Journal of Solid State Chemistry ( IF 3.3 ) Pub Date : 2018-10-10 , DOI: 10.1016/j.jssc.2018.10.002 Shufen Li , Jingyu Han , Limei Zhang , Wenqing Jiang , Dingxian Jia
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New Mn(II)-thioantimonate compounds [Mn(NH3)6]2[{Mn(NH3)3}2(μ3-SbS4)2]Cl2 (1), [Mn(NH3)6][{Mn(NH3)4}2(μ-SbS4)2]·2H2O (2), [Mn(NH3)6][{Mn2(μ-SbS4)2}(μ-N2H4)2] (3), and [{Mn(N2H4)}2{Mn(μ-SbS3)2(μ-N2H4)2}(μ-N2H4)2]n (4) were prepared in different hydrazine solution under solvothermal conditions. In 1, the tetrahedral SbS4 unit acts as a tridentate bridging ligand to connect the [Mn(NH3)3]2+ units into a 2-D lamellar anion [Mn(NH3)3(μ3-SbS4)2−]n containing 12-membered Mn3Sb3S6 heterorings. Two SbS4 ligands join two [Mn(NH3)4]2+ units with monodentate μ−1κ1S1: 2κ1S1 bridging mode, forming a binuclear [{Mn(NH3)4}2(μ-SbS4)2]2− anion in 2. In 3, the SbS4 ligand links [Mn2(μ-N2H4)2] units with tridentate bridging mode, to form a 1-D [{Mn2(μ-SbS4)2}(μ-N2H4)22−]n chain-like anion. Octahedral [Mn(NH3)6]2+ complex cation acts as the counter ion in compounds 1−3. In 4, the Mn(N2H4) units are interconnected into a neutral infinite [{Mn(N2H4)}2{Mn(μ-SbS3)2(μ-N2H4)2}(μ-N2H4)2]n chain by μ-SbS3 and μ-N2H4 bridging ligands. The trigonal pyramidal SbS3 unit adopts a tridentate bridging coordination mode μ−1κ2S1, S2:2κ2S1, S3. Compounds 1−4 exhibit tunable semiconducting band gaps varying in the range of 2.38−2.55 eV. Compounds 1 and 2 display higher photocatalytic activity in the degradation of crystal violet than in the degradation of methyl orange under visible light irradiation.
中文翻译：
Mn（II）与SbS 4和SbS 3配体的络合：肼溶剂热合成，硫代锑酸锰的晶体结构和光催化性能
新的Mn（II）化合物-thioantimonate [锰（NH 3）6 ] 2 [{的Mn（NH 3）3 } 2（μ 3 -SBS 4）2 ]氯2（1），[锰（NH 3）6 ] [{锰（NH 3）4 } 2（μ-的SbS 4）2 ]·2H 2 O（2），[锰（NH 3）6 ] [{的Mn 2（μ-的SbS 4）2 }（μ-N 2高4）2 ]（3），和[{锰（N 2 ħ 4）} 2 {锰（μ-的SbS 3）2（μ-N 2 ħ 4）2 }（μ-N 2 ħ 4）2 ] Ñ（4）在溶剂热条件下在不同的肼溶液中制备。在1中，四面体SbS 4单元充当三齿桥接配体，将[Mn（NH 3）3 ] 2+单元连接到二维层状阴离子[Mn（NH 3）3（μ 3 -SBS 4）2- ] ñ含有12元的Mn 3的Sb 3小号6杂环中。两个SB 4个配体连接两个[锰（NH 3）4 ] 2+单位单齿μ-1κ 1小号1：2κ 1 š 1桥接模式，形成一个双核[{的Mn（NH 3）4 } 2（μ-的SbS 4）2 ] 2-阴离子2。在3，在SBS 4配体连结[锰2（μ-N 2 ħ 4）2 ]单元具有三齿桥接模式，以形成1-d [{的Mn 2（μ-的SbS 4）2 }（μ-N 2 ħ 4）2 2- ] n链状阴离子。八面体[锰（NH 3）6 ] 2+配合物阳离子作为化合物中的抗衡离子1 - 3。在4中，Mn（N 2 H 4）单元互连成中性无限[{Mn（N 2 H 4）}2 {锰（μ-的SbS 3）2（μ-N 2 ħ 4）2 }（μ-N 2 ħ 4）2 ] Ñ由μ-的SbS链3和μ-N 2 ħ 4个桥连配体。三棱的SbS 3单元采用三齿桥接协调模式μ-1κ 2小号1，s ^ 2：2κ 2 s ^ 1，S ^ 3。化合物1 - 4表现出可调的半导体带隙，其变化范围为2.38-2.55 eV。在可见光照射下，化合物1和2在结晶紫的降解中比在甲基橙的降解中显示出更高的光催化活性。
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