Synthesis and Characterization of Octamethylenethiafulvalene Compoundswith Osmium, Iridium, Platinium and Gold Chloride

Printed in the Republic of Korea

Octamethylenethiafulvalene
,  ,      
  

  ^†*

  

†

(2001. 8. 23 )

Synthesis and Characterization of Octamethylenethiafulvalene Compounds with Osmium, Iridium, Platinium and Gold Chloride

Chan-kyou Jeong, Hong-Woo Lee, Young-Jin Kim, Sung-Nak Choi^†, and Young-Inn Kim*

Department of Chemical Education, Pusan National University, Pusan 609-735, Korea

†Department of Chemistry, Pusan National University, Pusan 609-735, Korea (Received August 23, 2001)

. Octamethylenethiafulvalene(OMTTF) HAuCl⁴3H²O THF    

(OMTTF)AuCl4  . (OMTTF)²PtCl4, (OMTTF)2IrCl62H²O, (OMTTF)OsCl5THF !" ##

H2PtCl6xH²O, H2IrCl6xH²O $ H²OsCl6 % &' ()*+  . , -." 

/0(EPR, 1 23), 450(IR, UV-Vis), 6/0(CV) 7 6/688 23 . 9:

; 4< 6/688= >? ~10⁻⁷ Scm⁻¹ @; A" 6/688 BCD .  3 OMTTF +
E Au, Pt, Ir, Os FG -+ 6 @H@ @IJK OMTTF= L6M @:, OMTTF
⁺N@:

OPQ+ RS . OMTTF
⁺N@: OPQ; T3" UV 6W X YZ . 1 [+
E (OMTTF)²IrCl62H²O $ (OMTTF)OsCl⁵THF= OMTTF
⁺ @: RS= \6 ]^ FG(Ir $ Os) _S, \6. @= `' ` 9ab@ RScd e  fD .

ABSTRACT. The charge-transfer compound (OMTTF)AuCl4 was prepared from the direct reaction of octamethylenethiafulvalene (OMTTF) with HAuCl4· xH2O in THF. (OMTTF)2PtCl4, (OMTTF)2IrCl6· 2H2O, and (OMTTF)OsCl5· THF were also formed using H2PtCl6· xH2O, H2IrCl6· xH2O and H2OsCl6, respectively.

The prepared compounds were characterized by magnetic (EPR, magnetic susceptibility), spectroscopic (IR, UV-Vis), electrochemical (CV) methods, and the powdered electrical conductivity measurement. The pow- dered electrical conductivities at room temperature were ~10⁻⁷ S · cm⁻¹. The experimental results show that OMTTF^·+ monocation radicals exist in all of the prepared compounds. The redox potential of OMTTF supports that OMTTF^{· +} is relatively stable. The magnetic properties indicate that there are significant magnetic inter- actions between the localized odd electrons on the central metal (Ir and Os) ions and the odd electrons resided on OMTTF^{· +} cation radicals in both (OMTTF)2IrCl6· 2H2O and (OMTTF)OsCl5· THF.

 

Tetrathiafulvalene(TTF) $ TTF /g+' h
&

/-i" 6/688 BC= 6@H -; 

 3 jk l" 6mn+ oJ p .¹ q rs" t+u 6/68 -i;  vw%, TTF x= TTF /g+ = &/-id 6mn+

y, h
6@FG -d 6zn+ 

% 6@H-id % p .² 6@FG -"

{|}; ~, €W r; ‚ !; €W Uƒ; ‚

 „O N'  9… BC†  f*‡+ 

 ˆ  f= l" ‰Š -i@ . ‹Œ= 6 zn+ -UV @ 0 @' Ž F(Au),

F(Pt), @{(Ir) $ ‘’“(Os) - TTF^2ex

= bis(ethylenedithio)tetrathiafulvalene(BEDT-TTF)^2h|

; 6@H -d % Šy . Šy, 

- ] TTF”
40*+ , Au, Pt, Ir 

-" 8• W; 4< 6/688 (10⁻³~10⁻⁴ S · cm⁻¹) BC– —, TTF²⁺+ L6M , Os 

-" 10⁻⁷S · cm⁻¹+ A" 6/688 Š%˜*+

™, TTF;  9…” 6/688 ]š' Z›d YZ .
40*+ , BEDT-TTF -"

