杂多蓝的合成策略、多维结构组装和磁性研究
摘要
多金属氧酸盐(Polyoxometalates,简写为POMs)能够获得一个或几个电子并保持结构不变。还原后的混价(V, VI)还原体系通常呈现出深蓝色因此也成还原态多酸为“杂多蓝”(Heteropoly blues,简写为HPBs)。杂多蓝中的还原电子既可以定域在某些特定的金属中心上，又可以离域在几个金属中心或整个多酸骨架上。因此，杂多蓝中还原电子的存在能够使杂多蓝端氧上的电子密度得到修饰，而这样的修饰不仅可以影响杂多蓝表面氧原子的配位能力，还可以影响其物理化学性质性质。杂多蓝也因此在很多领域都有其独特的应用前景，例如磁性，抗病毒，光催化和质子传导等领域。尽管杂多蓝在这些领域具有如此广阔的前景，但是与杂多酸相比，对杂多蓝合成和性质的研究却很少，关于杂多蓝的晶体结构报道也并不多。这主要是杂多蓝在合成和稳定性方面存在困难。极大地阻碍了杂多蓝的研究进展。因此开发稳定型杂多蓝的合成策略具有非常重要的意义。
本论文中，我们开发并拓展了一条合成稳定型杂多蓝的策略，合成了十个杂多蓝化合物并测定了它们的晶体结构。这个策略不仅适用于Keggin和Dawson结构杂多蓝的合成，而且适用于MoVI-MoV混合型杂多蓝和WVI-MoV混合型杂多蓝。采用电喷雾质谱监测反应过程中的溶液，成功地监测到了大量带有草酸根的杂多蓝中间体，探明了此类杂多蓝的形成过程是带有草酸根的[Mo_2~VO_4]~(2+)基团先嵌入到缺位多酸中，形成了带有草酸根的杂多蓝中间体，然后脱去草酸根形成目标杂多蓝。磁性研究发现，WVI-MoV混合型杂多蓝在室温下为顺磁性，而MoVI-MoV混合型杂多蓝在室温下为抗磁性，还原Mo的个数和位置也对这些杂多蓝的磁性产生了很大的影响。研究表明，通过调节还原Mo的个数和位置，能够实现对杂多蓝表面电子分布的调节。
1.采用[GeW_(10)Mo_2O_(40)]~(6-)作为建筑块，合成了两个杂多蓝配合物：H_2[α-GeW_(10)Mo~V_2O_(40)][Cu(DMF)_3H_2O]_25H_2O (1)H_4[α-GeW_(10)Mo~V_2O_(40)]_2[CuK_2(DMF)_6][K_4(DMF)_6](2)
这两个化合物代表了首例直接用W-Mo混合型杂多蓝作为建筑块，形成的基于杂多蓝的多维结构。研究表明，通过调节原料铜的用量能够实现对化合物维度的调控。磁性研究表明，这种两电子杂多蓝在室温下呈现出顺磁性。这与以往报道的两电子杂多蓝为抗磁性有所不同，这种磁性行为在杂多蓝中非常少见。
2.采用[α-SiW_(10)Mo_2O_(40)]~(6-)作为建筑块，在常规条件下合成了四个杂多蓝配合物：H_2[α-SiW_(10)Mo_2O_(40)][Cu(PDA)_2·H_2O]_2(3),H_2[α-SiW_(10)Mo_2O_(40)][Cu(DEF)_3·H_2O][Cu(DEF)_2·2H_2O]·6H_2O (4),H_2[α-SiW_(10)Mo_2O_(40)][Cu(DMF)_3H_2O]_26H_2O (5),H_4[α-SiW_(10)Mo_2O_(40)]_2[CuK_2(DMF)_6][Na_(0.75)K_(3.25)(DMF)_6](6)[PDA=propanediamide, DEF=N,N-diethylformamide and DMF=N,N-dimethyl formamide]。
化合物3-6是分别是零维结构，一维链结构，二维格子结构和三维结构。合成与稳定性研究表明：1，通过选择不同的配体和调节原料铜的用量可以实现对化合物维度的调控；2，四个化合物具有良好的热稳定性，氧化稳定性和酸碱稳定性。磁性研究表明，这种两电子杂多蓝在室温下呈现出顺磁性，这与以往报道的两电子杂多蓝为抗磁性有所不同。
3.拓展了一个新的常规合成杂多蓝的策略，合成了四个化合物：[(CH_3)_4N]_4H_2[GeW_(10)Mo_2O_(40)]·7H2O (7)[(CH_3)_4N]_3H_3[GeMo~(VI)_(10)Mo~V_2O_(40)]·12H_2O (8)[C_3N_2H_5]_7H[P_2_(W16)Mo~V_2O_(62)]·20H)2O (9)[CH_3)_4N]_7H_7Na[P)2W_(12)Mo~(VI2)Mo~V_4O_(62)]_(1.5)·18H_2O (10)
化合物7和8分别为WVI-MoV混合和MoVI-MoV混合的Keggin结构。化合物9和10分别为两电子还原和四电子还原的WVI-MoV混合Dawson结构。通过电喷雾质谱监测反应过程中的溶液，监测到了带有草酸根的杂多蓝中间体，探明了此类杂多蓝的形成机理。磁性研究发现，化合物7在室温下为顺磁性，化合物8在室温下为抗磁性，而具有不同还原电子数的化合物9和10的室温XmT值非常接近。研究表明，通过调节还原Mo的个数和位置能够调节电子在杂多蓝表面的分布。鉴于此类固体化合物可能体现出类半导体性质，通过测定固体紫外漫发射光谱，推导出了化合物7-10的能级差。
