ᐇ᪋ㄢ㢟␒ྕ%ᐇ᪋ㄢ㢟ྡ☢ᛶᮦᩱࢩ࢔ࣀᯫᶫ㹑㹫㸫㹁㹰㘒యࡢ⢊ᮎ᭷ᶵ⤖ᬗࡢᵓ㐀ゎᯒᐇ㦂㈐௵⪅ᡤᒓᶵ㛵ཬࡧẶྡ៞᠕⩏ሿ኱Ꮫ⛅ὠ㈗ᇛ㸦㸧౑⏝ࣅ࣮࣒ࣛ࢖ࣥ㹀㹊㸫㸯㸷㹀㸰ᐇ㦂⤖ᯝ࠙⥴ゝࠚ☢ᛶᮦᩱ࡜ࡋ࡚ࡢ⏘ᴗᛂ⏝ࢆ┠ᣦࡋࠊ⤖ᬗᵓ㐀ࡀᮍ▱ࡢ཯ᙉ☢ᛶయ6P '0)  +2 &U &1 +2ࡸࣇ࢙ࣜ☢
ᛶయ*G '0)  +2 &U &1 +2㸦ᅗ㸯㸧>@ࡢᐊ ࡟࠾ࡅࡿ⢊ᮎ⤖ᬗᵓ㐀ゎᯒࢆ⾜࠺ࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋྠᙧ࡜᥎ࡉࢀࡿ㔠ᒓ࢖࢜ࣥࢆ⨨᥮ࡋࡓㄏᑟయࠊ

