4P063ࢧ࢖ࢬ㑅ูࡋࡓ࣏ࣜ࢖ࣥศᏊࡢගㄏ㉳཯ᛂ㸦㏆␥኱࣭⌮ᕤ㸧‫ۑ‬࿴⏣㈨Ꮚࠊⱝᯘ▱ᡂ[ᗎ]࣏ࣜ࢖ࣥศᏊ H(C!C)nH (n!2)ࡣࠊsp ΰᡂⅣ⣲㙐ࡢᮎ➃ࢆỈ⣲࡛⤊➃ࡋࡓ┤⥺Ⅳ໬Ỉ⣲ศᏊ࡛࠶ࡾࠊ஧㔜⦰㏥ࡋࡓ෇⟄ᑐ⛠ࡢȧ㟁Ꮚ⣔ࢆᣢࡘࠋ࣏ࣜ࢖ࣥศᏊࡣࠊ⣸እ㡿ᇦ㸦200~340 nm㸧࡟チᐜ㑄⛣࡟ࡼࡿᙉ࠸྾཰ࢆ[1]ࠊ㏆⣸እ࠿ࡽྍど㡿ᇦ㸦300㹼480 nm㸧࡟࠿ࡅ࡚⚗ไ㑄⛣࡟ࡼࡿᙅ࠸྾཰ࢆࡶࡘࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿ[2-5]ࠋᡃࠎࡣࡇࢀࡲ࡛࡟ࠊ࣏ࣜ࢖ࣥศᏊ㸦n=5-7㸧ࢆྵࡴ⁐ᾮ࡟ࣚ࢘⣲ࢆῧຍࡍࡿࡇ࡜࡟ࡼࡗ࡚࣏ࣜ࢖ࣥศᏊࡢ⣸እ྾཰ᖏࡀᾘኻࡍࡿࡇ࡜ࢆሗ࿌ࡋࡓ[6,7]ࠋᮏ
◊✲࡛ࡣࠊࡇࡢ⣸እ྾཰ᖏࡢᾘኻࡀග↷ᑕ࡟ࡼࡗ࡚ᘬࡁ㉳ࡇࡉࢀࡿ஦ࢆぢฟࡋࡓࡢ࡛ࡇࢀࢆሗ࿌ࡍࡿࠋ
[ᐇ㦂]! ࣏ࣜ࢖ࣥศᏊࡢ⏕ᡂ㸸n-hexane ୰࡛ࢢࣛࣇ࢓࢖ࢺ⢊ᮎ࡟ࠊࣃࣝࢫ࣮ࣞࢨ࣮ග㸦Nd:YAG 532
nm, ~0.42 J/pulse, 10 Hz 㸧ࢆ↷ᑕࡋࠊᚓࡽࢀࡓ⁐ᾮ࠿ࡽ࣏ࣜ࢖ࣥศᏊ H(C!C)nH㸦n=4-8㸧ࢆࢧ࢖ࢬẖ࡟ศ㞳ࡋࡓࠋࣚ࢘⣲ῧຍᐇ㦂㸸C12H2 ࡢ hexane ⁐ᾮ࡟ 4"80 ಸ➼㔞ࡢࣚ࢘⣲ࢆῧຍࡋࠊ⣸እྍど྾཰ࢫ࣌ࢡࢺࣝࢆ ᐃࡋࡓࠋ⣸እ྾཰ᙉᗘࡢῶᑡ࡟ᑐࡍࡿᐊෆගࡢᙳ㡪㸸C10H2 ࡢ hexane⁐ᾮ࡟ 3 ಸ➼㔞ࡢ I2 