JP4379575B2 - Single molecule magnet and method for producing the same - Google Patents
Single molecule magnet and method for producing the same Download PDFInfo
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- JP4379575B2 JP4379575B2 JP2003177595A JP2003177595A JP4379575B2 JP 4379575 B2 JP4379575 B2 JP 4379575B2 JP 2003177595 A JP2003177595 A JP 2003177595A JP 2003177595 A JP2003177595 A JP 2003177595A JP 4379575 B2 JP4379575 B2 JP 4379575B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229910052751 metal Chemical class 0.000 claims description 41
- 239000002184 metal Chemical class 0.000 claims description 41
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- 150000004696 coordination complex Chemical class 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
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- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
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- 229910052735 hafnium Inorganic materials 0.000 claims description 4
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
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- 229910052702 rhenium Inorganic materials 0.000 claims description 4
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 claims description 3
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 3
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 3
- 230000005415 magnetization Effects 0.000 description 25
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- -1 diazo-pyridine compound Chemical class 0.000 description 9
- 239000000696 magnetic material Substances 0.000 description 9
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
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- 239000010949 copper Substances 0.000 description 6
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- 241000238366 Cephalopoda Species 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000002775 capsule Substances 0.000 description 4
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- 239000011572 manganese Substances 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- 125000004429 atom Chemical group 0.000 description 3
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- 238000010521 absorption reaction Methods 0.000 description 2
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
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- 229910017052 cobalt Inorganic materials 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
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- UIZLQMLDSWKZGC-UHFFFAOYSA-N cadmium helium Chemical compound [He].[Cd] UIZLQMLDSWKZGC-UHFFFAOYSA-N 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
