! " "' Áø?§Ðt!Än"ē©!ÁÐtē-"ēêćÛ 1c,nĊþoZ-Ĕēxöêć/(ēÄöõ!À Yt"`®×-ĔÄö!Eeü1Â-ÁÅĂ-đÀYtÉĒ2>6=8@"ēÛ !;4=Ã!1èđ9<5:>!ĒēvĎÉ"ÀwĂ»u*!&uĂ.-Ĕ ē;4=×n+"êć-Äv!Áø!ÁÍÖē2>6=8@!u Ă"ēzìÉÁĂ!»uË;4=m1F-ē%.±,-Ĕ#ē ê!Us!ÿ[ÌĆ1ē2>6=8@"rċ1d-Ĕ!*Usÿ[ !ÌĆ"ēÁÐt-¤Þ±î0.--Î³SĐđNMRĒ)GsH1( (ēuĂÉ¯T-!"w¡"Ĕ!h\tÀYt"ÁÐt X1«-(-Ĕ"ÀwĂ!»u¶1Ú]ô -SēêćÛ 2>6=8@++.-m!vO1ÝJ-Ĕ ÀwĂ»u¶ 2>6=8@p\"ÀYt"¼ĉÉĀÓ-À!TR,1ºX(!F+.- đ S = ( q /T ) ĒĔÀwĂ»u1ænf"ē.1ºp\-nfAä\(! đ S = (C /T ) dT = Cd (logT ) Ē1Æ-ĔÀwĂ»u(¼ĉÉĀÓæ0.- ð"¾1ĔAäÀwĂ!»u"ÀYtØA¶WW-!ē (¼ĉÉĀÓ1ëĔÀwĂ1đºXĒÕU-*2>6=8@+ .-!-Ĕ ÀwĂ!»u¶"rU 4 Ôč-đlĕĒĔ. .Â,ēNU-ë-ĔLD". .!¶!_ÅÂ-Ĕ ĖÀ¶ėÀ¨Mē~çÃ-òAuĂ!2 7<3@1^Zē27<3@^Z!~çÃ1 Z27<3@ºC!²+ÀwĂ1´'-Ĕ» uĄ¢ą1ëēòĂ(qđ1 g ÓĒē¤(PČ ďĔÀYtØB¶W!¯ñ(Æ+.ĔºU íã"àxº! 0.5%Ó-Ĕ¤ûē|÷éâ R-*ĔA°ÌúÒđåíĒ*-½À) \tb*-g?ÈÀ(»u-Ĕ ĖÏ{ù¬ÀĂ»uđDSCĒėòa¿Áø1xÑÉāâēºp\1ænf¸R?¸T -27<3@{1ïăēÕU*ÀĂ1»u-Ĕ¦øÉ[É»u!ºUíã"Ĕ A°ÌúÒ!½À)\tb*-g?ÈÀ(»uēÊÉN0.-qĔq !|÷j-ĔDSC "_Å!Ç-IÔč-!NÆ·ë-Ĕ_Å) íª¶!óÜ"£ 1 1a¿.Ĕ Ėái¶ėòÀ¹1ÀÉßfēu}Ã+u}Ã$!ºÙđáiĒ1í ªÀwĂ1´'-Ĕái¶!_Å,!ºÙ1Ïnf"yĂ!òđ mgĒàxQ µu-ĔKē¥ý,!ºÙvÄ-1vĎß«+Vu-!kĈ l 1. ÀwĂ»u¶!Uč

! / ¨Ç¯4L>KAM ."!ÚANBC #ue .Û )Ú #BABH " PY .Û ÚBABH # l ® Í1 Øq6Ù (Ú`{1 X -P "3I6It1 " ÚE

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Page 1: ! / ¨Ç¯4L>KAM ."!ÚANBC #ue .Û )Ú #BABH " PY .Û ÚBABH # l ® Í1 Øq6Ù (Ú`{1 X -P "3I6It1 " ÚE

NMR

S = ( q /T )

S = (C /T )dT = Cd (logT )

