Physical/Materials Chemistry Division, National Chemical Laboratory, Dr. Homi Bhabha Road, Pune, 411008, India.
Inorg Chem. 2011 May 2;50(9):3855-65. doi: 10.1021/ic1017246. Epub 2011 Mar 25.
Four new partially fluorinated metal organic frameworks (HF-MOFs) have been synthesized under different solvothermal conditions (H(2)O or dimethylformamide (DMF)) from transition metal cations [Co(2+) and Mn(2+)], 3-methyl pyridine (3-mepy) and 4,4'-(hexafluoroisopropylidene) bis(benzoic acid) (C(17)H(10)F(6)O(4), H(2)hfbba), to determine the influence of reaction conditions on the formation of MOFs. This family of materials displays a striking degree of structural similarity depending on the solvent of synthesis. HF-MOFs synthesized from H(2)O [Co-HFMOF-W, Co(hfbba)(3-mepy)(H(2)O) and Mn-HFMOF-W, Mn(hfbba)(3-mepy)(H(2)O)] contain three-dimensional connectivity whereas HF-MOFs synthesized from DMF Co-HFMOF-D, [Co(2)(hfbba)(2)(3-mepy)(2)]·(DMF)(3) and Mn-HFMOF-D, [Mn(2)(hfbba)(2)(3-mepy)]·(H(2)O) are two-dimensional in nature. Co-HFMOF-W and Mn-HFMOF-W are iso-structural polymeric materials. Thermal gravimetric analysis performed on as-synthesized HF-MOFs revealed that these compounds have high thermal stability (∼350 °C). The continuous decrease of the χT product with decreasing T for Co-HFMOF-D and Co-HFMOF-W respectively indicates the presence of antiferromagnetic exchange interaction between two Co(2+) (S = 3/2) metal centers within a cluster.
四种新的部分氟化金属有机骨架（HF-MOFs）在不同的溶剂热条件下（H2O 或二甲基甲酰胺（DMF））由过渡金属阳离子[Co2+和 Mn2+]、3-甲基吡啶（3-mepy）和 4,4'-(六氟亚异丙基)双（苯甲酸）（C17H10F6O4，H2hfbba）合成，以确定反应条件对 MOFs 形成的影响。这一系列材料显示出高度的结构相似性，取决于合成溶剂。由 H2O 合成的 HF-MOFs[Co-HFMOF-W、Co（hfbba）（3-mepy）（H2O）和 Mn-HFMOF-W、Mn（hfbba）（3-mepy）（H2O）]包含三维连接，而由 DMF 合成的 HF-MOFs Co-HFMOF-D、[Co2（hfbba）（2）（3-mepy）（2）]·（DMF）（3）和 Mn-HFMOF-D、[Mn2（hfbba）（2）（3-mepy）]·（H2O）是二维的。Co-HFMOF-W 和 Mn-HFMOF-W 是同构聚合物材料。对合成的 HF-MOFs 进行的热重分析表明，这些化合物具有很高的热稳定性（约 350°C）。Co-HFMOF-D 和 Co-HFMOF-W 的 χT 产物随温度的降低连续下降，分别表明在一个簇中两个 Co2+（S = 3/2）金属中心之间存在反铁磁交换相互作用。