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- INDBQWVYFLTCFF-UHFFFAOYSA-L cobalt(2+);dithiocyanate Chemical compound [Co+2].[S-]C#N.[S-]C#N INDBQWVYFLTCFF-UHFFFAOYSA-L 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- BMWBSEDTCDPYCU-UHFFFAOYSA-N methylidenecobalt Chemical compound [Co]=C BMWBSEDTCDPYCU-UHFFFAOYSA-N 0.000 description 1
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- Hard Magnetic Materials (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、光応答型単分子磁石及びその製造法に関する。更に詳しくは、光照射によって生成する有機ラジカル（カルベン）に由来する不対電子を強磁性相互作用によって配列させて得られる単分子磁石及びその製造法に関する。
【０００２】
【従来の技術】
有機ラジカルに強磁性的相互作用を持たせることによって、電子スピンを平行にそろえ、分子強磁性体を構築する試みが活発に行われている。分子磁性体は、無機磁性体に比較して成形が極めて容易であること、目的によって容易に物性の修飾ができること等から、様々な分野で新しい材料としての期待が集まっている。これまでの研究から、有機物で磁石を創るためには、（１）出来る限り多くのスピンを、（２）強い相互作用で平行に揃えて、（３）多次元的にメソスコピックな広がりを持って集積化する、ことが必要であると考えられてきた。
【０００３】
本発明者らは、有機スピン源として、磁気的相互作用が強い三重項カルベンを用い、金属との配位結合を介して一次元にスピンを集積することに成功している（非特許文献１参照。）。これらのカルベンは、２３０Ｋまで安定であり（通常のカルベンは１００Ｋ程度で化学反応し消滅する。）、室温においても安定な分子強磁性体の可能性を示唆するものである。しかしながら、得られたカルベンを含む金属錯体は、超高スピン常磁性体であり、残留磁化を有していない。
【０００４】
また、本発明者らは、金属イオンの３ｄスピンと配位子カルベンの２ｐスピンを三次元に高度集積し、残留磁化を有する分子磁性体の合成に成功した（非特許文献２、非特許文献３及び非特許文献４参照。）。しかし、これらはスピングラス様磁性材料であり、ナノマテリアルとしての応用が難しい為、残留磁化を有する単分子磁石の発明が望まれている。
【０００５】
その単分子磁性体構築のためには、ある程度大きなスピン量子数と負のゼロ磁場分裂パラメーター（Ｄ）が必要である。従来の単分子磁性体はマンガン原子を代表とする金属原子どうしをオキソ架橋でつなげたオリゴ及びポリ閉環金属錯体であり、スピン源は全て金属原子から供給されている（非特許文献５参照。）。
【０００６】
【非特許文献１】
「ジャーナル・オブ・ザ・アメリカン・ソサエテイ(J. Am. Chem. Soc.)」、（米国）、１９９７年、第１１９巻、ｐ．８２４６−８２５２
【非特許文献２】
「アプライド・マグネテイク・レゾナンス(Appl. Magn. Reson.)」、（オーストリア）、２００３年、第２３巻、ｐ．５０７
【非特許文献３】
「ポリヘドロン(Polyhedron)」、（オランダ）、２００１年、第２０巻、ｐ．１３８７−１３８９
【非特許文献４】
「ジャーナル・オブ・ザ・アメリカン・ソサエテイ(J. Am. Chem. Soc.)」、（米国）、２００１年、第１２３巻、ｐ．９６８５−９６８６
【非特許文献５】
「ネイチャー(Nature)」、（英国）、１９９３年、第３６５巻、ｐ．１４１−１４３
【０００７】
【発明が解決しようとする課題】
本発明は金属とカルベンをスピン源として用いたヘテロナスピン系で構築される、金属原子を一つしか用いない単分子磁石に関する。
【０００８】
【課題を解決するための手段】
本発明者らは、鋭意検討した結果、ジアゾ−ピリジン化合物と金属錯体又は金属塩を含む溶液に光照射することにより、残留磁化を有する単分子磁石が得られることを見出し、本発明を完成した。
【０００９】
即ち、本発明は式（１）
【００１０】
【化３】
（式中、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6及びＲ7は、それぞれ独立に、水素原子、メチル基、エチル基、ノルマルプロピル基、イソプロピル基、ノルマルブチル基、イソブチル基、セカンダリーブチル基、ターシャリーブチル基、メトキシ基、エトキシ基、ノルマルプロポキシ基、イソプロポキシ基、ノルマルブトキシ基、イソブトキシ基、セカンダリーブトキシ基又はターシャーリーブトキシ基を示す。）で表される化合物及び、金属錯体又は金属塩（該金属錯体及び金属塩の金属はＳｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｃｄ、Ｈｆ、Ｔａ、Ｗ、Ｒｅ、Ｏｓ、Ｉｒ、Ｐｔ、Ａｕ又はＨｇを示す。）を混合させた溶液に、光照射することにより得ることのできる分子磁石及びその製造法に関する。
【００１２】
【発明の実施の形態】
以下、本発明について詳細に説明する。
【００１３】
はじめに式（１）の各置換基を具体的に説明する。
【００１４】
式（１）で表される化合物の置換基Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6及びＲ7は、それぞれ独立に、水素原子、メチル基、エチル基、ノルマルプロピル基、イソプロピル基、ノルマルブチル基、イソブチル基、セカンダリーブチル基、ターシャリーブチル基、メトキシ基、エトキシ基、ノルマルプロポキシ基、イソプロポキシ基、ノルマルブトキシ基、イソブトキシ基、セカンダリーブトキシ基又はターシャーリーブトキシ基等が挙げられ、製造上の容易さから、好ましいＲ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6及びＲ7としては、水素原子、メチル基、又はメトキシ基が挙げられる。
【００１５】
式（１）で表される化合物における好ましい置換基の組み合わせを以下に示す。
【００１６】
１）Ｒ3、Ｒ4、Ｒ5、Ｒ6及びＲ7が、全て水素原子である、式（１）で表される化合物。
【００１７】
２）Ｒ1及びＲ２が、それぞれ独立して水素原子又はメチル基であり、Ｒ3、Ｒ4、Ｒ5、Ｒ6及びＲ7が全て水素原子である、式（１）で表される化合物。