Numerous heteropoly complexes (Pope's "Type I") can be reduced by addition of variousnumbers of electrons. The reduced systems of mixed valence (V, VI), which typically retainthe general structures of their oxidized parents and generally display dark blue color, comprisea large and potentially very important group of complexes generally known as the‘‘heteropoly blues”(HPBs). The excess electrons in blue species could be either localized ona certain metal center or delocalized as “extra” electrons over numerous metal centers, so thatthe electron density on outward oxygen atoms of POMs cluster are effectively modified.Consequently, such a modification could influence not only HPBs' coordination ability inassembling HPBs-based crystal frameworks, but also its electronic and molecular properties.Generally, heteropoly blues could behave as a special kind of solid materials with potentialfunction in magnetic, antiviral activity, photocatalytic and proton conductive properties.Several previous researches have demonstrated that heteropoly blues have unusualapplications in some areas.
Although heteropoly blues have considerable potential in application, in contrast withoxidative POMs, little attention has been paid to study the assembly and functionalization ofHPBs, which is mainly because that the instability and the difficulty in preparation of HPBsgreatly limit the research progress on HPBs. Therefore, it is of great interest to developapproaches to synthesize stable HPBs and study their electron properties.
In this paper, we develop a new strategy with general applicability to the synthesis ofHPBs. This strategy is not only applicable to the system of Keggin-type HPBs andDawson-type HPBs, but also applicable to the synthesis of MoVI-MoVmixed HPBs andWVI-MoVmixed HPBs. The electrospray ionization mass spectrometry (ESI-MS) was used toanalysis the assembly mechanism of this kind of HPBs. A detailed study of the magneticproperties was also carried out, which shows that the number of MoVand their location iscapable of adjusting the electron distribution in HPBs.
1．Utilizing heteropoly blue of [GeW_(10)Mo_2O_(40)]~(6-)as a building block, we synthesized twoheteropoly blue-based crystal architectures:H2[α-GeW_(10)Mo~V_2O_(40)][Cu(DMF)_3H_2O]_25H_2O (1)H_4[α-GeW_(10)Mo~V_2O_(40)]_2[CuK_2(DMF)_6][K_4(DMF)_6](2)
To our best knowledge, these two complexes represent the first example ofmultidimensional crystal frameworks directly using a heteropoly blue of mixedmolybdenum–tungsten as building block. In addition, we found that the different amount of the starting materials of Cu(II) could result in the structural assembly of2D and3D whileother experimental conditions remained.
