镍-Calixarene配合物的阴离子导向组装：构建孤立的{Ni 8 }，{Ni 20 }，{Ni 24 }和{Ni 32 }团簇,Crystal Growth & Design

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镍-Calixarene配合物的阴离子导向组装：构建孤立的{Ni ₈ }，{Ni ₂₀ }，{Ni ₂₄ }和{Ni ₃₂ }团簇
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2020-05-04 , DOI: 10.1021/acs.cgd.0c00426
Kaiyue Li _{1,

2} , Zhihua Zhuang _{2,

3} , Wei Chen _{2,

3} , Wuping Liao _{1,

2}

Affiliation

四个镍杯芳烃络合物，{Ni ₈（TC4A）₄L } ^2–（CIAC-244），{Ni ₃₂（TC4A）₈L ₈（CO ₃）₄（HCOO）₂ Cl ₈ } ^2–（CIAC-245），{Ni ₂₀（TC4A）₅L ₅（SO ₄）₅ Cl ₅ } ^5–（CIAC-246）和{Ni ₂₄（TC4A）₆L ₅（CO ₃）₅（SO ₄）（HCOO）Cl ₅ } ^4-（CIAC-247）（H ₄ TC4A =对-叔丁基硫杂杯[4]芳烃，H ₂L = 2,5-二氢-1,3,4-噻二唑-通过在溶剂热条件下引入不同的无机阴离子合成2,5-二硫醇）。CIAC-244的特征是通过将两个夹心状Ni _4-（TC4A）₂亚基与一个L配体连接而组装而成的铰接双哑铃状{Ni ₈ }实体。当将少量DMF引入反应系统时，CIAC-245以原位生成的CO ₃^2–阴离子获得了具有双碗形{Ni ₃₂ }扭曲结构的特征。尝试用SO ₄^2–阴离子替代CIAC-245中的CO ₃^2–阴离子导致形成由五个Ni ₄ -TC4A SBU，五个L配体构成的{Ni ₂₀ }配位轮（CIAC-246）和五种硫酸根阴离子。当同时添加大量硫酸镍和少量DMF时，{Ni ₂₄ }配比碗（CIAC-247），这可以认为是通过用CO ₃^2–阴离子代替SO ₄^2–桥并在CIAC-246中封端形成的。与具有夹心状Ni _4-（TC4A）₂二级建筑单元（SBU）的CIAC-244不同，其他三个具有羽毛球状Ni ₄ -TC4A SBU。CIAC-246对葡萄糖的氧化表现出有效的电催化活性。

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Anion-Directed Assembly of Nickel-Calixarene Complexes: Constructing Isolated {Ni8}, {Ni20}, {Ni24}, and {Ni32} Clusters

Four nickel-calixarene complexes, {Ni₈(TC4A)₄L}^2– (CIAC-244), {Ni₃₂(TC4A)₈L₈(CO₃)₄(HCOO)₂Cl₈}^2– (CIAC-245), {Ni₂₀(TC4A)₅L₅(SO₄)₅Cl₅}^5– (CIAC-246), and {Ni₂₄(TC4A)₆L₅(CO₃)₅(SO₄)(HCOO)Cl₅}^4– (CIAC-247) (H₄TC4A = p-tert-butylthiacalix[4]arene, H₂L = 2,5-dihydro-1,3,4-thiadiazole-2,5-dithiol), were synthesized by introducing different inorganic anions under the solvothermal conditions. CIAC-244 features a hinged double-dumbbell-like {Ni₈} entity assembled by linking two sandwich-like Ni₄-(TC4A)₂ subunits with one L ligand. When a little DMF was introduced into the reaction system, CIAC-245 featuring a twisted double-bowl-shaped {Ni₃₂} architecture was obtained with in situ generated CO₃^2– anions. The attempt to replace the CO₃^2– anions in CIAC-245 with the SO₄^2– anions led to the formation of a {Ni₂₀} coordination wheel (CIAC-246) constructed by five Ni₄-TC4A SBUs, five L ligands, and five sulfate anions. When much nickel sulfate and a little DMF were added simultaneously, {Ni₂₄} coordination bowl (CIAC-247) was obtained, which can be thought to form through substituting CO₃^2– anions for the SO₄^2– bridges and capping one end in CIAC-246. Different from CIAC-244 having sandwich-like Ni₄-(TC4A)₂ secondary building units (SBU), three others have some shuttlecock-like Ni₄-TC4A SBUs. CIAC-246 exhibits efficient electrocatalytical activity for the oxidation of glucose.

更新日期：2020-05-04

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