【００１８】
３）Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6及びＲ7が全て水素原子である、式（１）で表される化合物。
【００１９】
次に、単分子磁石の製造法について説明する。
【００２０】
式（１）で表される化合物及び、金属錯体又は金属塩を混合させた溶液に、光照射することにより、単分子磁石を製造することができる。
【００２１】
金属錯体又は金属塩における具体的な金属としては、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｃｄ、Ｈｆ、Ｔａ、Ｗ、Ｒｅ、Ｏｓ、Ｉｒ、Ｐｔ、Ａｕ、及びＨｇを挙げることができ、好ましくは、Ｎｉ、Ｃｏ、Ｃｕ、Ｍｎ、Ｆｅ、Ｃｒ及びＺｎを挙げることができ、より好ましくは、Ｃｏ、Ｎｉ及びＣｕを挙げることができる。
【００２２】
具体的な金属錯体又は金属塩を以下に示す。
【００２３】
具体的な金属錯体としては、Ｎｉ（ｈｆａｃ）2、Ｃｏ（ｈｆａｃ）2、Ｃｕ（ｈｆａｃ）2、Ｍｎ（ｈｆａｃ）2、Ｆｅ（ｈｆａｃ）2、Ｃｒ（ｈｆａｃ）2及びＺｎ（ｈｆａｃ）2が挙げられる。
【００２４】
具体的な金属塩としては、ＣｏＣｌ2、ＣｏＢｒ2、Ｃｏ（ＳＣＮ）2、Ｃｏ（ＣｌＯ4）2及びＣｏ（ＮＯ3）2が挙げられる。
【００２５】
好ましい、金属錯体又は金属塩としては、Ｃｏ（ｈｆａｃ）2、ＣｏＣｌ2、ＣｏＢｒ2及びＣｏ（ＳＣＮ）2が挙げられる。
【００２６】
式（１）で表される化合物と金属錯体又は金属塩とのモル比（［式（１）で表される化合物］：［金属錯体又は金属塩］モル比）は、通常６：１〜１：１の範囲を使用することができ、好ましくは、４：１〜２：１の範囲である。
【００２７】
式（１）で表される化合物及び、金属錯体の混合は、固体状態（溶剤を加えない状態）のまま、適当な溶剤に溶解した溶液状態又は高分子などにドーピングした状態で行うことが出来るが、通常、適当な溶剤に溶解した溶液状態で行うのが好ましい。
【００２８】
使用される溶媒は、式（１）で表される化合物及び、金属錯体又は金属塩を必要濃度以上溶解し、且つ磁性が得られる溶媒であれば特に限定はしないが、具体的には、エタノール、プロパノール等のアルコール系溶媒、塩化メチレン、クロロホルム等のハロゲン化炭化水素、テトラヒドロフラン、２−メチルテトラヒドロフラン、テトラヒドロピラン等の環状エーテル及びアセトニトリル、ブチロニトリル等のニトリル系溶媒等並びにこれらの溶媒の混合液が挙げられ、好ましくは、アルコール系溶媒、ニトリル系溶媒、環状エーテル及びアルコール系溶媒と環状エーテルの混合液が挙げられ、更に好ましくは、エタノール、ブチロニトリル、２−メチルテトラヒドロフラン及びエタノールと２−メチルテトラヒドロフランの混合液等が挙げられ、更に好ましくは、エタノールと２−メチルテトラヒドロフランの混合液が挙げられる。
【００２９】
式（１）で表される化合物及び、金属錯体又は金属塩を混合する温度は、通常−３０〜３０℃の範囲を使用することができ、好ましくは、０〜２０℃の範囲である。
【００３０】
式（１）で表される化合物及び、金属錯体又は金属塩を混合する時間は、混合する温度により変化するため、一概に決定できないが、例えば、２０℃の場合、０．１〜１０分間の範囲である。
【００３１】
式（１）で表される化合物及び、金属錯体又は金属塩を混合させることにより、式（１）で表される化合物を配位子とする有機金属錯体が生成するが、該有機金属錯体は、混合した溶液そのまま、又は一度単離した後に光照射することもできる（固体状態のまま、適当な溶剤に溶解した溶液状態又は高分子などにドーピングした状態等）。
【００３２】
光照射の光源としては、ジアゾ基の吸収波長である５００ｎｍ付近を含む光源であれば特に限定されないが、アルゴンイオンレーザー（５１４ｎｍ）、ヘリウムカドミウム（Ｈｅ−Ｃｄ）レーザー（４４２ｎｍ）、キセノンランプ、高圧水銀ランプ及びＹＡＧレーザーの２倍波（５３２ｎｍ）等が挙げられ、好ましくは、アルゴンイオンレーザー（５１４ｎｍ）を挙げることができる。
【００３３】
光照射の波長としては、ジアゾ基の吸収波長である５００ｎｍ付近を含む光源であれば特に限定されないが、通常４００ｎｍ以上の波長を使用することができ、好ましくは、４００〜５５０ｎｍの範囲である。
【００３４】
光照射時の温度は、生成したカルベンが安定であれば特に限定されないが、通常２０Ｋ以下の温度を用いることができ、好ましくは１５Ｋ以下である。
【００３５】
光照射の時間は、光照射時の温度と用いる波長、出力、又サンプルの濃度により変化するため、一概に決定できないが、例えば、１５Ｋの場合、アルゴンイオンレーザー（１５０ｍＷ）で５時間以上照射すれば充分である。
【００３６】
次に、式（１）で表される化合物の製造法について説明する。
【００３７】
式（１）で表される化合物は、反応式１に示す方法により製造することができる。
【００３８】
反応式１
【００３９】
【化４】
（式中、Ｒ1〜Ｒ7は、前記と同じ意味を表す。）
即ち、化合物（２）をＤＭＳＯ（ジメチルスルホキシド）中、Ｎ２Ｈ４（ヒドラジン）及びＮ２Ｈ４・ＨＣｌ（塩酸ヒドラジン）でヒドラゾン化し、更にＣＨ２Ｃｌ２（塩化メチレン）中、ＭｎＯ２（二酸化マンガン）で酸化することにより、式（１）で表される化合物を製造することができる。
【００４１】
【実施例】
以下、本発明について実施例を挙げて詳述するが、本発明はこれらの実施例に何ら限定されるものではない。
【００４２】
参考例１（化合物（３）（Ｒ1＝Ｒ2＝Ｒ3＝Ｒ4＝Ｒ5＝Ｒ6＝Ｒ7＝Ｈ）の合成）
【００４３】
【化５】
アルゴン雰囲気下、４−ベンゾピリジン１．０ｇ（６．０ｍｍｏｌ）を５ｍＬのＤＭＳＯに溶解させ、塩酸ヒドラジン４．１ｇ（６０ｍｍｏｌ）、無水ヒドラジン１．５ｍＬの順で加え９０℃で撹拌した。６時間撹拌後、反応溶液を氷水中にあけて１５分撹拌した。析出した乳白色固体を吸引濾過し、充分の水とジエチルエーテルで洗浄し、化合物（３）１．１ｇ（５．６ｍｍｏｌ）を得た。難溶解固体のため未精製のまま次の反応を行った。
【００４５】
IR(KBr): 1598、1566 cm-1
m.p. (℃): 78-81。
【００４６】
参考例２（化合物（４）（Ｒ1＝Ｒ2＝Ｒ3＝Ｒ4＝Ｒ5＝Ｒ6＝Ｒ7＝Ｈ）の合成）
【００４７】
【化６】