10⁻²~10⁻⁴S · cm⁻¹; 4< 6/688 BCœD .^2h q r= octamethylenethiafulvalene(OMTTF)

 6mn+ % Au, Pt, Ir, Os -d c

= 6@H -d y  . OMTTF

= TTF žŸd & —, TTF žŸ ¡
 @¢

+£¤Z y{ cy f*¥, OMTTF  6W

= DMF (OMTTF¦OMTTF
⁺ E1/2=0.18 V) TTF;  6W(TTF¦TTF
⁺ E1/2 0.00 V) &' Xd BC– . „O TTF N@: §¨” + OMTTF N@:8 ©n T3ª  fd «*+ ¬#

, .

, OMTTF-Au, Pt, Ir, Os -" /0, 4 50, 6/0 id 23% -{0 7

d *¥, TTF x= BEDT-TTF - 

% TTF žŸ ¡
; @¢+£¤Z y{; ­®

d ¯° Š± .

 

(OMTTF)AuCl4= Ar RS, OMTTF(1.0×10⁻³

²); THF  25 ml HAuCl⁴3H²O(3×10⁻⁴²);

THF  10 ml ³³M ”— ´ 2| HT 

  .  d µ¶y Šv' ‰

·" ¸¹; º6-" %% THF j+ %»¼ ½ D . %-" s¾ 9…+ 9: ¿À . (OMTTF)2PtCl6, (OMTTF)2IrCl62H²O, (OMTTF)OsCl5 THF !" THF   ## H²PtCl6xH²O,

H2IrCl6xH2O $ H2OsCl6 % &' ()*

+  . ' -; VÁ 4Â" (C, H, S) /àVrÄC(Å4Á) Æ*¥, Ç

X È hÉ .

(OMTTF)AuCl4Ç X(%): C, 25.82; H, 2.48; S, 19.69 ÆÊ X: C, 25.82; H, 2.47, S, 20.26. (OMTTF)² PtCl6 Ç X(%): C, 32.56; H, 3.12; S, 24.83 ÆÊ X: C, 32.18; H, 3.22, S, 25.40. (OMTTF)²IrCl62H²O Ç X(%): C, 31.55; H, 3.40; S, 24.06 ÆÊ X: C, 30.38; H, 3.36, S, 23.68. (OMTTF)OsCl5THF Ç

X(%): C, 28.75; H, 3.22; S, 17.05 ÆÊ X: C, 26.24;

H, 3.37, S, 17.81.

9:; 4<688= &{v  ËÁ Ì

( Í 5 m/m) @ 4<d ÎÏ% 6 ¤/ 2 3% r .³ EPR ’ÐÑÒ" Bruker Instruments ESP-300S % 77 K (CH2Cl2/DMF=

1:1) 9 23 . 1" 4~300 K :8 W

 SQUID ()*+ r*¥, ÓÔ Quantum Design; MPM⁵⁷d  . >Õ Ö@C= Pascal 9 % r V;  TIP(tempera- ture-independent paramagnetism)d Š3 . IR ’ ÐÑÒ" polaris FT-IR 45/ % KBr V×)

*+ (400~4000 cm⁻¹) vØ*¥, UV-Vis ’ÐÑÒ

" Shimadzu UV-1601PC 45/ % DMF 

 (200~1100 nm) r . ÙU66Î ÚÛ"

BAS CV-50W voltammetric analyzer % DMF (0.1 M TEAP)  36Ü ()*+ vØ . bÝ 6Ü" 1 mm Pt P’Þ, Š 6Ü" Ptß, Ú{

y ày 6Ü" Ag/Ag⁺(0.01 M AgNO3/0.1M TEAP CH3CN)d  .

