n t e r c a l a t e , thus a l l o w i n g p o s s i b l e chemical c o n t r o l of T . 0

2


2

2

c

c

Experimental The powdered tantalum s u l f i d e was p l a c e d i n a 4mm p y r e x tube w i t h the l i q u i d i n t e r c a l a t e o r a benzene s o l u t i o n o f the s o l i d i n t e r c a l a t e . The tube was evacuated and s e a l e d and the r e a c t i o n s c a r r i e d out i n i s o t h e r m a l baths a t 25, 100, 150 and 200°. Inter c a l a t i o n was e v i d e n t when the volume o f the chalcogenide increased. A f t e r i n t e r c a l a t i o n , the excess o r g a n i c r e a c t a n t s were removed by washing w i t h benzene f o l l o w e d by d r y i n g a t reduced p r e s s u r e . S u p p o r t i n g evidence f o r i n t e r c a l a t i o n was o b t a i n e d by powder x-ray d i f f r a c t i o n w i t h a G u i n i e r camera u s i n g CUKQ r a d i a t i o n . The c r i t i c a l s u p e r c o n d u c t i n g tem p e r a t u r e s were determined on powdered complexes by AC s u s c e p t i b i l i t y measurements. R e s u l t s and D i s c u s s i o n S e v e r a l mono- and d i s u b s t i t u t e d amines form complexes w i t h T a S ( T a b l e 2 ) . In g e n e r a l the amines which i n t e r c a l a t e d had p K > 9 . D i e t h y l a m i n e inter c a l a t e s i n two hours a t ambient temperatures to y i e l d a comçlex w i t h an i n t e r l a y e r d i s t a n c e i n c r e a s e (σ) o f 3.69 A and an onset o f s u p e r c o n d u c t i v i t y ( T ) o f 3.0°K. The d i b e n z y l amine complex was s u p e r c o n d u c t i n g at 2 7 ° K and the i n t e r l a y e r s p a c i n g was i n c r e a s e d by 6.39A. P i p e r i d i n e i n t e r c a l a t e s T a S and i n c r e a s e s the i n t e r l a y e r d i s t a n c e by 4.20A, but the complex i s not 2

a

Q

&

2


3.

HARTLESS A N D TROZZOLO

X

X

X

X

VAN DER

X

χ

WAALS BOND

χ

Μ

Μ

X

X

VAN DER WAALS BOND

X

χ

"χ

Χ

Μ


25

M

χ

Figure

Sulfide

X

M

X

Tantalum

Μ X

X

1.

Schematic

of structure

of TaS >

X

Χ

Χ

ο 6Α

Μ

M X

Χ

II

Χ

1

X

Χ

Χ Μ

M Χ

Χ

Χ

Figure 2. Schematic of structure of TaS> substituted pyridine complexes

TABLE I SYNTHESIS OF T a S

TaS

2

CH -(CH ), -NH 5

2

7

2

2

COMPLEXES

TEMP. (°C)

TIME (DAYS)

8(A)

T (»K>

—

—

6.05

0.8

200

1

40

30

0

5 81

3.5

50

3.0


26

E X T E N D E D INTERACTIONS B E T W E E N

T 6A i

METAL

IONS

x~^( χ M M X X X

0

25 A

Figure


50A

3. Schematic of structure TaS> (octade calamine

of

X X X M M X X X

TABLE 2 TdS - AMINE COMPLEXES 2

SYNTHESIS INTERCALATE

TEMP. C O

T I M E (DAYS)

B(l)

T (*K)

25

3.6a

3.0

150

4.02

150

6.39

2.7

25

6.15

2.4

3

4.20

NS

8

3.65

1.8

0

CH,CHo CH3CH2 CHJCH2CH2CH2

>

>-H

CH3CH2CH2CH2

;N-H

0-CH

0 - C H

2

2

C M N~N

-
J-NH

H

O

s

N—NH CH

Qj-NH

0

2

3

2

25

14

13.00,6.26

100

5

6.26,4.08

2.9,2.4

2.9

25

10

3.14,1.66

2.4,1.8

150

5

3.48,2.09

2.5,1.6

0

H-C-NH-NH-C-H

TABLE 4 CORRELATION OF PKa .CHARGE DENSITY (ACT) AND THE TEMPERATURE FOR THE ONSET OF SUPERCONDUCTIVITY (To) INTERCALATE H N-NH 2

CH

pKq

Δσ

T CK)

2

7.93

.3795

4.9

2

7.21

.3608

4.0

2

7.87

.3485

3.3

5.2

.3429

2.0

Q

3

^N-NH CH 3

CH X

3

N~NH

N-NH,


3.