1 g

0.5%

DSC

Page 2: ! / ¨Ç¯4L>KAM ."!ÚANBC #ue .Û )Ú #BABH " PY .Û ÚBABH # l ® Í1 Øq6Ù (Ú`{1 X -P "3I6It1 " ÚE

10 mK

S = kB ln W

1 kB ln 2

MMX MMX

2MMX

Pt2(n-BuCS2)4I 33

3 3 1

2 Pt CS2

Pt2(MeCS2)4I Pt2(dta)4I

CS2

Pt2(n-PrCS2)4I

Pt2(n-BuCS2)4I Pt2(n-PrCS2)4I 4

5,6

CS2

Pt2(n-BuCS2)4I

Page 3: ! / ¨Ç¯4L>KAM ."!ÚANBC #ue .Û )Ú #BABH " PY .Û ÚBABH # l ® Í1 Øq6Ù (Ú`{1 X -P "3I6It1 " ÚE

Pt2(n-BuCS2)4I Pt2(n-PrCS2)4I

4. Pt2(n-BuCS2)4I Pt2(n-PrCS2)4I

trsS

+ 2

2 x 2 = 4 ++ + + 2

2 ++ + +

ZrW2O8

440 K

WO4

2 WO4

2Rln2

Rln2 2

WO4

MMX Pt2(MeCS2)4I CS2

Pt2(n-BuCS2)4I Pt2(n-PrCS2)4I R ln 210

4 4

CS2

5. ZrW2O8

Page 4: ! / ¨Ç¯4L>KAM ."!ÚANBC #ue .Û )Ú #BABH " PY .Û ÚBABH # l ® Í1 Øq6Ù (Ú`{1 X -P "3I6It1 " ÚE

7 11

NMR

1 ms

NMR

1000

1957

ANBC(16) 7

1600

813

6. ANBC BABH

Page 5: ! / ¨Ç¯4L>KAM ."!ÚANBC #ue .Û )Ú #BABH " PY .Û ÚBABH # l ® Í1 Øq6Ù (Ú`{1 X -P "3I6It1 " ÚE

10.

ANBC BABH

ANBC(16) SmC SmA

BABH(8) SmC

8 SmC ANBC

BABH

ANBC BABH SmC 9

7 BABH

ANBC

BABH BABH 6 1

0.5 J K-1 (mol of CH2)-1

ANBC BABH SmC

SmC

BABH

SmC

ANBC 10 nC

= 14 14

SmC 8

ANBC BABH

1114 MMX

Page 6: ! / ¨Ç¯4L>KAM ."!ÚANBC #ue .Û )Ú #BABH " PY .Û ÚBABH # l ® Í1 Øq6Ù (Ú`{1 X -P "3I6It1 " ÚE

RT HT 1

BABH ANBC

15,16

17 18,19

1 (2005).

2 M. Yamashita, S. Takaishi, A. Kobayashi, H. Kitagawa, H. Matsuzaki, H. Okamoto, Coord. Chem. Rev., 250,

2335 (2006). 3 M. Mitsumi, K. Kitamura, A. I. Morinaga, Y. Ozawa, M. Kobayashi, K. Toriumi, Y. Iso, H. Kitagawa & T.

Mitani, Angew. Chem., 41, 2767 (2002). 4 M. Mitsumi, S. Umebayashi, Y. Ozawa, K. Toriumi, H. Kitagawa & T. Mitani, Chem. Lett., 258 (2002). 5 S. Ikeuchi, K. Saito, Y. Nakazawa, A. Sato, M. Mitsumi, K. Toriumi & M. Sorai, Phys. Rev. B, 66, 115110

(2002). 6 S. Ikeuchi, K. Saito, Y. Nakazawa, M. Mitsumi, K. Toriumi & M. Sorai, J. Phys. Chem. B, 108, 387 (2004). 7 K. Saito & Y. Yamamura, Thermochim. Acta, 431, 21 (2005).

8 L. Pauling, J. Am. Chem. Soc., 57, 2680 (1935)., 9 Y. Yamamura, T. Tsuji, K. Saito & M. Sorai, J. Chem. Thermodyn., 36, 525 (2004). 10 Y. Miyazaki, Q. Wang, A. Sato, K. Saito, M. Yamashita, H. Kitagawa, T. Mitani & M. Sorai, J. Phys. Chem.

B, 106, 197 (2002). 11 K. Saito, M. Ikeda & M. Sorai, J. Therm. Anal. Calor., 70, 345 (2002). 12 , 41, 379 (2006). 13 S. Kutsumizu, H. Mori, M. Fukatami & K. Saito, J. Appl. Crystallogr., 40, s279 (2007). 14 M. Sorai & K. Saito, Chem. Rec., 3, 29 (2003). 15 L.J. de Jongh & A.R. Miedema. Adv. Phys., 50, 947 (2001). 16 , 28, 200 (2001). 17 H. Akutsu, K. Saito & M. Sorai, Phys. Rev. B, 61, 4346 (2000). 18 , 36, 191 (2001). 19 S. Ikeuchi, Y. Miyazaki, S. Takeda, T. Akutagawa, S. Nishihara, T. Nakamura & K. Saito, J. Chem. Phys.,

123, 044514 (2005).