  

9:; 4< 6/688= ~10⁻⁷Scm⁻¹(Table 1 à) @+
8• W; 6/688 BCD . @ X" &' ()*+ ' TTF x= BEDT- TTF FG@:(Au, Pt, Ir, Os); 6@H -;

6/688 á(σRT=10⁻⁴~10⁻² Scm⁻¹) A" X@

. @= TTF $ BEDT-TTF 6@H -= TTF x= BEDT-TTF”
40*+ , —, OMTTF

-= OMTTF” L6M oJ OMTTF⁺¹+ RS¥, OMTTF⁺¹ FG @:; 36/0 9ab

≅

@ jk Þ/ âã*+ ä3, . Ú{y q r

 ' OMTTF -; 6/688” jk A"

«*+ ÓIJ åâ, OMTTF⁺” L6M , « æ çèO y• [3  OMTTF⁺; éº ê9@ ë 0*+ @IJ   ì" «*+ ×íoD .

4< EPR ’ÐÑÒd 9: 23*¥, Fig.

1 # -; EPR ’ÐÑÒd BCD . (OMTTF) AuCl4 (OMTTF)OsCl5THF= î0Z ïÞ Š

%mJ, g ðñX, <g>, d r . (OMTTF)²PtCl6 (OMTTF)2IrCl62H²O= !( g
 g^ 4{ˆ

 fD . EPR òOóC g X $ ïÞ-ïÞ |Ÿ

(∆Hpp)d Table 1 š´ . >Õ -; g ðñ X" <g> ~2.009@¥, ô{' >õd BC– . @ X

" & 6; g X x= TTF /g+ ' TTF
⁺ N

@: OPQ; g X jk &' «@ .⁴ „O Æ Ê r' EPR ïÞ= # -; OMTTF
⁺N@

: OPQ ;' «*+ ä2oD . Ú{y FG @ : ;' EPR ïÞ= vØo  ì± . „O FG

@:@  id ö÷B, øÜ 9ab@ އ

+ q ÆÊ ¿= 23o  ì= «*+ ¬#, . 1d 4~300 K :8 W 23*¥, Fig. 2 :8 ‚ „ù 1d BCD . (OMTTF⁺)2- Table 1. The electrical conductivities, EPR parameters, and magnetic properties of powdered (OMTTF)mMCln compounds

Compound σrt (S · cm⁻¹)

EPR parameters Magnetic moment^c g value^a ∆Hppb (BM)

(OMTTF)AuCl4 < 10⁻⁷ <g>=2.009 8 1.62

(OMTTF)2PtCl6 < 10⁻⁷ g||=2.013

g
=2.009

16 -

(OMTTF)2IrCl6 2H2O < 10⁻⁷ g||=2.014 g
=2.009

21 1.09

(OMTTF)OsCl5 THF < 10⁻⁷ <g>=2.007 15 1.32

aThe listed g values were measured at room temperature.

bThe values are peak-to-peak linewidth (Gauss).

cThe magnetic moments were measured at room temperature.

Fig. 1. The X-band EPR spectra of OMTTF metal com- pounds. 1: (OMTTF)AuCl4, 2: (OMTTF)2PtCl6, 3: (OMTTF)2

IrCl6· 2H2O, 4: (OMTTF)OsCl5· THF.

Fig. 2. Temperature dependence of magnetic susceptibility for (OMTTF)mMCln compounds.
: (OMTTF)AuCl4,
: (OMTTF)2IrCl6· 2H2O, _: (OMTTF)OsCl5· THF.

PtCl6=  id BCœ*¥, (OMTTF)AuCl4, (OMTTF)2IrCl62H²O $ (OMTTF)OsCl⁵THF= : 8” úÁ— 1@ M û” ” A" : 8= jk üŸM û” . Ú»B 1; : 8 „ù ‚= Curie-Weiss )ý(χ=C/(T-Θ))= 0

o  ì± . &ë/>þÑ(effective magnetic moment, µeff)= µeff=2.828 + Ç*¥, 9:

; &ë/>þÑ X" Table 1 š´ . (OMTTF)AuCl4; &ë/>þÑ X(1.62 BM)" 1 ÿ; \6” BC= ’
; X(1.73 BM) á Á b" X@ . ]^ FG Au"  3

OMTTF+
E Au(IV) @:*+ 6@H@ @IJK

Au(IV)¦Au(III)+ UVo¥, Au(III)" d⁸ 6 €;

 id ö= . „O (OMTTF)AuCl⁴; &ë />þÑ= OMTTF
⁺N@: OPQ ;' &ë />þÑ+ ¬#, . (OMTTF)2PtCl6= EPR [

§¨” +  id BCD . @»' [+

ÓIJå â, (OMTTF
⁺)2
4" OMTTF
⁺N@: O PQ _S, \6. @ `' `(antifer- romagnetic) id ”i «*+ ä3oD .