ࢆῧຍࡋࠊග↷ᑕ࡜㐽ගࢆ 10 ศࡎࡘ஺஫࡟⾜࠸ࠊ⣸እྍど྾཰ࢫ࣌ࢡࢺࣝࢆᐃࡋࡓࠋḟ࡟ࠊࣟࣥࢢࣃࢫࣇ࢕ࣝࢱ࣮ࢆ⏝࠸࡚↷ᑕࡍࡿගࡢἼ㛗ࢆ㑅ᢥࡋࠊ཯ᛂࡀ࡝ࡢἼ㛗࡛㐍⾜ࡍࡿ࠿ࢆ᳨ドࡋࡓࠋ㐃⥆ኚ໬ἲ࡟ࡼࡿ཯ᛂᙜ㔞ࡢỴᐃ㸸ྠ⃰ᗘࡢ C10H2 ࠾ࡼࡧ I2 ࡢ hexane⁐ᾮࢆㄪᩚࡋࡓࠋC10H2 ࡜ I2 ࡢ hexane ⁐ᾮࢆయ✚ẚ 9 ᑐ 1 ࡛ΰྜࡋࠊㄪᩚࡋࡓ⁐ᾮ࡟⺯ගⅉࡢ
ගࢆ 10 ศ㛫↷ᑕࡋࠊ྾཰ࢫ࣌ࢡࢺࣝ ᐃࢆ⾜ࡗࡓࠋࡇࡢ᧯సࢆ࣏ࣜ࢖ࣥࡢ⣸እ㒊ࡢ྾཰ࡀ࡞ࡃ࡞
ࡿࡲ࡛⧞ࡾ㏉ࡋ⾜ࡗࡓࠋC10H2㸸I2 ࡢΰྜẚ 8.5:1.5ࠊ7.5:2.5ࠊ7:3ࠊ5:5ࠊ3:7ࠊ1:9 ࡟ࡘ࠸࡚ࡶྠᵝࡢᐇ㦂ࢆ⾜ࡗࡓࠋᚓࡽࢀࡓࢫ࣌ࢡࢺࣝࡢゎᯒ࠿ࡽ C10H2 ࡜ I2 ࡢ཯ᛂᙜ㔞ࢆồࡵࡓࠋ[⤖ᯝ࡜⪃ᐹ] ᅗ 1 ࡣ࣏ࣜ࢖ࣥ⁐ᾮ࡟ᑐࡍࡿ I2 ῧຍ㔞ࢆኚ໬ࡉࡏࡓヨᩱࡢ྾཰ࢫ࣌ࢡࢺࣝࢆ㔜ࡡࡓࡶࡢ࡛࠶ࡿࠋࣚ࢘⣲ῧຍ㔞ࡢቑຍ࡟క࠸ࠊ࣏ࣜ࢖ࣥศᏊࡢ⣸እ྾཰ᙉᗘࡀῶᑡࡋ࡚࠸ࡿࡇ࡜ࡀศ ࠿ ࡿ ࠋ ᖹ ⾮ ཯ ᛂ ᘧ ࢆ C12H2 㸩 n(I2)
C12H2(I2)n ࡜௬ᐃࡋࠊ⣸እ྾཰ᙉᗘࡢῶᑡ㔞ࡢࣚ࢘⣲ῧຍ㔞౫Ꮡᛶࢆゎᯒࡍࡿࡇ࡜࡟ࡼ4ࡗ࡚ n=3 ࡜Ỵᐃࡋࡓࠋࡇࡢ⤖ᯝࡣࠊ1 ศᏊࡢI2absorbance࣏ࣜ࢖ࣥ࡟ 3 ศᏊࡢࣚ࢘⣲ࡀ཯ᛂࡍࡿ࡜⣸እ྾཰ᖏࡀᾘኻࡍࡿࡇ࡜ࢆព࿡ࡍࡿࠋ
ᅗ 2 ࡟ࠊC10H2/I2 ⁐ᾮ࡟ග↷ᑕ࡜㐽ගࢆ