2. Four heteropoly blue complexes constructed from Keggin-type heteropoly blue ofmolybdenum–tungsten clusters and Cu(II) ions as linkers：H_2[α-SiW_(10)Mo_2O_(40)][Cu(PDA)_2·H_2O]_2(3),H_2[α-SiW_(10)Mo_2O_(40)][Cu(DEF)_3·H_2O][Cu(DEF)_2·2H_2O]·6H_2O (4),H_2[α-SiW_(10)Mo_2O_(40)][Cu(DMF)_3H_2O]_26H_2O (5),H_4[α-SiW_(10)Mo_2O_(40)]_2[CuK_2(DMF)_6][Na_(0.75)K_(3.25)(DMF)_6](6)[PDA=propanediamide, DEF=N,N-diethylformamide and DMF=N,N-dimethyl formamide]. have been synthesized byconventional reactions and characterized by single-crystal X-ray diffraction, elementalanalysis, IR spectroscopy, thermogravimetry, X-ray powder diffraction (XRD) and UVspectra. The amount of Cu(II) and the nature of the ligand (DMF, DEF and PDA) can controlboth the linkage pattern of Cu(II) ions and the dimensionality of the frameworks; thisdemonstrates for the first time the possibility to assemble heteropoly blue architectures indifferent dimensionality ranging from zero-dimensional (0D) to one-dimensional (1D),two-dimensional (2D) and three-dimensional (3D). The magnetic investigation showed thatthe positive magnetic moment could be observed under room temperature, which should be ofunusual results in magnetochemistry of the two-electron reducted heteropoly blue. Thestability and formation conditions of the four compounds are also discussed.
3. A new strategy with general applicability to the synthesis of HPBs has been developedand four representative stable heteropoly blues (HPBs) were obtained：[(CH_3)_4N]_4H_2[GeW_(10)Mo_2O_(40)]·7H_2O (7)[(CH_3)_4N]_3H_3[GeMo~(VI)_(10)Mo~V_2O_(40)]·12H_2O (8)[C_3N_2H_5]_7H[P_2_(W16)Mo~V_2O_(62)]·20H)2O (9)[CH_3)_4N]_7H_7Na[P)2W_(12)Mo~(VI2)Mo~V_4O_(62)]_(1.5)·18H_2O (10)
The electrospray ionization mass spectrometry (ESI-MS) was used to analysis theassembly mechanism of this kind of HPBs. A detailed study of the magnetic properties wasalso carried out, which shows that the number of MoVand their location is capable ofadjusting the electron distribution in HPBs. Finally, the optical band gaps of1–4have alsobeen investigated in details to explore conductivity potentials.
本论文中，我们开发并拓展了一条合成稳定型杂多蓝的策略，合成了十个杂多蓝化合物并测定了它们的晶体结构。这个策略不仅适用于Keggin和Dawson结构杂多蓝的合成，而且适用于MoVI-MoV混合型杂多蓝和WVI-MoV混合型杂多蓝。采用电喷雾质谱监测反应过程中的溶液，成功地监测到了大量带有草酸根的杂多蓝中间体，探明了此类杂多蓝的形成过程是带有草酸根的[Mo_2~VO_4]~(2+)基团先嵌入到缺位多酸中，形成了带有草酸根的杂多蓝中间体，然后脱去草酸根形成目标杂多蓝。磁性研究发现，WVI-MoV混合型杂多蓝在室温下为顺磁性，而MoVI-MoV混合型杂多蓝在室温下为抗磁性，还原Mo的个数和位置也对这些杂多蓝的磁性产生了很大的影响。研究表明，通过调节还原Mo的个数和位置，能够实现对杂多蓝表面电子分布的调节。
