Exploring and expanding the Fe-terephthalate metal-organic framework phase space by coordination and oxidation modulation.
Exploring and expanding the Fe-terephthalate metal-organic framework phase space by coordination and oxidation modulation.
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DOI：
10.1039/d1mh01663f
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发表时间：
2021-11-29
影响因子：
13.3
通讯作者：
Forgan RS
中科院分区：
文献类型：
--
作者：
Bara D;Meekel EG;Pakamorė I;Wilson C;Ling S;Forgan RS
相纯金属-有机框架（MOF）-通过有机连接体连接的金属簇的网络固体-的合成通常由于从一种金属-配体组合形成多个不同相的可能性而复杂化。例如，迄今为止报道了至少六种对苯二甲酸铁MOF，在文献中有许多仅基于衍射数据错误分配相的例子。在这里，我们表明，调制的自组装可以用来影响自组装的Fe-terephthalate MOFs的动力学。我们全面评估了添加配位调节剂和pH调节剂对合成结果的影响，并探讨了Fe前体氧化态（氧化调节）的影响以及抗衡阴离子对形成的相的作用。在这样做的过程中，我们揭示了这个相系统的热力学景观，揭示了调制的机制，提供了强大的路线相纯材料，通常作为单晶，并引入两个新的对苯二甲酸铁MOFs已经复杂的系统。这些结果突出了调制自组装的潜力，为已经得到重要研究的系统带来精确控制和新的结构多样性。Fe-terephthalate金属有机框架的调制自组装允许对相形成进行精细控制，提供对动力学和热力学景观的洞察，以及在已经充分研究的复杂系统中发现新材料。
The synthesis of phase pure metal–organic frameworks (MOFs) – network solids of metal clusters connected by organic linkers – is often complicated by the possibility of forming multiple diverse phases from one metal–ligand combination. For example, there are at least six Fe-terephthalate MOFs reported to date, with many examples in the literature of erroneous assignment of phase based on diffraction data alone. Herein, we show that modulated self-assembly can be used to influence the kinetics of self-assembly of Fe-terephthalate MOFs. We comprehensively assess the effect of addition of both coordinating modulators and pH modulators on the outcome of syntheses, as well as probing the influence of the oxidation state of the Fe precursor (oxidation modulation) and the role of the counteranion on the phase(s) formed. In doing so, we shed light on the thermodynamic landscape of this phase system, uncover mechanistics of modulation, provide robust routes to phase pure materials, often as single crystals, and introduce two new Fe-terephthalate MOFs to an already complex system. The results highlight the potential of modulated self-assembly to bring precision control and new structural diversity to systems that have already received significant study. Modulated self-assembly of Fe-terephthalate metal–organic frameworks allows fine control over phase formation, offers insight into kinetic and thermodynamic landscapes, and the discovery of novel materials in an already well-studied complex system.
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影响因子：
4.6
作者：
Goesten, Maarten G.;Magusin, Pieter C. M. M.;Gascon, Jorge
通讯作者：
Gascon, Jorge
影响因子：
4.6
作者：
Bauer, Sebastian;Serre, Christian;Stock, Norbert
通讯作者：
Stock, Norbert
影响因子：
3.1
作者：
Gia-Thanh Vuong;Minh-Hao Pham;Trong-On Do
通讯作者：
Trong-On Do
影响因子：
6.7
作者：
Choi, Sora;Cha, Wonhee;Oh, Moonhyun
通讯作者：
Oh, Moonhyun
用于磁共振/光学成像和靶向药物输送的智能多功能纳米级金属有机框架的可控合成
影响因子：
9.5
作者：
Gao, Xuechuan;Zhai, Manjue;Damirin, Alatangaole
通讯作者：
Damirin, Alatangaole