C12H2+I2 (8.6 eq.)
C12H2+I2 (17.2 eq.)
C12H2+I2 (86.1 eq.)

2I2W-bands 䢢䢢C H
122forbidden

㸦252 nm㸧ࡢ᫬㛫ኚ໬ࢆ♧ࡋࡓࠋ‫ࡣە‬ග↷0250

ᑕࠊ‫ࡣۑ‬㐽ග᮲௳࡛ࡢ྾ගᗘࢆ♧ࡍࠋᅗ 2ῶᑡࡍࡿࡇ࡜ࡀศ࠿ࡿࠋ

C12H2+I2 (4.3 eq.)

C12H2+I2 (21.5 eq.)஺஫࡟⾜ࡗࡓ㝿ࡢࠊC10H2 ࡢ⣸እ྾཰ᙉᗘ

ࡼࡾࠊගࢆ↷ᑕࡋࡓ᫬ࡢࡳ⣸እ྾཰ᙉᗘࡀ

C12H2

䢢C12H2allowed

300

350

400
450
500
wavelength (nm)

550

600

650


ᅗ㸯.࣏ࣜ࢖ࣥ/ࣚ࢘⣲ΰྜ⁐ᾮࡢ⣸እྍど྾཰ࢫ࣌ࢡࢺࣝኚ໬ࡢ I2 ῧຍ㔞౫Ꮡᛶ.

ᅗ 3 ࡟ C10H2/I2 ⁐ᾮ࡟Ἴ㛗㑅ᢥⓗ࡟ගࢆ0.7↷ᑕࡋࡓ㝿ࡢ C10H2 ࡢ⣸እ྾཰ᙉᗘ㸦2520.6ᗘࡢῶᑡࡀぢࡽࢀࡿࠋࣚ࢘⣲ศᏊࡢ྾཰ᖏ

0.4
0.30.2(440-640 nm , ᅗ 1)࡜⺯ගⅉࡢἼ㛗㡿ᇦࡀ㔜

0.1࡞ࡗ࡚࠸ࡿࡇ࡜࠿ࡽࠊࣚ࢘⣲ศᏊࡀගࢆ྾཰0.0ࡋ࣏ࣜ࢖ࣥศᏊ࡜཯ᛂࡍࡿ࡜⪃࠼ࡽࢀࡿࠋ

0204060㐃⥆ኚ໬ἲ࡟ࡼࡿ࣏ࣜ࢖ࣥศᏊ࡜ࣚ࢘⣲0.7

ࡉࢀࡿᴟ್㸦0.25㸧ࡼࡾ࣏ࣜ࢖ࣥࡀከࡃῶᑡ

0.6

ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿ㸦0.7"0.8㸧ࠋ㸦ࡇࡢ཯

0.5
absorbanceࡓࠋC10H2㸸I2 ࡀ 1㸸3 ࡛཯ᛂࡍࡿሙྜ࡟ᮇᚅࢆ♧ࡋ࡚࠸ࡿࠋ㸧྾ගᗘࡢῶᑡศࡢᴟ್࡟࠾

0.30.2ࡿࣚ࢘⣲ศᏊࡢ཯ᛂ㔞 n ࢆᘧ[ࣔࣝศ⋡㸻

0.1

1/1+n]ࡼࡾ n=1/3"1/6 ࡜ồࡵࡓࠋ

0.0> 610 nm> 570 nm
> 515 nm
> 455 nm
> 435 nm
> 385 nm0ࡇࡢ⤖ᯝ࠿ࡽࠊC10H2㸩3I2!X+R+2I2㸦X㸸Ᏻᐃ໬ྜ≀ࠊR㸸㧗཯ᛂᛶࣛࢪ࢝ࣝ㸧ࡢࡼ࠺࡟ᡠࡿ࡜࠸࠺཯ᛂᶵᵓࡀ⪃࠼ࡽࢀࡿࠋࡋ࠿

depletion of C10H2

ࡓ n=1/3"1/6 ࡜࠸࠺್࠿ࡽࣚ࢘⣲ 1 ศᏊࡀᾘ䲑䲏
0.00.00࠙ཧ⪃ᩥ⊩ࠚ

2400.43"6 ᅇ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡿࠋࡇࡢሙࢆ೉ࡾ࡚࠾♩⏦ࡋୖࡆࡲࡍࠋ

2000.60.2ࡢຍ⸨❧ஂඛ⏕࡟኱ኚ࠾ୡヰ࡟࡞ࡾࡲࡋࡓࠋ

120
160
time(min)䢢䢢䢢C10H2/I2
absorbance before irradiation
0.8
deplition after irradiation㈝ࡉࢀࡿࡲ࡛࡟㈝ࡸࡉࢀࡿ࣏ࣜ࢖ࣥศᏊࡣ
[ㅰ㎡] ᮏ◊✲ࢆ㐍ࡵࡿ࡟࠶ࡓࡾࠊᇛす኱Ꮫ80

