多酸基单分子磁体的设计与合成
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摘要
单分子磁体的特殊性质及其在信息存储、量子计算等方面展现出的重大而潜在应用价值，使得多酸化学家们对开展基于多酸的单分子磁体研究产生了浓厚兴趣，设计合成新型多酸基单分子磁体成为崭新的研究热点。本论文旨在设计新型多酸基单分子磁体。通过总结近5年关于多酸基单分子磁体的合成策略，借鉴并设计新合成路线，构筑了系列具有单分子磁体行为或潜在单分子磁体行为的新型多酸化合物，研究了这些化合物的合成、结构、磁性质，并探讨了多酸基单分子磁体的设计合成策略与规律。
1.利用各种多阴离子为结构导向剂，与{Cu~(II)Ln~(III)}和{Ni~(II)Ln~(III)}席夫碱配合物单元结合，合成了八例新型多酸基席夫碱杂化化合物1-8。磁性研究表明化合物3和6为首例多酸担载的3d-4f杂金属簇单分子磁体。Na_4[CuL~1]_2[Mo_8O_(26)]·6DMF (1)L~1=1,3-propanediylbis(2-iminomethylene-6-methoxy-phenol)Na_3[Ni_2L_2K(H_2O)]_2[IMo_6O_(24)]·3H_2O (2)[{CuTbL(H_2O)_3}_2{IMo_6O_(24)}]Cl.2MeOH.8H_2O (3)[{CuDyL(H_2O)_3}_2{IMo_6O_(24)}]Cl·2MeOH·8H_2O (4)Na[{CuGdL(H_2O)_3}_2{IMo_6O_(24)}]Cl_2·2MeOH8H_2O (5)[{CuTbL(H_2O)_2}_2{AlMo_6O_(12)(OH)_6}_2]·MeOH·10H_2O (6)[{CuDyL(H_2O)_2}_2{AlMo_6O_(18)(OH)_6}_2]·MeOH·8H_2O (7)[{CuGdL(H_2O)_2}_2{AlMo_6O_(18)(OH)_6}_2] MeOH`10H_2O (8)L=N, N’-bis(3-methoxysalicylidene)ethylene-1,2-diamine
2.利用α-Keggin型多阴离子[PMo_(12)O_(40)]~(3-)作为磁性单元的稀释剂，均匀分散具有D2d对称性的单核稀土-吡啶氮氧化物配位片段，构筑了一系列多酸-稀土配合物离子型晶体。对化合物10-13的磁性研究表明，化合物10具有显著的与频率相关的缓慢磁弛豫行为，是一类具有潜在单分子磁体性质的复合晶态材料。[Dy(2,2'-bipyridyl–N-N'-dioxide)_3(H_2O)][PMo_(12)O_(40)]·H_2O·CH_3CN (9)[Dy(bpyno)_4][PMo_(12)O_(40)]·2H_2O (10)[Tb(bpyno)_4][PMo_(12)O_(40)]·2H_2O (11)[Er(bpyno)_4][PMo_(12)O_(40)]·2H_2O (12)[Ho(bpyno)_4][PMo_(12)O_(40)]·2H_2O (13)bpyno=4,4'-dimethyl-2,2'-bipyridyl–N, N'-dioxide
3.利用[As_2W_(19)O_(67)(H_2O)]~(14-)多阴离子作为无机多齿配体，与稀土离子反应，合成得到三例一维链状的新型稀土多酸聚合物，并对其磁性质和荧光性质进行了初步探究。但是该系列化合物并没有获得预期的单分子磁体行为，对其中的可能原因进行了初步分析。Na_(10)[Tb_6(H_2O)_(22){As_4W_(44)(OH)_2(proline)_2O_(151)}]·20H_2O (14)Na_(10)[Dy_6(H_2O)_(22){As_4W_(44)(OH)_2(proline)_2O_(151)}]·25H_2O (15)Na_(10)[Nd_6(H_2O)_(26){As_4W_(44)(OH)_2(proline)_2O_(151)}]·31H_2O (16)
Single-molecule magnets (SMMs) have attracted great attention due to the potentialapplication in the area of high-density magnetic memories and quantum computing devices.Nowadays, the design and synthesis of polyoxometalate (POM)-based SMMs is becoming ahot topic in POM chemistry. The aim of this thesis is to design and synthesis of newPOM-based SMMs. Based on various synthetic strategies summarized from the publicationsin recent five years, a series of new POM-based hybrid compounds with SMM or potentialSMM behaviors have been synthesized. The syntheses, structures and magnetic properties ofthese compounds were investigated. In addition, the synthetic strategies and rules were alsostudied.