1 /%= /"  @ BC†  f .

%/ χ(T)" ]^ FG @: _S, 6 ’

 ;' /*+ Curie-Weiss )ý „ «@ . χOMTTF= OMTTF OPQ; /%8@¥, δ(T)= FG @ : OMTTF; 9ab ;' /0 U*+

# -; -{0 Uƒ ;á 7y  ' /0 Ud @ . (OMTTF)²IrCl62H²O

OMTTF= N@: OPQ OMTTF
⁺+ RS¥, ]^

FG Ir" Ir(IV)  9…+ d⁵ 6 €+ \6” 'ÿ RS' . Ú»B Ù' IrCl⁶²⁻ Ž" Ir⁺⁴ @:.

; ` 9ab ;á ’
; XŠ Á 0

" 1.6~1.7 BM; Xd BC= «*+ eK f .⁵ (OMTTF⁺)OsCl5THF- Os(IV) @:" d⁴6  €d ö= . Os(IV) @:" ’
-8c  

 9ab@ jk  «*+ eK f*¥ ’
;

&ë/>þÑ(2.8 BM)Š jk b" Xd BC– . 9: 
4; Os(IV) -; &ë/>þÑ X

" 1.2~1.7 BM+ Šy oD .⁶9: r' (OMTTF)² IrCl62H²O (OMTTF)OsCl⁵THF; &ë/>þ

Ñ= ## 1.09 $ 1.32 BM@D (Table 1à). Ú»

B @. -.; 1; :8;R" Curie-Weiss )ý 0o  ì± . „O FG @: OMTTF OPQ @; /0 U b@ Þn @IJ ¥,

  χ(T) /%= δ(T)” ]šn b' [ + %s . [Ô (OMTTF)²IrCl62H²O (OMTTF)- OsCl5THF; &ë/>þÑ X@ ## 
4;

IrCl62−$ OsCl⁵⁻ Ž; &ë/>þÑ XŠ 8 0n 2 3, «*+ ÓIJ åâ, IrCl⁶²⁻$ OsCl⁵⁻ _S,

\6 OMTTF
⁺N@: OPQ RS= \6

@= ` 9ab@ @IJi «*+ ä3 oD . Ú»B q ÆÊ @. 9abd 4{ 

=  .

IR ’ÐÑÒ" 400~4000 cm⁻¹W KBr 

()*+ vØ*¥, L6M @:' OMTTF
⁺N

@: OPQ -; IR ’ÐÑÒ jk & .^7-9 OMTTF 4 ; h
C-H Ï sH, C-H  sH

$ C=C Ï sH (d Table 2 š´ . ó

/; C-H  sH" 9 (, k (

,  (, Û (*+ BCD . @.

sH (" OMTTF - $ TTF /g+ ' 4  c= -d % ›;+ [3 .

@¢+e Z; C-H Ï sH" 2,840~3,000 cm⁻¹

W BCB= «*+ eK f . OMTTF ;

ó/; C-H  sH] C-H 9 ("

~1,400 cm⁻¹
Œ vØoD . 1,350~1,550 cm⁻¹

Œ; ! "=  (*+ %s . ËÁ 7

@9; #e Z$; k (" 720 cm⁻¹

Œ vØo¥, n-e Z; ËÁ ” bd% &"

' + @H, . @¢+e Z; ƒk= y{

’Ñ(Z ;á )* &" '  !, . OMTTF 4;  (" ~780 cm⁻¹ vØ oD*¥, q ÆÊ ' -; ƒk=

810~820 cm⁻¹ !oJ OMTTF
⁺ N@: OPQ

; 7 ïÞ+ %s .¹⁰

6! ’ÐÑÒ" DMF  9… 200~1,100 nm W vØ*¥ Ú [= Table 2 š´

 . ' OMTTF-FG -; 6! ’Ð ÑÒ" OMTTF 4= +{ ~668 nm `' !