ιιARTLESS A N D T R O Z Z O L O

Tantalum

29

Sulfide

intercalate. The c r i t i c a l s u p e r c o n d u c t i n g t e m p e r a t u r e s f o r t h e h y d r a z i n e , 1 , 1 - d i m e t h y l h y d r a z i n e and m e t h y l h y d r a z i n e complexes a r e 4 . 9 * 3-3°K, whereas t h e p K s a r e 7.93* 7.21 and 7.87 r e s p e c t i v e l y . T h i s has been o b s e r v e d by D i S a l v o f o r amine-TaS2 complexes i n w h i c h an i n c r e a s e i n p K may produce an i n c r e a s e o r d e c r e a s e i n T . T h i s i s c o n f i r m e d by n u c l e a r q u a d r u p o l e r e s o n a n c e d a t a where t h e e l e c t r o n d e n s i t y i n t h e nonbonding n i t r o g e n o r b i t a l s o f h y d r a z o n e s does n o t c o r r e l a t e w i t h T o f t h e i n t e r c a l a t e d complexes. Bray and Sauer have o b s e r v e d t h e same e f f e c t f o r p y r i d i n e - T a S complexes ( 1 6 ) · The c o r r e l a t i o n o f n u c l e a r q u a d r u p o l e resonance d e r i v e d charge d e n s i t i e s w i t h To i s c o m p l i c a t e d by t h e f o r m a t i o n o f two phase complexes-complexes w h i c h have two d i s t i n c t i n t e r l a y e r d i s t a n c e s . F o r example, t h e complex formed between T a S and 1 - p h e n y l - l methylhydrazine has i n t e r l a y e r distance increases o f 13.00 and 6.26 A and t h e Sauer and Bray o c c u p a t i o n number f o r t h e h y d r a z i n e i s Ο.388. The t e m p e r a t u r e f o r t h e o n s e t o f s u p e r c o n d u c t i v i t y f o r t h e complex s h o u l d be > 4.9°K, b u t t h e t r a n s i t i o n o c c u r s a t 2.9°K. The s y n t h e s i s c o n d i t i o n , i n t e r l a y e r d i s t a n c e i n c r e a s e , and t h e t e m p e r a t u r e f o r t h e o n s e t o f s u p e r c o n d u c t i v i t y o f some Ta.S amide complexes a r e i n c l u d e d i n T a b l e 5. The i n t e r c a l a t i o n o f N-methylformamide under v a r i o u s r e a c t i o n c o n d i t i o n s p r o d u c e s d i f f e r e n t complexes. The complex formed a t ajnbient t e m p e r a t u r e s had an i n t e r l a y e r s p a c i n g o f 3.65 A and T = 4.2°K. The complex formed a t 100° had an i n t e r l a y e r s p a c i n g o f 3.00 A and was s u p e r c o n d u c t i n g a t 2.4°K. I f t h e r e a c t i o n i s c a r r i e d o u t a t 90° w i t h u l t r a s o n i c m i x i n g of the reactants, the i n t e r l a y e r distance increases to ^50 Κ and t h e complex i s s u p e r c o n d u c t i n g a t 2.7°K. This evidence supports the previous o b s e r v a t i o n that t h e r e i s no c o r r e l a t i o n between t h e i n t e r l a y e r d i s t a n c e and t h e t e m p e r a t u r e f o r t h e o n s e t o f s u p e r c o n d u c t i v i t y (9). D i - n - b u t y l formamide, N - m e t h y l f o r m a n i l i d e , and d i f o r m y l h y d r a z i n e a l s o f o r m complexes w i t h T a S . D i f o r m y l h y d r a z i n e formed a two phase complex w i t h i n t e r l a y e r s p a c i n g i n c r e a s e s o f 3.48 and 2 . 0 9 Κ and showed two t r a n s i t i o n s f o r t h e o n s e t o f s u p e r c o n d u c t i v i t y a t 2.5 and 1.6°K. I n t e r p r e t a t i o n o f t h e r e s u l t s o f t h e amide complexes i s c o m p l i c a t e d by t h e t e n d e n c y o f t h e s e m o l e c u l e s t o decompose under t h e r e a c t i o n c o n d i t i o n s . Elemental a n a l y s i s i n d i c a t e s the p o s s i b i l i t y o f t h e i n t e r c a l a t i o n o f more than one s p e c i e f o r t h e N-methylformamide complex. The t e n d e n c y o f amide i n t e r c a l a t e s t o decompose has p r e v i o u s l y been o b s e r v e d by D i S a l v o . a