1G '0)  +2 &U &1 +2 ࡣ ᵓ 㐀 ᪤ ▱ ࡛ ࠶ ࡾ >@ ࠊ
1G '0)  +2 )H &1 +2ࡣࠊࢩ࢔ࣀᯫᶫ GIศᏊ☢ᛶయ࡛ึࡵ࡚ࠊග☢ᛶไᚚࡀほ ࡉࢀࡓ>@ࠋ    ᅗ㸯 GIศᏊ☢ᛶయࡢ☢ᛶ>@ 㢮⦕㘒యࡢ⤖ᬗᵓ㐀>@ࡶࠊ࡯ࡰྠᙧ࡛࠶ࡿ࡜ண᝿ࡉࢀࡿࡀࠊࣛࣥࢱࢽࢻ཰⦰࡟ࡼࡿ⣔⤫ⓗ࡞࢖༙࢜ࣥᚄࡀ㢧ⴭ࡟ぢࡽࢀࡿࡇ࡜࡜ࠊࢩ࢔ࣀᯫᶫ㏆ഐࡢࢃࡎ࠿࡞㓄఩ᵓ㐀ኚ໬࡛ࡍࡽࠊ☢ᛶ࡟⏒኱࡞ᙳ㡪ࢆཬࡰࡍࡇ࡜࠿ࡽࠊఱࡽ࠿ࡢ஦᝟࡟ࡼࡾࠊⰋዲ࡞༢⤖ᬗࡀᚓࡽࢀ࡞࠿ࡗࡓࡾࠊ༢⤖ᬗ ;⥺⤖ᬗᵓ㐀ゎᯒ࡛఩┦ࡀỴᐃ࡛ࡁ࡞࠿ࡗࡓ໬ྜ≀࡛࠶ࡗ࡚ࡶࠊDELQLWLR ⢊ᮎ⤖ᬗᵓ㐀ゎᯒ࡟ࡼࡗ࡚ࠊ❧యᵓ㐀ࢆỴᐃࡍࡿࡇ࡜ࡣ㔜せ࡛࠶ࡿࠋࡲࡓࠊ㓄఩Ỉࡢᩘࡸࢩ࢔ࣀᯫᶫᵝᘧࢆไᚚࡍࡿࡇ࡜࡛ࠊ୍ḟඖ㙐>@ࡸ஧ḟඖ>@࡞࡝ࠊᵓ㐀ḟඖᛶࡢ␗࡞ࡿศᏊ☢ᛶయࡶ▱ࡽࢀ࡚࠾ࡾࠊࢡࣜࢫࢱ࣭࢚ࣝࣥࢪࢽ࢔ࣜࣥࢢࡢぢᆅ࠿ࡽࡶࠊ⯆࿡ࡀᣢࡓࢀࡿࠋ࠙ᐇ㦂᪉ἲࠚヨᩱࡣࣜࣥࢹ࣐ࣥ࢞ࣛࢫ࢟ࣕࣆ࣮ࣛࣜ㸦ȭPP㸧࡟඘ሸࡋࡓࠋྜᡂࣂࢵࢳࡢ␗࡞ࡿヨᩱࡢ
6P '0)  +2 &U &1 +2㸦㸧ࠊྠᙧᵓ㐀࡜ண᝿ࡉࢀࠊ༢⤖ᬗ࡟ࡼࡿᵓ㐀ゎᯒ῭ࡳ>@㸦ᅗ㸰㸸Monoclinic, P21/n, a=19.881(5), b=8.885(8), c=17.634(7)ύ, ȕ=96.04(3)°,V=3097(3)ύ3, Z=4㸧࡛࠶ࡿ6P '0)  +2 )H &1 +2㸦㸧ࠊࡑࡋ࡚*G '0)  +2 &U &1 +2㸦㸧ࡢྜィ✀㢮ࢆ⏝࠸ࡓࠋࡲࡎึࡵ࡟ࠊᐊ ࠊἼ㛗ύࠊ↷ᑕ᫬㛫ศ㛫ࡢ᮲௳࡛ࠊࢫࣆࢼ࣮࡛ᅇ㌿ࡉࡏ࡞ࡀࡽࠊ኱ᆺ䝕䝞䜲䝅䜵䝷䞊䜹䝯䝷䜢⏝䛔䛶 ᐃࡋࡓࠋࡉࡽ࡟ࠊ❅⣲྿௜ప ⿦⨨ࢆ⏝࠸࡚ࠊ㹉࡟෭༷ࡋ࡚ࠊἼ㛗㸬ύࠊ↷ᑕ᫬㛫ศ㛫ࡢ᮲௳࡛ࠊྠᵝ࡟ ᐃࢆ⾜ࡗࡓࠋiᅗ㸰 6P '0)  +2 )H &1 +2㸦㸧ࡢᵓ㐀 ᕥ ࡜ࠊἼ㛗 ύ㸦&X.Ș㸧࡜ࡋ࡚ኚ᥮ࡋࡓ ;5' ࣃࢱ࣮ࣥ ྑ >@࠙ᐃ⤖ᯝ࣭⪃ᐹࠚࡲࡎࠊᐊ ࠊἼ㛗 ύࠊ↷ᑕ᫬㛫  ศ㛫ࡢ᮲௳࡛ ᐃࢆ⾜ࡗࡓࠋࡇࡢ࡜ࡁࠊ㗦࠸ࣆ࣮ࢡࡀከᩘ⌧ࢀࡿࡇ࡜ࢆ☜ㄆࡋࡓ㸦ᅗ㸱㸧ࠋゎᯒࢯࣇࢺ㹂㸿㹑㹆࡟ࡼࡾࠊ༢ᩳᬗ⣔࠾ࡼࡧ୕ᩳᬗ⣔࡜ࡋ࡚ࠊೃ⿵࡜࡞ࡿ᱁ᏊᐃᩘࡢỴᐃࢆヨࡳࡓࡀࠊᐃࡵࡿࡇ࡜ࡀ࡛ࡁ࡞࠿ࡗࡓࠋ