1.采用[GeW_(10)Mo_2O_(40)]~(6-)作为建筑块，合成了两个杂多蓝配合物：H_2[α-GeW_(10)Mo~V_2O_(40)][Cu(DMF)_3H_2O]_25H_2O (1)H_4[α-GeW_(10)Mo~V_2O_(40)]_2[CuK_2(DMF)_6][K_4(DMF)_6](2)
这两个化合物代表了首例直接用W-Mo混合型杂多蓝作为建筑块，形成的基于杂多蓝的多维结构。研究表明，通过调节原料铜的用量能够实现对化合物维度的调控。磁性研究表明，这种两电子杂多蓝在室温下呈现出顺磁性。这与以往报道的两电子杂多蓝为抗磁性有所不同，这种磁性行为在杂多蓝中非常少见。
2.采用[α-SiW_(10)Mo_2O_(40)]~(6-)作为建筑块，在常规条件下合成了四个杂多蓝配合物：H_2[α-SiW_(10)Mo_2O_(40)][Cu(PDA)_2·H_2O]_2(3),H_2[α-SiW_(10)Mo_2O_(40)][Cu(DEF)_3·H_2O][Cu(DEF)_2·2H_2O]·6H_2O (4),H_2[α-SiW_(10)Mo_2O_(40)][Cu(DMF)_3H_2O]_26H_2O (5),H_4[α-SiW_(10)Mo_2O_(40)]_2[CuK_2(DMF)_6][Na_(0.75)K_(3.25)(DMF)_6](6)[PDA=propanediamide, DEF=N,N-diethylformamide and DMF=N,N-dimethyl formamide]。
化合物3-6是分别是零维结构，一维链结构，二维格子结构和三维结构。合成与稳定性研究表明：1，通过选择不同的配体和调节原料铜的用量可以实现对化合物维度的调控；2，四个化合物具有良好的热稳定性，氧化稳定性和酸碱稳定性。磁性研究表明，这种两电子杂多蓝在室温下呈现出顺磁性，这与以往报道的两电子杂多蓝为抗磁性有所不同。
3.拓展了一个新的常规合成杂多蓝的策略，合成了四个化合物：[(CH_3)_4N]_4H_2[GeW_(10)Mo_2O_(40)]·7H2O (7)[(CH_3)_4N]_3H_3[GeMo~(VI)_(10)Mo~V_2O_(40)]·12H_2O (8)[C_3N_2H_5]_7H[P_2_(W16)Mo~V_2O_(62)]·20H)2O (9)[CH_3)_4N]_7H_7Na[P)2W_(12)Mo~(VI2)Mo~V_4O_(62)]_(1.5)·18H_2O (10)
化合物7和8分别为WVI-MoV混合和MoVI-MoV混合的Keggin结构。化合物9和10分别为两电子还原和四电子还原的WVI-MoV混合Dawson结构。通过电喷雾质谱监测反应过程中的溶液，监测到了带有草酸根的杂多蓝中间体，探明了此类杂多蓝的形成机理。磁性研究发现，化合物7在室温下为顺磁性，化合物8在室温下为抗磁性，而具有不同还原电子数的化合物9和10的室温XmT值非常接近。研究表明，通过调节还原Mo的个数和位置能够调节电子在杂多蓝表面的分布。鉴于此类固体化合物可能体现出类半导体性质，通过测定固体紫外漫发射光谱，推导出了化合物7-10的能级差。
Numerous heteropoly complexes (Pope's "Type I") can be reduced by addition of variousnumbers of electrons. The reduced systems of mixed valence (V, VI), which typically retainthe general structures of their oxidized parents and generally display dark blue color, comprisea large and potentially very important group of complexes generally known as the‘‘heteropoly blues”(HPBs). The excess electrons in blue species could be either localized ona certain metal center or delocalized as “extra” electrons over numerous metal centers, so thatthe electron density on outward oxygen atoms of POMs cluster are effectively modified.Consequently, such a modification could influence not only HPBs' coordination ability inassembling HPBs-based crystal frameworks, but also its electronic and molecular properties.Generally, heteropoly blues could behave as a special kind of solid materials with potentialfunction in magnetic, antiviral activity, photocatalytic and proton conductive properties.Several previous researches have demonstrated that heteropoly blues have unusualapplications in some areas.