n

d

a

a

0

Q


2

2

0

2

Q

2


30

E X T E N D E D INTERACTIONS B E T W E E N

METAL

IONS

TABLE 5 T 0 S - AMIDE COMPLEXES 2

SYNTHESIS INTERCALATE


Η 0 I II CHj-N—C—H

CH CH CH CH2 J-C-H CH CH CH CH 3

2

3

2

8(A)

TEMP. C O

TIME (DAYS)

25 100 90

30MINS. 14 14

150

4

3.97

150

5

3.48,2.09

200

30

6.05

3.65 3.00 ~50

2

0 II

CH 0 ® - N —C-H 3

TABLE 6 COMLEXES EXHIBITING TWO PHASES

SYNTHESIS TEMP. CO

INTERCALATE

N—NH

2

CH, H

v

/ C

H

3

TIME (DAYS)

8(2)

25

14

13.00,6.26

100

5

6.26,4.08

ToCK)

2.9 2.9,2.4

3

Ν

100

30

4.85

2.7

I

150

30

4.85,3.95

2.7,1.5

150

60

3.95

1.5

100

30

13.63,7.58

3.5

CH CH 0-P=0 2

0

in

2

CHx CH CH 3

CH

s?

3

I

> - P = O

CH

3

N

/ \ CH CH 3

4.2 2.4 2.7

2

H-C-NH-NH-C-H

2

0

2

0 II

TaS

T ÇK)

3


2.5,1.6

3.

HARTLESS AND TROZZOLO

Tantalum

Sulfich

31

The p r e c e d i n g p a r a g r a p h r e f e r r e d t o the f o r m a t i o n o f a two-phase complex between T a S and d i f o r m y l h y d r a z i n e i n w h i c h the complex had two i n t e r l a y e r s p a c i n g s and two t e m p e r a t u r e s f o r the o n s e t o f s u p e r c o n d u c t i v i t y . The f o r m a t i o n o f two phase complexes appears t o be f a i r l y g e n e r a l and t h e r e are i n t e r e s t i n g r e l a t i o n s h i p s between σ, To, and r e a c t i o n c o n d i t i o n s (Table 6 ) . Reaction of 1-methyl-l-phenylhydrazine w i t h T a S a t ambient t e m p e r a t u r e s y i e l d e d a two-phase complgx w i t h i n t e r l a y e r d i s t a n c e i n c r e a s e s o f 13*00 and 6.26 A w h i c h was s u p e r c o n d u c t i n g a t 2.9°K. R e a c t i o n at h i g h e r t e m p e r a t u r e s y i e l d e d a complex i n w h i c h the 13.00 A d i s t a n c e d i s a p p e a r e d and a new d i s t a n c e (4.08 K) appeared. The 6.26 A i n t e r l a y e r d i s t a n c e i n c r e a s e was p r e s e n t i n b o t h complexes. The same appearance and d i s a p p e a r a n c e o f s p a c i n g s was o b s e r v e d i n the f o r m a t i o n o f d i e t h y l methylamidophosphate complexes. The complex formed a t 100° had one i n t e r l a y e r d i s t a n c e o f 4.85 $ and one t e m p e r a t u r e f o r the o n s e t o f s u p e r c o n d u c t i v i t y . The complex formed a t 150° had 3.95 A and 1.5°K f o r the i n t e r l a y e r d i s t a n c e i n c r e a s e and s u p e r c o n d u c t i n g t r a n s i t i o n , r e s p e c t i v e l y . At i n t e r m e d i a t e r e a c t i o n c o n d i t i o n s , the complex formed had b o t h i n t e r l a y e r d i s t a n c e i n c r e a s e s and b o t h superconducting t r a n s i t i o n s . From p r e v i o u s r e s u l t s t h e d e c r e a s e i n the t r a n s i t i o n t e m p e r a t u r e w i t h a d e c r e a s e i n i n t e r l a y e r s p a c i n g cannot be a t t r i b u t e d s o l e l y t o the i n t e r l a y e r d i s t a n c e change. I t seems r e a s o n a b l e t h a t the i n c r e a s e d tempera t u r e s and r e a c t i o n t i m e s a l l o w the i n t e r c a l a t e t o r e a c h an e q u i l i b r i u m o r i e n t a t i o n where e l e c t r o n d o n a t i o n t o the u n f i l l e d m e t a l l i c bands i s l e s s e f f i c i e n t , t h e r e b y c a u s i n g a d e c r e a s e i n the t r a n s i t i o n temperature. 2