アルゴン雰囲気下、化合物（３）３５０ｍｇ（１．７８ｍｍｏｌ）の７ｍＬ塩化メチレン溶液中に活性二酸化マンガン１．５６ｇ（１８ｍｍｏｌ）を 加え、室温で遮光しながら撹拌した。２時間後、反応溶液を吸引濾過し無機物を除き、溶媒を減圧留去し、オイル状固体を得た。短いシリカゲルカラムクロマトグラフィーにより、濾過で除去できなかった無機物を除き、溶媒を減圧留去して、赤色固体３０５ｍｇ（１．５６ｍｍｏｌ）得た。この固体をヘキサン−ジエチルエーテル混合溶媒に溶かし、４℃で静置して化合物（４）の赤色結晶を得た。
【００４９】
1H-NMR(270MHz,CDCl3)δ：
8.47(dd, J＝4.6, 1.7 Hz, 2H), 7.36 (m, 5H), 7.07 (dd, J＝ 4.6, 1.7 Hz, 2H)
IR(KBr): 2044 cm-1
m.p. (℃): 59-61。
【００５０】
実施例１（コバルト錯体を用いる単分子磁石の製造）
化合物（４）の濃度が８０ｍｍｏｌ／Ｌとなる２−メチルテトラヒドロフラン溶液を調製した。Ｃｏ（ＳＣＮ）2（チオシアン酸コバルト）の濃度が２０ｍｍｏｌ／Ｌとなるエタノールと２−メチルテトラヒドロフランの混合溶液（エタノール：２−メチルテトラヒドロフラン＝１：９（ｖ／ｖ））を調製し、２種類の溶液を１：１（ｖ／ｖ）で混合した。この溶液５０μＬをマイクロシリンジにとり、磁化測定装置（ＳＱＵＩＤ）用の透明なカプセルに移す。試料が入ったカプセルをＳＱＵＩＤのプローブに挿入し、温度２Ｋにおいて磁場０〜５Ｔの範囲で磁化の測定を行った。結果を図１中の黒塗りのプロットとして示した。この結果は、コバルトのスピン（Ｓ＝３／２）と溶媒分子の反磁性の和を反映し、残留磁化は持たない。次に、プローブの中を５〜１０Ｋ以下に保ちながら、アルゴンイオンレーザー（５１４ｎｍ）で試料を照射し、５０００ Ｏｅで磁化の変化をモニターした結果を図２に示す。照射時間とともに、磁化が増加して行くのが観測できる。これは、試料の光分解により生じたカルベンのスピンとコバルトのスピンが強磁性的に相互作用していることを示している。磁化の増加が飽和したら光照射を終了し、再び温度２Ｋにおいて、磁場０〜５Ｔ、５Ｔ〜−５Ｔ、−５Ｔ〜５Ｔの順で磁化の測定を行った。結果を図１中の白抜きのプロットとして示した。図１で明らかなように、外部磁場０に於いて、明確な残留磁化（６．５×１０ 3 ｅｍｕ・Ｏｅ・ｍｏｌ -1 ）が観測された。更に、交流磁化率の温度依存性の測定を５Ｇで１〜１０００Ｈｚの速度で行い、図３に示す。その結果、虚数項χ’’のピークトップの温度は測定周波数に依存し、周波数が大きくなるに従って、高温側に移動した。この結果と図1のヒステレシス特性を合わせると、得られたカルベン−コバルト錯体は単核単分子磁石であることがわかる。又、生成した分子磁性体の温度を９０Ｋまで上昇させカルベンを消失させた後、再び１０Ｋ以下で磁化を測定すると残留磁化は認められなくなることから、当該コバルト錯体の光照射によるカルベンの発生に伴って単核単分子磁石が生成したことが証明された。
【００５１】
比較例１（銅錯体を用いる分子磁性体の製造）
化合物（４）の濃度が８ｍｍｏｌ／Ｌとなるエタノールの溶液を調製した。Ｃｕ（ＮＯ３）2（硝酸銅）の濃度が４ｍｍｏｌ／Ｌとなるエタノール溶液を調製し、２種類の溶液を１：１（ｖ／ｖ）で混合した。この溶液５０μＬをマイクロシリンジにとり、磁化測定装置（ＳＱＵＩＤ）用の透明なカプセルに移す。試料が入ったカプセルをＳＱＵＩＤのプローブに挿入し、プローブの中を５〜１０Ｋ以下に保ちながら、アルゴンイオンレーザー（５１４ｎｍ）で試料を照射した。実施例１と同様の操作により磁化の磁場依存性の測定を行い、９個のスピンが平衡に揃った常磁性体が観測された。又、残留磁化は認められなかった。
【００５２】
【発明の効果】
本実施例によれば、光応答型単分子磁石を得ることができる。熱的安定性を克服できれば、単分子磁石は透明な磁性体であるため、広範囲な応用が可能となる。例えば、磁性インクとして利用すると、情報の記録が可能な印刷物を容易に製造でき、あるいは、磁性トナーとして利用すると、定着性の向上、解像度の向上、色彩の向上、印刷スピードの向上等が期待される。また、有機溶媒に溶かして、薄膜を形成できるため、リソグラフィーにより、光照射した部分に磁気回路を書き込むことができる。
【００５３】
そして、本実施例によれば、残留磁化を示す光応答型単分子磁石を得ることができる。熱的安定性を克服できれば、単分子磁石は透明な磁性体であるため、広範囲な応用が可能となる。例えば、磁性インクとして利用すると、情報の記録が可能な印刷物を容易に製造でき、あるいは、磁性トナーとして利用すると、定着性の向上、解像度の向上、色彩の向上、印刷スピードの向上等が期待される。また、有機溶媒に溶かして、薄膜を形成できるため、リソグラフィーにより、光照射した部分に磁気回路を書き込むことができる。
【００５４】
本発明により、残留磁化を示す光応答型単分子磁石を製造することができた。
【図面の簡単な説明】
【図１】 実施例１の化合物（４）及びコバルト錯体の混合物における、光照射前（黒塗り）と光照射後（白抜き）の、２Ｋでの磁化の磁場依存性と、光照射後のヒステリシスを示す。
図において、縦軸は磁化｛Magnetization (emu・Oe/mol)｝を表し、横軸は磁界｛H (Oe)｝を表す。
【図２】 実施例１における、光照射（アルゴンイオンレーザー（５１４ｎｍ））の照射時間（分）経過における、化合物（４）及びコバルト錯体の混合物の５０００ Ｏｅでの磁化の変化を示す。
図において、縦軸は磁化｛Magnetization (emu・Oe/mol)｝を表し、横軸は光照射（アルゴンイオンレーザー（５１４ｎｍ））の照射時間（分）｛Irradiation Time (min.)｝を表す。
【図３】 光照射後の、化合物（４）及びコバルト錯体の混合物における交流磁化率の温度依存性（１Ｈｚ、１０Ｈｚ、１００Ｈｚ、５００Ｈｚ、１０００Ｈｚでそれぞれ測定）を示す。
図において、縦軸は交流磁化率｛χ’(emu/mol)｝を表し、横軸は温度｛T (K)｝を表す。ここで○：１Ｈｚ、□：１０Ｈｚ、△：１００Ｈｚ、▽：５００Ｈｚ、◆：１０００Ｈｚでのそれぞれ測定曲線を表す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photoresponsive single molecule magnet and a method for producing the same. More specifically, the present invention relates to a single molecule magnet obtained by arranging unpaired electrons derived from organic radicals (carbene) generated by light irradiation by ferromagnetic interaction, and a method for producing the same.