 "” vØoD . @ ! "= OMTTF
⁺N@:

OPQ ;' 7 ïÞ+ áÂ, . @»' 500 nm

@; A" '  ­,; ! "= ¾ π-4 x T⋅

χ_{( )T} =χ
_{ T( )}+χ_OMTTF+δ_{( )T}

OPQ; 4  6 6@ ;' ïÞ+ eK f . TTF
⁺Cl -" ~580 nm
Œ ! "” Š y oD .¹¹ OMTTF
⁺= TTF⁺ á A" '  ­ , ! "” vØoD . OMTTF
⁺= TTF žŸ

¡
; @¢+£¤Z y{ âã TTF
⁺ á O PQ 6 @; 36/0 -. b@ Á úÁ%

´' '  ­, 6 !” @IJs «*+ × í, . BEDT-TTF
⁺N@: OPQ" ~970 nm; ­

, 6 6@” vØoD .

ÙU6Î6)(CV) ;á -UV 6W 23

*¥, Ú [= Table 3 š´ . ò6W (E1/2)= NÜ 6W(Ec) Ü 6W(Ea); ðñ X*+

r . /¼0 ïÞ 6W(E^1/21)= OMTTF/OMTTF⁺,

?¼0 ïÞ 6W(E1/2

2)= OMTTF⁺/OMTTF²⁺ -U V ø ' 6W@ . ' FG-OMTTF; ïÞ 6W(E^1/21 $ E^1/22)= OMTTF 4 á Á ;

Table 2. Selected vibrational frequencies (cm⁻¹) and electronic transitions in (OMTTF)mMCln compounds

Compound Vibrational mode

λmax (nm) in DMF νCH2 δCH2 ωCH2 τCH2 ρCH2 νC=C

OMTTF 2936

2906 2895 2854 2833

1622 1439 1424

1348 1325 1263 1238

1167 1154 1136

785 774

1022 1004 990

307, 476

(OMTTF)AuCl4 2947

2861 1624 1545 1481 1447

1352 1269 1242

1175 821 991 244, 326, 435(sh), 461, 515(sh), 668

(OMTTF)2PtCl6 2940 2857

1543 1415

1364 1346 1263 1242

1173 1136

820 991 274, 325, 435(sh), 461, 516(sh), 668

(OMTTF)2IrCl6· 2H2O 2936 2859

1543 1481 1427

1358 1346 1263 1240

1173 1136

814 991 265, 326, 435(sh), 460, 515(sh), 668

(OMTTF)OsCl5· THF 2938 2878

1541 1431

1346 1265 1240

1173 814 991 259, 326, 398(sh), 435(sh), 460, 540(sh), 665

ν: stretching, δ: scissoring, ω: wagging, τ: twisting, ρ: rocking, sh: sholder

Table 3. The peak potential values (Ep) versus Ag/Ag⁺ in cyclic voltammograms for OMTTF metal compounds (DMF solution)

Compound Epc(V) E(V) Epa(V) Process

OMTTF 0.15

0.41

0.18 0.44

0.20 0.47

OMTTF⁺/OMTTF OMTTF²⁺/OMTTF⁺

(OMTTF)AuCl4 -0.10-

0.18

-0.06- 0.21

-0.03- 0.24

OMTTF⁺/OMTTF OMTTF²⁺/OMTTF⁺

(OMTTF)2PtCl6 -0.08-

0.18

-0.04- 0.21

-0.01- 0.24

OMTTF⁺/OMTTF OMTTF²⁺/OMTTF⁺

(OMTTF)2IrCl62H2O -0.01-

0.27

0.02 0.29

0.05 0.31

OMTTF⁺/OMTTF OMTTF²⁺/OMTTF⁺

(OMTTF)OsCl5THF -0.01-

0.26

0.02 0.29

0.04 0.32

OMTTF⁺/OMTTF OMTTF²⁺/OMTTF⁺

X vØoD . OMTTF 4Š = FG-OMTTF

- OMTTF” ©n 1d Š%2 . OMTTF
⁺

N@: OPQ; T3" E^1/22 E^1/21; 3@ v , «*+ ä3ˆ  f*¥, Vhodorkovsky¹² !" @

«d r•% logK=E^1/22-E1/21/0059 V *+ BC

D .  *+
E r' TTF; logK=3.90, BEDT-TTF

= logK=2.03, Ú{y OMTTF= logK=4.41 @D . 4, OMTTF
⁺@ TTF
⁺ $ BEDT-TTF
⁺N@: OP QŠ T3cd Š%2 . @»' [= TTF $ BEDT-TTF”
40*+ , —, q ÆÊ r ' OMTTF-FG - = OMTTF” L6M

@:oJ OMTTF
⁺*+ RS= Œ÷ 5¾%

2 .