2

Summary A number o f o r g a n i c i n t e r c a l a t e d complexes o f the 2H-phase o f T a S have been p r e p a r e d w h i c h have i n c r e a s e d i n t e r l a y e r s p a c i n g s and enhanced c r i t i c a l superconducting temperatures. There i s a d i r e c t c o r r e l a t i o n between the n u c l e a r q u a d r u p o l e resonance d e r i v e d charge d e n s i t i e s o f the i n t e r c a l a t e w i t h the enhanced s u p e r c o n d u c t i n g t e m p e r a t u r e s o f h y d r a z i n e complexes. Some o r g a n i c i n t e r c a l a t e s form two phase complexes w h i c h may have one o r two t e m p e r a t u r e s f o r the o n s e t o f s u p e r c o n d u c t i v i t y . 2


32

EXTENDED INTERACTIONS BETWEEN METAL IONS Literature

Cited

1. Voorhoeve, J . M. and Robbins, M., J. Solid State Chem., (1970), 1, 134. 2. Huisman, R., Kadijk, F., and Jellinek, F., J. Less-Common Metals, (1970), 21, 187. 3.

Omloo, W. P. F. Α. Μ., and Jellinek, F., J. LessCommon Metals, (1970), 20, 121.


4. Rudorff, W., Chimia (1965), 19, 489. 5. Rudorff, W. and Sich, H. H., Angew. Chem., (1959), 71, 724. 6.

Freeman, A. G. and Johnston, J. H., Carbon (Oxford), (1971), 9, 667.

7. Grim, R. E.,"ClayMinerology,"McGraw-Hill, New York, N.Y., 1968. 8. Weiss, A. and Rudhardt, R., Z. Naturforsch., Β (1969), 24, 265, 355, 1066. 9. Gamble, F. R., DiSalvo, F. J., Klemm, R. Α., and Geballe, T. H., Science (1970), 168, 568. 10.

Gamble, F. R., Osiecki, J. H., Cais, M., Pisharody, R., DiSalvo, F. J., and Geballe, T. H., Science, (1971), 174, 493.

11.

DiSalvo, F. J., Schwall, R., Geballe, T. H., Gamble, F. R., and Osiecki, J. Η., Phys. Rev. Lett., (1971), 27, 310.

12.

Ehrenfreund, E., Gossard, A. C., and Gamble, F. R., J. Phys. Rev. Β (1972) 5, 1708.

13.

Beal, A. R. and Liang, W. Y., Phil. Mag. (1973), 27, 1397.

14.

Bardeen, J., Cooper, L. N. and Schrieffer, J. R., Phys. Rev., (1957), 108, 1175.

15.

Sauer, Enrique G. and Bray, P. J., J. Chem. Phys., (1972), 56, 820.


3.

16.

HARTLESS

AND

TROZZOLO

Tantalum

Sulfide

B r a y , P. J. and S a u e r , E n r i q u e G., Communications, (1972), 11, 1239.

33

Solid

State

Acknowledgment


The a u t h o r s acknowledge helpful d i s c u s s i o n s w i t h F. J. D i S a l v o , Jr., G. W. Hull, T. H. G e b a l l e , D. W. Murphy and F. J. Padden, Jr. We particularly thank G. W. Hull f o r t h e superconductivity data.


Synthesis and Properties of Some New Organic Intercalation

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