[0002]
[Prior art]
Many attempts have been made to construct molecular ferromagnets by aligning electron spins in parallel by imparting ferromagnetic interactions to organic radicals. Molecular magnetic materials are much easier to mold than inorganic magnetic materials, and can be easily modified in physical properties depending on the purpose. Therefore, expectations for new materials in various fields are increasing. From the research so far, in order to create magnets with organic matter, (1) as many spins as possible, (2) align in parallel with strong interactions, and (3) have a multidimensional mesoscopic spread. It has been considered necessary to integrate.
[0003]
The present inventors have succeeded in integrating spins in one dimension through a coordinate bond with a metal using a triplet carbene having a strong magnetic interaction as an organic spin source (Non-patent Document 1). reference.). These carbenes are stable up to 230K (ordinary carbenes chemically react and disappear at about 100K), suggesting the possibility of stable molecular ferromagnets even at room temperature. However, the obtained metal complex containing carbene is an ultra-high spin paramagnetic substance and has no remanent magnetization.
[0004]
In addition, the present inventors have succeeded in synthesizing a molecular magnetic material having remanent magnetization by highly integrating 3d spin of a metal ion and 2p spin of a ligand carbene in three dimensions (Non-Patent
[0005]
In order to construct the unimolecular magnetic material, a somewhat large spin quantum number and a negative zero-field splitting parameter (D) are required. Conventional monomolecular magnets are oligo- and poly-ring-closed metal complexes in which metal atoms typified by manganese atoms are connected by oxo bridges, and all spin sources are supplied from metal atoms (see Non-Patent Document 5). .
[0006]
[Non-Patent Document 1]
“Journal of the American Society (J. Am. Chem. Soc.)” (USA), 1997, Vol. 119, p. 8246-8252
[Non-Patent Document 2]
“Appl. Magn. Reson.” (Austria), 2003, Vol. 23, p. 507
[Non-Patent Document 3]
“Polyhedron” (Netherlands), 2001, Vol. 20, p. 1387-1389
[Non-Patent Document 4]
“Journal of the American Society (J. Am. Chem. Soc.)” (USA), 2001, Vol. 123, p. 9685-9686
[Non-Patent Document 5]
“Nature” (UK), 1993, 365, p. 141-143
[0007]
[Problems to be solved by the invention]
The present invention relates to a single-molecule magnet using only one metal atom, which is constructed in a heterospin system using a metal and a carbene as a spin source.