Intensity

Intensity



㻤㻜㻜㻜㻜

Sm(DMF)4(H2O)3Cr(CN)6.H2O

㻣㻜㻜㻜㻜㻝㻞㻜㻜㻜㻜

Sm(DMF)4(H2O)3Cr(CN)6.H2O

㻝㻜㻜㻜㻜㻜

㻢㻜㻜㻜㻜㻤㻜㻜㻜㻜㻡㻜㻜㻜㻜㻠㻜㻜㻜㻜㻟㻜㻜㻜㻜㻢㻜㻜㻜㻜㻞㻜㻜㻜㻜㻝㻜㻜㻜㻜㻠㻜㻜㻜㻜㻞㻜㻜㻜㻜㻜㻜㻝㻡㻟㻜㻠㻡㻢㻜㻣㻡

2T/degree㻜㻜㻝㻡㻟㻜㻠㻡㻢㻜㻣㻡

2T/degree

Intensity

Intensity㻝㻞㻜㻜㻜㻜

Sm(DMF)4(H2O)3Fe(CN)6.H2O

㻝㻜㻜㻜㻜㻜㻢㻜㻜㻜㻜㻤㻜㻜㻜㻜㻢㻜㻜㻜㻜㻠㻜㻜㻜㻜㻞㻜㻜㻜㻜

Gd(DMF)4(H2O)3Cr(CN)6.H2O

㻡㻜㻜㻜㻜㻜㻠㻜㻜㻜㻜㻟㻜㻜㻜㻜㻞㻜㻜㻜㻜㻝㻜㻜㻜㻜㻜㻜㻝㻡㻟㻜㻠㻡㻢㻜

2T/degreeᅗ㸱 ᐊ

㻣㻡㻜㻝㻡㻟㻜㻠㻡㻢㻜㻣㻡

2T/degreeἼ㛗 ύࡢ ;5' ࣉࣟࣇ࢓࢖ࣝ ᕥୖ ࠊྑୖ ࠊᕥୗ ࠊྑୗ  ࡘ࡙࠸࡚ࠊ㹉࡟෭༷ࡋ࡚ࠊἼ㛗 ύࠊ↷ᑕ᫬㛫  ศ㛫ࡢ᮲௳࡛ࠊ ᐃࢆ⾜ࡗࡓ㸦ᅗ㸲㸧ࠋྠᵝ࡟㗦࠸ࣆ࣮ࢡࡀከᩘ⌧ࢀࠊἼ㛗ኚ໬࡟ࡼࡿᅇᢡゅࡢኚ໬㸦ࣆ࣮ࢡศ㞳㛫㝸ࡢኚ໬㸧ࡸࠊ↷ᑕ᫬㛫ᘏ㛗࡟ࡼࡿᙉᗘࢹ࣮ࢱࡢ㉁ࡢྥୖࡀぢࡽࢀࡓࠋࡇࢀࡽࢆ⏝࠸࡚ࠊゎᯒࢯࣇࢺ㹂㸿㹑㹆࡟ࡼࡾ᱁ᏊᐃᩘࡢỴᐃࢆヨࡳࡓࡀࠊࡸࡣࡾࠊᐃࡲࡽ࡞࠿ࡗࡓࠋྠᙧᵓ㐀࡜ண᝿ࡉࢀࡿ༢⤖ᬗ  ࡢ⤖ᯝࢆධຊࡍࡿࡇ࡜࡟ࡼࡾࠊᅇᢡࣆ࣮ࢡࡢண᝿ࢆྜࢃࡏ࡚⾲♧ࡋࡓ࡜ࡇࢁࠊᾘ⁛๎࠿ࡽண᝿ࡉࢀࡿࣆ࣮ࢡࡼࡾࠊࡣࡿ࠿࡟ከᩘࡢᅇᢡࣆ࣮ࢡࡀほࡉࢀ࡚࠸ࡿ஦ࡀࠊ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡇࡢࡼ࠺࡞ഴྥࡣࠊ ࡘࡢヨᩱ඲࡚࡟ࡘ࠸࡚ࠊྠᵝ࡟ㄆࡵࡽࢀࡓࠋ

