3-(4-Methylthiophenyl)acetylacetone – ups and downs of flexibility in the synthesis of mixed metal–organic frameworks. Ditopic bridging of hard and soft cations and site-specific desolvation,CrystEngComm

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3-(4-Methylthiophenyl)acetylacetone – ups and downs of flexibility in the synthesis of mixed metal–organic frameworks. Ditopic bridging of hard and soft cations and site-specific desolvation
CrystEngComm ( IF 2.6 ) Pub Date : 2020/01/06 , DOI: 10.1039/c9ce01932d
Hans Gildenast _{1,

2,

3,

4} , Stephanie Nölke _{1,

2,

3,

4} , Ulli Englert _{1,

2,

3,

4,

5}

Affiliation

3-(4-Methylthiophenyl)pentane-2,4-dione (HacacSMePh) combines a Pearson-hard β-diketone and a soft thioether group in its periphery; after deprotonation, it may act as a heterobifunctional linker between metal cations. Coordination of the β-diketo site to trivalent cations afforded a series of M(acacSMePh)₃ metal complexes with dangling thioether moieties. Crosslinking of the mononuclear M(acacSMePh)₃ building units via the SMe functionalities with Ag^I cations resulted in mixed metal–organic frameworks (MMOFs). All bimetallic networks with M^III = Co, Al, Cr, Fe, Ga are isostructural. Statistical occupancy of the M^III site by two different cations may be possible and has been proven for Al^III and Ga^III. The MMOFs are semiporous and contain two co-crystallized chloroform molecules in the asymmetric unit. One of these CHCl₃ molecules may be partially removed while maintaining the structural integrity of the network.

中文翻译：

3-（4-甲基硫代苯基）乙酰丙酮–混合金属-有机骨架合成中的弹性起伏。硬和软阳离子的异位桥接和特定位置的去溶剂化

3-（4-甲基硫代苯基）戊烷-2,4-二酮（HacacSMePh）在其外围结合了一个Pearson-硬β-二酮和一个软硫醚基团; 去质子化后，它可以充当金属阳离子之间的异双功能连接基。β-二酮位点与三价阳离子的配位提供了一系列带有悬空硫醚部分的M（acacSMePh）₃金属配合物。单核M（acacSMePh）₃建筑单元通过SMe功能与Ag ^I阳离子的交联导致金属-有机混合框架（MMOF）。M ^III = Co，Al，Cr，Fe，Ga的所有双金属网络都是同构的。M ^III的统计占用率由两个不同的阳离子引起的位点可能是可能的，并已被Al ^III和Ga ^III证实。MMOF是半多孔的，在不对称单元中包含两个共结晶的氯仿分子。这些CHCl ₃分子之一可以部分除去，同时保持网络的结构完整性。

更新日期：2020-02-13

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