[0008]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that a monomolecular magnet having residual magnetization can be obtained by irradiating a solution containing a diazo-pyridine compound and a metal complex or metal salt with light, thereby completing the present invention. .
[0009]
That is, the present invention provides the formula (1)
[0010]
[Chemical 3]
(Wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, And an isobutyl group, a secondary butyl group, a tertiary butyl group, a methoxy group, an ethoxy group, a normal propoxy group, an isopropoxy group, a normal butoxy group, an isobutoxy group, a secondary butoxy group, or a tertiary butoxy group. And metal complexes or metal salts (the metals of the metal complexes and metal salts are Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd) , Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, or Hg.) Can be obtained by irradiating with light. The present invention relates to a molecular magnet and a manufacturing method thereof.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0013]
First, each substituent of formula (1) will be specifically described.
[0014]
The substituents R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 in the compound represented by the formula (1) are each independently a hydrogen atom, a methyl group, an ethyl group, or a normal propyl group. , Isopropyl, normal butyl, isobutyl, secondary butyl, tertiary butyl, methoxy, ethoxy, normal propoxy, isopropoxy, normal butoxy, isobutoxy, secondary butoxy or tertiary butoxy In view of ease of production, preferred R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 include a hydrogen atom, a methyl group, or a methoxy group.
[0015]
Preferred combinations of substituents in the compound represented by the formula (1) are shown below.
[0016]
1) The compound represented by the formula (1), wherein R 3 , R 4 , R 5 , R 6 and R 7 are all hydrogen atoms.
[0017]
2) R 1 and R 2 are each independently a hydrogen atom or a methyl group, and R 3 , R 4 , R 5 , R 6 and R 7 are all hydrogen atoms, and are represented by formula (1) Compound.
[0018]
3) The compound represented by the formula (1), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are all hydrogen atoms.
[0019]
Next, the manufacturing method of a single molecule magnet is demonstrated.
[0020]
A monomolecular magnet can be produced by irradiating a solution obtained by mixing the compound represented by formula (1) and a metal complex or metal salt with light.
[0021]
Specific metals in the metal complex or metal salt include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, and Cd. , Hf, Ta, W, Re, Os, Ir, Pt, Au, and Hg, preferably Ni, Co, Cu, Mn, Fe, Cr, and Zn, more preferably , Co, Ni and Cu.
[0022]
Specific metal complexes or metal salts are shown below.
[0023]
Specific metal complexes include Ni (hfac) 2 , Co (hfac) 2 , Cu (hfac) 2 , Mn (hfac) 2 , Fe (hfac) 2 , Cr (hfac) 2, and Zn (hfac) 2. Can be mentioned.
[0024]
Specific metal salts, CoCl 2, CoBr 2, Co (SCN) 2, Co (ClO 4) 2 and Co (NO 3) 2 and the like.
[0025]
Preferred metal complexes or metal salts include Co (hfac) 2 , CoCl 2 , CoBr 2 and Co (SCN) 2 .
[0026]
The molar ratio of the compound represented by the formula (1) and the metal complex or metal salt ([the compound represented by the formula (1)]: [metal complex or metal salt] molar ratio) is usually 6: 1 to 1. : 1 range can be used, preferably in the range of 4: 1 to 2: 1.
[0027]
The compound represented by the formula (1) and the metal complex can be mixed in a solid state (a state in which no solvent is added), in a solution state dissolved in an appropriate solvent, or in a state doped with a polymer. However, it is usually preferable to carry out in a solution state dissolved in an appropriate solvent.
[0028]
The solvent used is not particularly limited as long as it is a solvent that dissolves the compound represented by the formula (1) and the metal complex or metal salt in a necessary concentration or more and can obtain magnetism. Alcohol solvents such as propanol, halogenated hydrocarbons such as methylene chloride and chloroform, cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and tetrahydropyran, and nitrile solvents such as acetonitrile and butyronitrile, and a mixture of these solvents. Preferred examples include alcohol solvents, nitrile solvents, cyclic ethers, and mixed solutions of alcohol solvents and cyclic ethers, more preferably ethanol, butyronitrile, 2-methyltetrahydrofuran, and ethanol and 2-methyltetrahydrofuran. List of liquid mixture Is, more preferably, a mixture of ethanol and 2-methyl tetrahydrofuran.
[0029]
The temperature at which the compound represented by the formula (1) and the metal complex or metal salt are mixed can usually be in the range of -30 to 30 ° C, and preferably in the range of 0 to 20 ° C.
[0030]
The time for mixing the compound represented by the formula (1) and the metal complex or metal salt varies depending on the temperature to be mixed, and therefore cannot be determined unconditionally. It is a range.
