Modulating crystal packing and magnetic properties of nitroxide free radicals by halogen bonding

Pang X.; Zhao X.R.; Wang H.; Sun H.-L.; Jin W.J.

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Modulating crystal packing and magnetic properties of nitroxide free radicals by halogen bonding

机译：通过卤素键调节氮氧化物自由基的晶体堆积和磁性

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By combining a halogen bonding donor of 1,4-diiodotetrafluorobenzene (1,4-DITFB) or 1,2-diiodotetrafluorobenzene (1,2-DITFB) with 4-benzoyloxy-2,2,6,6-tetramethyl-piperidine-1-oxy free radical (BTEMPO, 1), two novel cocrystals, BTEMPO·1,4-DITFB (2) and BTEMPO·2(1,2-DITFB) (3), featuring a one-dimensional (1D) zigzag chain and a cyclic tetrameric structure, respectively, were constructed via halogen bonding. Furthermore, by tuning the halogen bonding between BTEMPO and halogen bonding donors, the packing modes of organic free radicals in both 2 and 3 are successfully modulated to result in side-by-side 1D mode in 2 and head-to-head dimer manner in 3. Magnetic studies reveal that in all compounds the organic radicals are antiferromagnetically coupled; however, the magnetic coupling in 2 and 3 is stronger than that in 1, indicating the modulating effect of halogen bonding on magnetic properties that are further confirmed by quantum chemistry calculations.

机译：通过将1,4-二碘四氟苯（1,4-DITFB）或1,2-二碘四氟苯（1,2-DITFB）的卤素键供体与4-苯甲酰氧基-2,2,6,6-四甲基-哌啶-1结合-氧自由基（BTEMPO，1），两个新的共晶体BTEMPO·1,4-DITFB（2）和BTEMPO·2（1,2-DITFB）（3），具有一维（1D）曲折链和通过卤素键分别构建环状四聚体结构。此外，通过调节BTEMPO和卤素键供体之间的卤素键，成功地调节了2和3中有机自由基的堆积模式，从而以2和头对头二聚体的方式并排形成一维模式。 3.磁性研究表明，在所有化合物中，有机基团都是反铁磁耦合的;然而，在2和3中的磁耦合强于在1中的磁耦合，这表明卤素键对磁性能的调节作用已被量子化学计算进一步证实。

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《Crystal growth & design》 |2013年第8期|共7页
作者
Pang X.; Zhao X.R.; Wang H.; Sun H.-L.; Jin W.J.;
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正文语种 eng
中图分类 54.9;
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Modulating crystal packing; magnetic properties; halogen bonding;

机译：调节晶体堆积;磁性;卤素键;

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1. Modulating crystal packing and magnetic properties of nitroxide free radicals by halogen bonding [J] . Pang X., Zhao X.R., Wang H., Crystal growth & design . 2013,第8期

机译：通过卤素键调节氮氧化物自由基的晶体堆积和磁性
2. Synthesis, structures, and magnetic properties of a series of lanthanum(III) and gadolinium(III) complexes with chelating benzimidazole-substituted nitronyl nitroxide free radicals. Evidence for antiferromagnetic Gd-III-radical interactions [J] . Lescop C., Belorizky E., Luneau D., Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics . 2002,第13期

机译：一系列具有螯合苯并咪唑取代的硝酰基硝基氧自由基的镧（III）和g（III）配合物的合成，结构和磁性能。反铁磁Gd-III-自由基相互作用的证据
3. Crystal packing effects on the magnetic slow relaxation of TB(III)-nitronyl nitroxide radical cyclic dinuclear clusters [J] . Pointillart F., Bernot K., Poneti G., Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics . 2012,第22期

机译：晶体堆积对TB（III）-亚硝酰基硝基氧自由基环状双核团簇的磁慢弛豫的影响
4. A hydroxyl-containing nitronyl nitroxide radical and its Dy (III) complex: Structure and magnetic properties [C] . Peng Hu, Fengping Xiao, Xiange Wu, International Conference on Materials Science, Resource and Environmental Engineering . 2017

机译：含羟基的氮氮氧化物基团及其DY（III）复合物：结构和磁性
5. "Living"/controlled radical polymerization: From emulsion atom transfer radical polymerization to the synthesis of new nitroxides for stable free radical polymerization. [D] . Chan-Seng, Delphine. 2007

机译：“活性” /受控自由基聚合：从乳液原子转移自由基聚合到合成新的氮氧化物以稳定自由基聚合。
6. Halogen and Hydrogen Bonding Interplay in the Crystal Packing of Halometallocenes [O] . Karina Shimizu, João Ferreira da Silva 2018

机译：卤金属茂晶体包装中的卤素和氢键相互作用
7. Synthesis, crystal structures, and magnetic properties of nitroxide radical-coordinated manganese(II) and cobalt(II) complexes [O] . Yan-Li Gao, Cuifang Tian, Pingqiang Gao, 2021

机译：硝基氧化物自由基协调锰（II）和钴（II）配合物的合成，晶体结构和磁性。
8. EPR (Electron Paramagnetic Resonance) Observation of Nitroxide Free Radicals during Thermal Decomposition of 2,4,6-Trinitrotoluene and Related Compounds [R] . McKinney, T. M., Warren, L. F., Goldberg, I. B., 1986

机译：EpR（电子顺磁共振）观察2,4,6-三硝基甲苯及相关化合物热分解过程中的氮氧自由基

Modulating crystal packing and magnetic properties of nitroxide free radicals by halogen bonding

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