1. Eight new POM-based Shciff-base hybrids have been isolated by the reaction of{TM~(II)Ln~(III)}(TM=Ni or Cu) Schiff-base complexes and different POM units. In thesestructures, POM can be viewed as structure-directing agents. Magnetic studies reveal thatcompound3and6are the first POM-supported3d-4f heterometallic SMMs.Na_4[CuL~1]_2[Mo_8O_(26)]·6DMF (1)L1=1,3-propanediylbis(2-iminomethylene-6-methoxy-phenol)Na_3[Ni2L2K(H_2O)]2[IMo_6O_(24)]·3H_2O (2)[{CuTbL(H_2O)_3}_2{IMo_6O_(24)}]Cl.2MeOH.8H_2O (3)[{CuDyL(H_2O)_3}_2{IMo_6O_(24)}]Cl·2MeOH·8H_2O (4)Na[{CuGdL(H_2O)_3}_2{IMo_6O_(24)}]Cl_22MeOH8H_2O (5)[{CuTbL(H_2O)_2}_2{AlMo_6O_(12)(OH)_6}_2]·MeOH·10H_2O (6)[{CuDyL(H_2O)_2}_2{AlMo_6O_(18)(OH)_6}_2]·MeOH·8H_2O (7)[{CuGdL(H_2O)_2}_2{AlMo_6O_(18)(OH)_6}_2] MeOH10H_2O (8)L=N, N’-bis(3-methoxysalicylidene)ethylene-1,2-diamine
2. When α-Keggin-type polyanions [PMo_(12)O_(40)]~(3-)were used as magnetic diluting agentsto disperse the mononuclear lanthanide-pridine-N-O coordination complex units, five newionic crystal compounds based on [Ln(bpyno)_4]3+and [PMo_(12)O_(40)]3-units were prepared.Magnetic measurements indicate that compound10exhibits frequency dependent ac magneticsusceptibilities indicative of slow relaxation of the magnetization and possible SMMbehaviors.[Dy(2,2'-bipyridyl–N-N'-dioxide)_3(H_2O)][PMo_(12)O_(40)]·H_2O·CH_3CN (9)[Dy(bpyno)_4][PMo_(12)O_(40)]·2H_2O (10)[Tb(bpyno)_4][PMo_(12)O_(40)]·2H_2O (11)[Er(bpyno)_4][PMo_(12)O_(40)]·2H_2O (12) [Ho(bpyno)_4][PMo_(12)O_(40)]·2H_2O (13)bpyno=4,4'-dimethyl-2,2'-bipyridyl–N, N'-dioxide
3. When [As_2W_(19)O_(67)(H_2O)]~(14-)were used as multi-dentate inorganic ligands to react withvarious lanthanides cations, three new one-dimensional POM-based lanthanide complexeswere isolated. The magnetic and luminescent properties of compound14and15have beeninvestigated, but no SMM behaviors were found. The possible reason was predicted.Na_(10)[Tb_6(H_2O)_(22){As_4W_(44)(OH)_2(proline)_2O_(151)}]·20H_2O (14)Na_(10)[Dy_6(H_2O)_(22){As_4W_(44)(OH)_2(proline)_2O_(151)}]·25H_2O (15)Na_(10)[Nd_6(H_2O)_(26){As_4W_(44)(OH)_2(proline)_2O_(151)}]·31H_2O (16)
1.利用各种多阴离子为结构导向剂，与{Cu~(II)Ln~(III)}和{Ni~(II)Ln~(III)}席夫碱配合物单元结合，合成了八例新型多酸基席夫碱杂化化合物1-8。磁性研究表明化合物3和6为首例多酸担载的3d-4f杂金属簇单分子磁体。Na_4[CuL~1]_2[Mo_8O_(26)]·6DMF (1)L~1=1,3-propanediylbis(2-iminomethylene-6-methoxy-phenol)Na_3[Ni_2L_2K(H_2O)]_2[IMo_6O_(24)]·3H_2O (2)[{CuTbL(H_2O)_3}_2{IMo_6O_(24)}]Cl.2MeOH.8H_2O (3)[{CuDyL(H_2O)_3}_2{IMo_6O_(24)}]Cl·2MeOH·8H_2O (4)Na[{CuGdL(H_2O)_3}_2{IMo_6O_(24)}]Cl_2·2MeOH8H_2O (5)[{CuTbL(H_2O)_2}_2{AlMo_6O_(12)(OH)_6}_2]·MeOH·10H_2O (6)[{CuDyL(H_2O)_2}_2{AlMo_6O_(18)(OH)_6}_2]·MeOH·8H_2O (7)[{CuGdL(H_2O)_2}_2{AlMo_6O_(18)(OH)_6}_2] MeOH`10H_2O (8)L=N, N’-bis(3-methoxysalicylidene)ethylene-1,2-diamine
2.利用α-Keggin型多阴离子[PMo_(12)O_(40)]~(3-)作为磁性单元的稀释剂，均匀分散具有D2d对称性的单核稀土-吡啶氮氧化物配位片段，构筑了一系列多酸-稀土配合物离子型晶体。对化合物10-13的磁性研究表明，化合物10具有显著的与频率相关的缓慢磁弛豫行为，是一类具有潜在单分子磁体性质的复合晶态材料。[Dy(2,2'-bipyridyl–N-N'-dioxide)_3(H_2O)][PMo_(12)O_(40)]·H_2O·CH_3CN (9)[Dy(bpyno)_4][PMo_(12)O_(40)]·2H_2O (10)[Tb(bpyno)_4][PMo_(12)O_(40)]·2H_2O (11)[Er(bpyno)_4][PMo_(12)O_(40)]·2H_2O (12)[Ho(bpyno)_4][PMo_(12)O_(40)]·2H_2O (13)bpyno=4,4'-dimethyl-2,2'-bipyridyl–N, N'-dioxide