[0031]
By mixing the compound represented by the formula (1) and the metal complex or metal salt, an organometallic complex having the compound represented by the formula (1) as a ligand is generated. Alternatively, the mixed solution can be irradiated with light as it is or once isolated (in a solid state, a solution state dissolved in an appropriate solvent, a state doped with a polymer, or the like).
[0032]
The light source for light irradiation is not particularly limited as long as it is a light source including about 500 nm which is the absorption wavelength of the diazo group, but an argon ion laser (514 nm), a helium cadmium (He—Cd) laser (442 nm), a xenon lamp, a high pressure Examples include a mercury lamp and a double wave (532 nm) of a YAG laser, and an argon ion laser (514 nm) is preferable.
[0033]
The wavelength of the light irradiation is not particularly limited as long as it is a light source including about 500 nm which is the absorption wavelength of the diazo group, but a wavelength of 400 nm or more can usually be used, and is preferably in the range of 400 to 550 nm.
[0034]
The temperature at the time of light irradiation is not particularly limited as long as the generated carbene is stable, but a temperature of 20K or lower can be usually used, and preferably 15K or lower.
[0035]
The time of light irradiation varies depending on the temperature at the time of light irradiation, the wavelength to be used, the output, and the concentration of the sample. Therefore, for example, in the case of 15K, it is irradiated with an argon ion laser (150 mW) for 5 hours or more. Is enough.
[0036]
Next, the manufacturing method of the compound represented by Formula (1) is demonstrated.
[0037]
The compound represented by Formula (1) can be produced by the method shown in Reaction Formula 1.
[0038]
Reaction formula 1
[0039]
[Formula 4]
(In the formula, R 1 to R 7 represent the same meaning as described above.)
That is, the compound (2) was hydrazoned with N 2 H 4 (hydrazine) and N 2 H 4 · HCl (hydrazine hydrochloride) in DMSO (dimethyl sulfoxide), and further MnO 2 (CH 2 Cl 2 (methylene chloride) in MnO 2 ( By oxidizing with manganese dioxide), the compound represented by the formula (1) can be produced.
[0041]
【Example】
Hereinafter, although an example is given and the present invention is explained in full detail, the present invention is not limited to these examples at all.
[0042]
Reference Example 1 (Synthesis of Compound (3) (R 1 = R 2 = R 3 = R 4 = R 5 = R 6 = R 7 = H))
[0043]
[Chemical formula 5]
Under an argon atmosphere, 1.0 g (6.0 mmol) of 4-benzopyridine was dissolved in 5 mL of DMSO, 4.1 g (60 mmol) of hydrazine hydrochloride and 1.5 mL of anhydrous hydrazine were added in this order, and the mixture was stirred at 90 ° C. After stirring for 6 hours, the reaction solution was poured into ice water and stirred for 15 minutes. The precipitated milky white solid was filtered by suction and washed with sufficient water and diethyl ether to obtain 1.1 g (5.6 mmol) of Compound (3). The following reaction was carried out without purification because it was a hardly soluble solid.
[0045]
IR (KBr): 1598, 1566 cm -1
mp (° C): 78-81.
[0046]
Reference Example 2 (Synthesis of Compound (4) (R 1 = R 2 = R 3 = R 4 = R 5 = R 6 = R 7 = H))
[0047]
[Chemical 6]
Under an argon atmosphere, 1.56 g (18 mmol) of active manganese dioxide was added to a 7 mL methylene chloride solution of 350 mg (1.78 mmol) of the compound (3), and the mixture was stirred at room temperature while being protected from light. After 2 hours, the reaction solution was suction filtered to remove inorganic substances, and the solvent was distilled off under reduced pressure to obtain an oily solid. The inorganic substances that could not be removed by filtration were removed by short silica gel column chromatography, and the solvent was distilled off under reduced pressure to obtain 305 mg (1.56 mmol) of a red solid. This solid was dissolved in a hexane-diethyl ether mixed solvent and allowed to stand at 4 ° C. to obtain a red crystal of compound (4).
[0049]
1 H-NMR (270 MHz, CDCl 3 ) δ:
8.47 (dd, J = 4.6, 1.7 Hz, 2H), 7.36 (m, 5H), 7.07 (dd, J = 4.6, 1.7 Hz, 2H)
IR (KBr): 2044 cm -1
mp (° C): 59-61.