ii

Intensity

Intensity㻟㻡㻜㻜㻜㻠㻡㻜㻜㻜㻟㻜㻜㻜㻜㻠㻜㻜㻜㻜

Sm(DMF)4(H2O)3Cr(CN)6.H2O

Sm(DMF)4(H2O)3Cr(CN)6.H2O

㻟㻡㻜㻜㻜㻞㻡㻜㻜㻜㻟㻜㻜㻜㻜㻞㻜㻜㻜㻜㻞㻡㻜㻜㻜㻝㻡㻜㻜㻜㻞㻜㻜㻜㻜㻝㻡㻜㻜㻜㻝㻜㻜㻜㻜㻝㻜㻜㻜㻜㻡㻜㻜㻜㻡㻜㻜㻜㻜㻜㻜㻝㻡㻟㻜㻠㻡㻢㻜㻣㻡㻜㻝㻡㻟㻜

2T/degree

㻠㻡㻢㻜

㻣㻡

2T/degree

IntensityIntensity㻠㻜㻜㻜㻜㻤㻜㻜㻜

Sm(DMF)4(H2O)3Fe(CN)6.H2O

㻟㻡㻜㻜㻜

㻣㻜㻜㻜

㻟㻜㻜㻜㻜㻢㻜㻜㻜㻞㻡㻜㻜㻜㻡㻜㻜㻜㻞㻜㻜㻜㻜㻠㻜㻜㻜㻝㻡㻜㻜㻜

㻟㻜㻜㻜

㻝㻜㻜㻜㻜

㻞㻜㻜㻜

㻡㻜㻜㻜㻝㻜㻜㻜㻜

Gd(DMF)4(H2O)3Cr(CN)6.H2O

㻜㻜

㻝㻡

㻟㻜

㻠㻡㻢㻜

㻣㻡

2T/degree㻜㻝㻡㻟㻜㻠㻡㻢㻜㻣㻡

2T/degreeᅗ㸲 .Ἴ㛗 ύࡢ ;5' ࣉࣟࣇ࢓࢖ࣝ ᕥୖ ࠊྑୖ ࠊᕥୗ ࠊྑୗ  ᅗ㸳࡟ࠊపゅ㡿ᇦࡢ  ࡢ༢⤖ᬗࢹ࣮ࢱ࠿ࡽኚ᥮ࡋࡓ ;5' ࡜ࠊᐇ㦂࡟ࡼࡿ ;5' ࣃࢱ࣮ࣥࡢẚ㍑ࢆ
♧ࡍࠋἼ㛗 ύύ࡜ࡶ࡟ࠊࢩ࣑࣮ࣗࣞࢩࣙࣥ࡜ᐇ㦂ࡢ୍⮴ࡀࠊⰋࡃ࡞࠸ࡇ࡜ࡀࢃ࠿ࡿࠋ