3.利用[As_2W_(19)O_(67)(H_2O)]~(14-)多阴离子作为无机多齿配体，与稀土离子反应，合成得到三例一维链状的新型稀土多酸聚合物，并对其磁性质和荧光性质进行了初步探究。但是该系列化合物并没有获得预期的单分子磁体行为，对其中的可能原因进行了初步分析。Na_(10)[Tb_6(H_2O)_(22){As_4W_(44)(OH)_2(proline)_2O_(151)}]·20H_2O (14)Na_(10)[Dy_6(H_2O)_(22){As_4W_(44)(OH)_2(proline)_2O_(151)}]·25H_2O (15)Na_(10)[Nd_6(H_2O)_(26){As_4W_(44)(OH)_2(proline)_2O_(151)}]·31H_2O (16)
Single-molecule magnets (SMMs) have attracted great attention due to the potentialapplication in the area of high-density magnetic memories and quantum computing devices.Nowadays, the design and synthesis of polyoxometalate (POM)-based SMMs is becoming ahot topic in POM chemistry. The aim of this thesis is to design and synthesis of newPOM-based SMMs. Based on various synthetic strategies summarized from the publicationsin recent five years, a series of new POM-based hybrid compounds with SMM or potentialSMM behaviors have been synthesized. The syntheses, structures and magnetic properties ofthese compounds were investigated. In addition, the synthetic strategies and rules were alsostudied.
1. Eight new POM-based Shciff-base hybrids have been isolated by the reaction of{TM~(II)Ln~(III)}(TM=Ni or Cu) Schiff-base complexes and different POM units. In thesestructures, POM can be viewed as structure-directing agents. Magnetic studies reveal thatcompound3and6are the first POM-supported3d-4f heterometallic SMMs.Na_4[CuL~1]_2[Mo_8O_(26)]·6DMF (1)L1=1,3-propanediylbis(2-iminomethylene-6-methoxy-phenol)Na_3[Ni2L2K(H_2O)]2[IMo_6O_(24)]·3H_2O (2)[{CuTbL(H_2O)_3}_2{IMo_6O_(24)}]Cl.2MeOH.8H_2O (3)[{CuDyL(H_2O)_3}_2{IMo_6O_(24)}]Cl·2MeOH·8H_2O (4)Na[{CuGdL(H_2O)_3}_2{IMo_6O_(24)}]Cl_22MeOH8H_2O (5)[{CuTbL(H_2O)_2}_2{AlMo_6O_(12)(OH)_6}_2]·MeOH·10H_2O (6)[{CuDyL(H_2O)_2}_2{AlMo_6O_(18)(OH)_6}_2]·MeOH·8H_2O (7)[{CuGdL(H_2O)_2}_2{AlMo_6O_(18)(OH)_6}_2] MeOH10H_2O (8)L=N, N’-bis(3-methoxysalicylidene)ethylene-1,2-diamine
2. When α-Keggin-type polyanions [PMo_(12)O_(40)]~(3-)were used as magnetic diluting agentsto disperse the mononuclear lanthanide-pridine-N-O coordination complex units, five newionic crystal compounds based on [Ln(bpyno)_4]3+and [PMo_(12)O_(40)]3-units were prepared.Magnetic measurements indicate that compound10exhibits frequency dependent ac magneticsusceptibilities indicative of slow relaxation of the magnetization and possible SMMbehaviors.[Dy(2,2'-bipyridyl–N-N'-dioxide)_3(H_2O)][PMo_(12)O_(40)]·H_2O·CH_3CN (9)[Dy(bpyno)_4][PMo_(12)O_(40)]·2H_2O (10)[Tb(bpyno)_4][PMo_(12)O_(40)]·2H_2O (11)[Er(bpyno)_4][PMo_(12)O_(40)]·2H_2O (12) [Ho(bpyno)_4][PMo_(12)O_(40)]·2H_2O (13)bpyno=4,4'-dimethyl-2,2'-bipyridyl–N, N'-dioxide
3. When [As_2W_(19)O_(67)(H_2O)]~(14-)were used as multi-dentate inorganic ligands to react withvarious lanthanides cations, three new one-dimensional POM-based lanthanide complexeswere isolated. The magnetic and luminescent properties of compound14and15have beeninvestigated, but no SMM behaviors were found. The possible reason was predicted.Na_(10)[Tb_6(H_2O)_(22){As_4W_(44)(OH)_2(proline)_2O_(151)}]·20H_2O (14)Na_(10)[Dy_6(H_2O)_(22){As_4W_(44)(OH)_2(proline)_2O_(151)}]·25H_2O (15)Na_(10)[Nd_6(H_2O)_(26){As_4W_(44)(OH)_2(proline)_2O_(151)}]·31H_2O (16)
引文
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