[0050]
Example 1 (Production of a single molecule magnet using a cobalt complex)
A 2-methyltetrahydrofuran solution having a concentration of compound (4) of 80 mmol / L was prepared. A mixed solution of ethanol and 2-methyltetrahydrofuran (ethanol: 2-methyltetrahydrofuran = 1: 9 (v / v)) with a Co (SCN) 2 (cobalt thiocyanate) concentration of 20 mmol / L was prepared. Was mixed 1: 1 (v / v). 50 μL of this solution is taken in a microsyringe and transferred to a transparent capsule for a magnetization measuring device (SQUID). The capsule containing the sample was inserted into a SQUID probe, and the magnetization was measured in a magnetic field of 0 to 5 T at a temperature of 2K. The results are shown as black plots in FIG. This result reflects the sum of the spin of cobalt (S = 3/2) and the diamagnetism of the solvent molecules, and has no residual magnetization. Next, FIG. 2 shows the result of monitoring the change in magnetization at 5000 Oe by irradiating the sample with an argon ion laser (514 nm) while keeping the inside of the probe at 5 to 10K or less. It can be observed that the magnetization increases with the irradiation time. This indicates that the carbene spin and the cobalt spin generated by photolysis of the sample interact ferromagnetically. When the increase in magnetization was saturated, the light irradiation was terminated, and the magnetization was measured again in the order of
[0051]
Comparative Example 1 (Production of molecular magnetic material using copper complex)
An ethanol solution in which the concentration of compound (4) was 8 mmol / L was prepared. An ethanol solution in which the concentration of Cu (NO 3 ) 2 (copper nitrate) was 4 mmol / L was prepared, and the two types of solutions were mixed at 1: 1 (v / v). 50 μL of this solution is taken in a microsyringe and transferred to a transparent capsule for a magnetization measuring device (SQUID). The capsule containing the sample was inserted into a SQUID probe, and the sample was irradiated with an argon ion laser (514 nm) while keeping the inside of the probe at 5 to 10K or less. The magnetic field dependence of magnetization was measured by the same operation as in Example 1, and a paramagnetic material in which nine spins were in equilibrium was observed. Further, no residual magnetization was observed.
[0052]
【The invention's effect】
According to the present embodiment, a photoresponsive monomolecular magnet can be obtained. If the thermal stability can be overcome, the single-molecule magnet is a transparent magnetic material, and thus can be used in a wide range of applications. For example, when used as a magnetic ink, it is possible to easily produce a printed matter on which information can be recorded, or when used as a magnetic toner, improvement in fixing property, improvement in resolution, improvement in color, improvement in printing speed, etc. are expected. The In addition, since a thin film can be formed by dissolving in an organic solvent, a magnetic circuit can be written in a portion irradiated with light by lithography.
[0053]
And according to a present Example, the photoresponsive type monomolecular magnet which shows a residual magnetization can be obtained. If the thermal stability can be overcome, the single-molecule magnet is a transparent magnetic material, and thus can be used in a wide range of applications. For example, when used as a magnetic ink, it is possible to easily produce a printed matter on which information can be recorded, or when used as a magnetic toner, improvement in fixing property, improvement in resolution, improvement in color, improvement in printing speed, etc. are expected. The In addition, since a thin film can be formed by dissolving in an organic solvent, a magnetic circuit can be written in a portion irradiated with light by lithography.
[0054]
According to the present invention, a photoresponsive monomolecular magnet exhibiting remanent magnetization could be manufactured.
[Brief description of the drawings]
FIG. 1 shows the magnetic field dependence of magnetization at 2K before light irradiation (black coating) and after light irradiation (outlined) in the mixture of compound (4) and cobalt complex of Example 1, and after light irradiation. Shows hysteresis.
In the figure, the vertical axis represents magnetization {Magnetization (emu · Oe / mol)}, and the horizontal axis represents magnetic field {H (Oe)}.
2 shows a change in magnetization at 5000 Oe of a mixture of a compound (4) and a cobalt complex in the course of irradiation time (minutes) of light irradiation (argon ion laser (514 nm)) in Example 1. FIG.
In the figure, the vertical axis represents magnetization {Magnetization (emu · Oe / mol)}, and the horizontal axis represents irradiation time (minute) {Irradiation Time (min.)} Of light irradiation (argon ion laser (514 nm)).
FIG. 3 shows the temperature dependence of AC magnetic susceptibility (measured at 1 Hz, 10 Hz, 100 Hz, 500 Hz, and 1000 Hz, respectively) in a mixture of compound (4) and cobalt complex after light irradiation.
In the figure, the vertical axis represents AC magnetic susceptibility {χ ′ (emu / mol)}, and the horizontal axis represents temperature {T (K)}. Here, ◯: 1 Hz, □: 10 Hz, Δ: 100 Hz, ▽: 500 Hz, and ♦: 1000 Hz, respectively, represent measurement curves.
Claims (14)
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| JP4651111B2 (en) * | 2006-03-09 | 2011-03-16 | 国立大学法人九州大学 | Single molecule magnet |
| JP4748670B2 (en) * | 2006-03-09 | 2011-08-17 | 国立大学法人九州大学 | Magnetic recording element |
| CN110729090B (en) * | 2018-11-19 | 2023-08-29 | 中国人民解放军陆军勤务学院 | Polynuclear single-molecule magnet |
| CN117024337B (en) * | 2023-08-09 | 2026-03-20 | 电子科技大学 | Stable biradical single-molecule devices containing anchoring groups and their synthesis methods |
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| CN103714932B (en) * | 2013-12-30 | 2016-04-20 | 北京工业大学 | A kind of Co zero dimension single molecular magnets material and preparation method and application thereof |
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