Intensity㻝㻞㻜㻜㻜㻜㻝㻜㻜㻜㻜㻜㻤㻜㻜㻜㻜㻢㻜㻜㻜㻜㻠㻜㻜㻜㻜㻞㻜㻜㻜㻜㻜㻡㻝㻜㻝㻡㻞㻜

2T/degreeIntensity㻠㻜㻜㻜㻜㻟㻡㻜㻜㻜㻟㻜㻜㻜㻜㻞㻡㻜㻜㻜㻞㻜㻜㻜㻜㻝㻡㻜㻜㻜㻝㻜㻜㻜㻜㻡㻜㻜㻜㻜㻡㻝㻜㻝㻡

2T/degree㻞㻜ᅗ㸳 ࡢᐇྑ ࡜ࢩ࣑࣮ࣗࣞࢩࣙࣥ ;5' ᕥ
iiiୖẁᐊύୗẁ.ύ ༢⤖ᬗᵓ㐀ゎᯒࢆヨࡳࡓ㝿ࠊࡑࡢ᫬ࡢྜᡂ࣭⤖ᬗᡂ㛗᮲௳ୗ࡛ࡣࠊ⤖ᬗᛶࡀᝏࡃࠊ┤᥋ἲ࡟ࡼࡿ఩┦Ỵᐃࡀᅔ㞴࡛࠶ࡗࡓࠋࡑࡢ⤖ᬗᛶ୙Ⰻࡣࠊ⁐፹㸦Ỉ࠾ࡼࡧ㹂㹋㹄㸧⏺㠃࠿ࡽࠊ⮬ᕫ㞟ྜⓗ࡟ྜᡂࡍࡿ᪉ἲ࡟ࡼࡾࠊ࡜ࡾࡇࡲࢀࡿ⤖ᬗỈࡀ୙Ᏻᐃ㸦㏿ࡸ࠿࡟ኻࢃࢀࡿ㸧࡛࠶ࡿࡇ࡜࡟㉳ᅉࡋ࡚࠸ࡓࠋ௒ᅇࡢᐇ㦂࡛ࡣࠊࡑࡢ༢⤖ᬗヨᩱࢆࡍࡾࡘࡪࡋ࡚⢊ᮎヨᩱࢆㄪ〇ࡋࡓࡀࠊ༢⤖ᬗ௨ୖ࡟⤖ᬗỈࡀኻࢃࢀࡸࡍ࠸༴㝤ᛶࡀ࠶ࡿࠋࡋࡓࡀࡗ࡚ࠊࡇࡢࡼ࠺࡞≉ᛶࡢヨᩱᢅ࠺ࡓࡵ࡟ࡣࠊ௒ᚋࡢᐇ㦂࡛ࡣࠊ⁐፹ࢆྵࡴ‵ᘧἲ࡛ヨᩱㄪ〇ࢆ⾜࠺࡞࡝ࡢᨵၿࡀࠊᚲせ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ࠙⤖ㄽࠚ ࠊ6P '0)  +2 )H &1 +2  ࠊ*G '0)  +2 &U &1 +2  ☢ᛶᮦᩱ6P '0)  +2 &U &1 +2 ࡢDELQLWLR⢊ᮎ⤖ᬗᵓ㐀ゎᯒࢆヨࡳࡓࠋᴟࡵ࡚㗦࠸ᅇᢡࣆ࣮ࢡࡀᚓࡽࢀࠊ㧗㍤ᗘࡢᨺᑕග฼⏝ࠊἼ㛗ኚ໬ࠊ෭༷ᐃࡢ᭷⏝ᛶࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡲࡓࠊ ᐃ᮲௳࡟ࡼࡽࡎࠊ⤖ᬗỈࡢ᭷↓࡟㉳ᅉࡍࡿ࡜ᛮࢃࢀࡿ」ᩘࡢ⤖ᬗࡢΰᅾ࡜ᛮࢃࢀࡿࠊከᩘࡢࣆ࣮ࢡࡀ ᐃࡉࢀࡓࠋヨᩱㄪᩚἲࡢᨵၿࡀࠊ௒ᚋࡢ㔜せ࡞ㄢ㢟࡛࠶ࡿࠋ࠙ཧ⪃ᩥ⊩ࠚ
[1] T. Akitsu, Y. Einaga, Inorg. Chim. Acta., 359 (2006) 1421.
[2] G. Li, T. Akisu, O. Sato, Y. Einaga, J. Am. Chem. Soc., 125 (2003) 12396.
[3] T. Akitsu, Y. Einaga, Polyhedron, 25 (2006) 2655.
[4] T. Akitsu, Y. Einaga, Asian Chem. Lett. in press.
[5] W.-T. Chen, M.-S. Wang, L.-Z. Cai, G. Xu, T. Akitsu, M. Akita-Tanaka, G.-C. Guo, and J.-S. Huang,
Cryst. Growth. Des., 6 (2006) 1738.
[6] G. Li, T. Akisu, O. Sato, Y. Einaga,, J Coord. Chem. 57 (2004) 855.

iv