Although heteropoly blues have considerable potential in application, in contrast withoxidative POMs, little attention has been paid to study the assembly and functionalization ofHPBs, which is mainly because that the instability and the difficulty in preparation of HPBsgreatly limit the research progress on HPBs. Therefore, it is of great interest to developapproaches to synthesize stable HPBs and study their electron properties.
In this paper, we develop a new strategy with general applicability to the synthesis ofHPBs. This strategy is not only applicable to the system of Keggin-type HPBs andDawson-type HPBs, but also applicable to the synthesis of MoVI-MoVmixed HPBs andWVI-MoVmixed HPBs. The electrospray ionization mass spectrometry (ESI-MS) was used toanalysis the assembly mechanism of this kind of HPBs. A detailed study of the magneticproperties was also carried out, which shows that the number of MoVand their location iscapable of adjusting the electron distribution in HPBs.
1．Utilizing heteropoly blue of [GeW_(10)Mo_2O_(40)]~(6-)as a building block, we synthesized twoheteropoly blue-based crystal architectures:H2[α-GeW_(10)Mo~V_2O_(40)][Cu(DMF)_3H_2O]_25H_2O (1)H_4[α-GeW_(10)Mo~V_2O_(40)]_2[CuK_2(DMF)_6][K_4(DMF)_6](2)
To our best knowledge, these two complexes represent the first example ofmultidimensional crystal frameworks directly using a heteropoly blue of mixedmolybdenum–tungsten as building block. In addition, we found that the different amount of the starting materials of Cu(II) could result in the structural assembly of2D and3D whileother experimental conditions remained.
2. Four heteropoly blue complexes constructed from Keggin-type heteropoly blue ofmolybdenum–tungsten clusters and Cu(II) ions as linkers：H_2[α-SiW_(10)Mo_2O_(40)][Cu(PDA)_2·H_2O]_2(3),H_2[α-SiW_(10)Mo_2O_(40)][Cu(DEF)_3·H_2O][Cu(DEF)_2·2H_2O]·6H_2O (4),H_2[α-SiW_(10)Mo_2O_(40)][Cu(DMF)_3H_2O]_26H_2O (5),H_4[α-SiW_(10)Mo_2O_(40)]_2[CuK_2(DMF)_6][Na_(0.75)K_(3.25)(DMF)_6](6)[PDA=propanediamide, DEF=N,N-diethylformamide and DMF=N,N-dimethyl formamide]. have been synthesized byconventional reactions and characterized by single-crystal X-ray diffraction, elementalanalysis, IR spectroscopy, thermogravimetry, X-ray powder diffraction (XRD) and UVspectra. The amount of Cu(II) and the nature of the ligand (DMF, DEF and PDA) can controlboth the linkage pattern of Cu(II) ions and the dimensionality of the frameworks; thisdemonstrates for the first time the possibility to assemble heteropoly blue architectures indifferent dimensionality ranging from zero-dimensional (0D) to one-dimensional (1D),two-dimensional (2D) and three-dimensional (3D). The magnetic investigation showed thatthe positive magnetic moment could be observed under room temperature, which should be ofunusual results in magnetochemistry of the two-electron reducted heteropoly blue. Thestability and formation conditions of the four compounds are also discussed.
3. A new strategy with general applicability to the synthesis of HPBs has been developedand four representative stable heteropoly blues (HPBs) were obtained：[(CH_3)_4N]_4H_2[GeW_(10)Mo_2O_(40)]·7H_2O (7)[(CH_3)_4N]_3H_3[GeMo~(VI)_(10)Mo~V_2O_(40)]·12H_2O (8)[C_3N_2H_5]_7H[P_2_(W16)Mo~V_2O_(62)]·20H)2O (9)[CH_3)_4N]_7H_7Na[P)2W_(12)Mo~(VI2)Mo~V_4O_(62)]_(1.5)·18H_2O (10)
The electrospray ionization mass spectrometry (ESI-MS) was used to analysis theassembly mechanism of this kind of HPBs. A detailed study of the magnetic properties wasalso carried out, which shows that the number of MoVand their location is capable ofadjusting the electron distribution in HPBs. Finally, the optical band gaps of1–4have alsobeen investigated in details to explore conductivity potentials.
引文
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