1.0ࡋࠊᅗ㸲࠿ࡽࠊ཯ᛂ⤊஢ᚋ࡟ C10H2 ࡀṧࡿࡇX ࡟ࣚ࢘⣲ࡀྵࡲࢀ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋࡲ

40

400
500
600
wavelength(nm)ᅗ 3. Ἴ㛗㑅ᢥࡋࡓග↷ᑕ࡟ࡼࡿ࣏ࣜ࢖ࣥศ
Ꮚࡢ྾ගᗘࡢῶᑡ㸦252 nm㸧. ᤄධᅗࡣ⺯ගⅉࡢගᙉᗘࡢἼ㛗ศᕸ.

࡟ࠊ୍ᗘ C10H2 ࡜཯ᛂࡋࡓ I2 ࡀ෌ࡧ཯ᛂ⣔࢖ࢡࣝࡣ᭷㝈࡛࠶ࡿࡇ࡜ࠊࡼࡗ࡚Ᏻᐃ⏕ᡂ≀1400.4ࡅࡿࣔࣝศ⋡࠿ࡽࠊ1 ศᏊࡢ࣏ࣜ࢖ࣥ࡟ᑐࡍ

࡜ࡀศ࠿ࡿࡓࡵ I2 ࡀ཯ᛂ⣔࡟ᡠࡿ࡜࠸࠺ࢧ

120

ᅗ 2. ࣏ࣜ࢖ࣥศᏊࡢ྾ගᗘࡢῶᑡ㸦252 nm㸧.
ග↷ᑕ㸦‫ە‬㸧ࠊ㐽ග㸦‫ۑ‬㸧ศᏊࡢ཯ᛂᙜ㔞ࡢỴᐃࡢࡓࡵᅗ 4 ࢆసᡂࡋᛂࡢᏳᐃ࡞⏕ᡂ≀ࡣ C10H2(I2)3 ࡛ࡣ࡞࠸ࡇ࡜

80
100time(min)

0.20

0.40

0.60

0.80

1.00

mol fraction of C10H2[C10H2]/[C10H2]+[I2]ᅗ 4. ග↷ᑕ࡟ࡼࡗ࡚ῶᑡࡋࡓ C10H2ࡢ྾ගᗘ㸦252 nm㸧.‫ە‬ග↷ᑕ࡟ࡼࡗ࡚ῶᑡࡋࡓ྾ගᗘࠊ‫ۑ‬ග↷ᑕ๓ࡢ྾ගᗘ.

1. R. Eastmond, T.R. Johnson, D.R.M. Walton,Tetrahedron 28 (1972) 4601.
2. E. Kloster-Jensen, H.-J. Haink, H. Christen, Helv. Chim. Acta
57 (1974) 1731.
3. H.-J. Haink, M. Jungen, Chem. Phys. Lett. 61 (1979) 319.
4. H. Ding, T.W. Schmidt, T. Pino, F. Güthe, J.P. Maier, Phys. Chem. Chem. Phys. 5 (2001) 4772.
5. T. Wakabayashi, H. Nagayama, K. Daigoku, Y. Kiyooka, K. Hashimoto, Chem. Phys. Lett. 446 (2007) 65.
6. Y.Wada, T.Wakabayashi, R.Osada, T.Kato, ➨ 36 ᅇࣇ࣮࣭ࣛࣞࣥࢼࣀࢳ࣮ࣗࣈࢩ࣏ࣥࢪ࣒࢘.
7. Y.Wada, T.Wakabayashi, R.Osada, T.Kato, ➨ 25 ᅇ໬Ꮫ཯ᛂウㄽ఍.

absorbance of C10H2

ࡰ඲࡚ࡢἼ㛗࡟࠾࠸࡚࣏ࣜ࢖ࣥศᏊࡢ྾ග

0.5
absorbancenm㸧ࡢ᫬㛫ኚ໬ࢆ♧ࡋࡓࠋ⺯ගⅉࡢගࡢ࡯PhotoirradiationOFFON