 

OMTTF ÁŽFG(Au, Pt, Ir, Os) -+

E (OMTTF)AuCl⁴, (OMTTF)2PtCl6, (OMTTF)2IrCl6 2H2O $ (OMTTF)OsCl5THF  . @. 

-  OMTTF= L6M oJ OMTTF
⁺ N

@: OPQ+ RS . @»' 6mn;  9 …= 6mn N@: OPQ; T3 vǔ f

d e  fD . , OMTTF-FG -" >?

8• ­,; 6/688 BCD*¥, y• Ÿ

 OMTTF
⁺; éº ê9@ ë0*+ @IJ    ì" «*+ ä3oD . @»' [= í[3 X- ß [3 r ;á YZ%6 ˆ «@ .

q r= 'ÔSí 70/Ãr(2001-1-12200- 001-1)  V*+ 8oD.

   

1. Hatfield, W. E. Molecular Metals
NATO Conference Series, Plenum Press New York, 1979.

2. (a) Kim, Y. I.; Hatfield, W. E. Inorg. Chim. Acta 1991, 188, 15. (b) Kim, Y. I.; Hatfield, W. E. Inorg. Chim.

Acta 1991, 189, 237. (c) Kim, Y. I.; Hatfield, W. E.

Inorg. Chim. Acta 1993, 204, 261. (d) Kim, Y. I.; Choi, S. N.; Jung, W. S. Bull. Korean Chem. Soc. 1994, 15, 465. (e) Jeong, C. K.; Kim, Y. I.; Choi, S. N. Bull.

Korean Chem. Soc. 1996, 17, 1061. (f) Kim, M. K.;

Kim, Y. I.; Moon, S. B.; Choi, S. N. Bull. Korean Chem. Soc. 1996, 17, 1167. (g) Park, E. J.; Lee, H. W.;

Kim, Y. I. Bull. Korean Chem. Soc. 1997, 18, 1308. (h) Jeong, C. K.; Kim, Y. I. Bull. Korean Chem. Soc. 1999, 20, 1509.

3. Moon, S. B.; Kim, Y. I. Bull. Korean Chem. Soc. 1995, 16, 511.

4. Wudl, F.; Smith G. M.; Hafnagel, E. J. J. Chem. Soc., Chem. Commun. 1970, 1453.

5. Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Boch- mann, M. Advanced Inorganic Chemistry; 6th Eds.;

John Wiley Sons, Inc: 1999.

6. Figgis, B. N.; Lewis, J. The Magnetic Properties of Transition Metal Complexes in Prog. Inorg. Chem.

1964, 6, 37.

7. Inoue, M.; Inoue, M. B. J. Chem. Soc., Chem. Com- mun. 1985, 1043.

8. Komatsu, T.; Sato, H.; Nakamura, T.; Matsukawa, N.;

Yamochi, H.; Saito, G.; Kusunoki, M.; Sakaguchi, K.;

Kagoshima, S. Bull. Chem. Soc. Jpn. 1995, 68, 2233.

9. Silverstein, R. M.; Bassler, G. C.; Morrill, T. C. Spec- trometric Identification of Organic Compounds Fourth ed; Jon-Wiley & Sons: New York, 1976.

10. Williams, J. M.: Ferraro, J. R.; Thorn, R. J.; Cahson, K.

D.; Geiser, U.; Wang, H. H.; Kini, A. M.; Whangbo, M.

H. Organic Superconductors; Prentice Hall: 1992.

11. Torrance, J. B.; Scott, B. A.; Welber, B.; Kaufman, F.

B.; Seiden, P. E. Phys. Rev. B. 1979, 19, 730.

12. Vhodorkovsky, V.; Edzifna,
A.; Neilands, O. J. Mol.

Elect. 1989, 5, 33.