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Synthesis, structure, luminescence, and magnetic properties of a single-ion magnet, "$$mer$$"-[Tris($$N$$-[(imidazol-4-yl)-methylidene]-DL-phenylalaninato)terbium(III) and related "$$fac$$"-DL-alaninato derivative

"$$mer$$"-[Tris($$N$$-[(imidazol-4-yl)-methylidene]-DL-phenylalaninato)terbium(III)とその関連誘導体"$$fac$$"-DL-Alaninatoに基づいた単イオン磁石の合成,構造,発光および磁性

山内 卓*; 藤波 武*; 松本 尚英*; 餅田 直剛*; 石田 尚行*; 砂月 幸成*; 渡邉 雅之   ; 槌本 昌信*; Coletti, C.*; Re, N.*

Yamauchi, Suguru*; Fujinami, Takeshi*; Matsumoto, Naohide*; Mochida, Naotaka*; Ishida, Takayuki*; Sunatsuki, Yukinari*; Watanabe, Masayuki; Tsuchimoto, Masanobu*; Coletti, C.*; Re, N.*

N$$_{6}$$O$$_{3}$$ドナーを含む配位環境の異なる2種類のテルビウム錯体を合成した。すなわち${it "fac"}$-[Tb$$^{rm III}$$(HL$$^{rm DL-ala}$$)$$_{3}$$]7H$$_{2}$$O(${bf 1}$)および${it "mer"}$-[Tb$$^{rm III}$$(HL$$^{rm DL-phe}$$)$$_{3}$$]7H$$_{2}$$O (${bf 2}$)を合成した。ここで、H$$_{2}$$L$$^{rm DL-ala}$$とH$$_{2}$$L$$^{rm DL-phe}$$は、それぞれ${it N}$-[(imidazol-4-yl)methylidene]-DL-alanine and -DL-phenylalanineである。磁性データをテルビウムイオン(4f$$^{8}$$, ${it J}$=6, ${it S}$=3, ${it L}$=3, ${it g$_{J}$}$=3/2, $$^{7}$$F$$_{6}$$)に係る結晶場分裂効果を含んだスピンハミルトニアンにより解析を行った。基底状態のシュタルク分裂を磁性解析により評価し、どちらの錯体もエネルギー順位パターンがIsingタイプの磁気異方性を示すことを明らかにした。また、高い効率(量子収率0.50, 0.61)での発光も観察され、$$^{5}$$D$$_{4}$$ $$rightarrow$$ $$^{7}$$F$$_{6}$$遷移の微細構造が磁性解析の結果とよく一致することも明らかにした。

Two Tb$$^{rm III}$$ complexes with same N$$_{6}$$O$$_{3}$$ donor atoms but different coordination geometries,${it "$fac$"}$-[Tb$$^{rm III}$$(HL$$^{rm DL-ala}$$)$$_{3}$$]7H$$_{2}$$O (${bf 1}$) and ${it "$mer$"}$-[Tb$$^{rm III}$$(HL$$^{rm DL-phe}$$)$$_{3}$$]7H$$_{2}$$O (${bf 2}$), were synthesized, where H$$_{2}$$L$$^{rm DL-ala}$$ and H$$_{2}$$L$$^{rm DL-phe}$$ are ${it N}$-[(imidazol-4-yl)methylidene]-DL-alanine and -DL-phenylalanine, respectively. The magnetic data were analyzed by a spin Hamiltonian including the crystal field effect on Tb$$^{rm III}$$ ion (4f$$^{8}$$, ${it J}$ = 6, ${it S}$ = 3, ${it L}$ = 3, ${it g$_{J}$}$ = 3/2, $$^{7}$$F$$_{6}$$). The Stark splitting of the ground state $$^{7}$$F$$_{6}$$ was evaluated from the magnetic analysis, and the energy diagram pattern indicated an easy-plane and easy-axis (Ising type) magnetic anisotropies for ${bf 1}$ and ${bf 2}$, respectively. Highly efficient luminescences with $$phi$$ = 0.50 and 0.61 for ${bf 1}$ and ${bf 2}$, respectively, were observed, and the luminescence fine structure due to the $$^{5}$$D$$_{4}$$ $$rightarrow$$ $$^{7}$$F$$_{6}$$ transition is in good accordance with the energy diagram determined from the magnetic analysis.

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パーセンタイル:63.97

分野:Chemistry, Inorganic & Nuclear

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