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Assembly of Hybrid Organic-Organometallic Materials through Mechanochemical Acid-Base Reactions

机译:通过机械化学酸碱反应组装有机-有机金属杂化材料

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摘要

Manual grinding of the organometallic complex[Fe(eta~5-C_5H_4COOH)_2]with a number of solid bases,namely 1,4-diazabicyclo[2.2.2]octane,C_6H_12N_2,1,4-phenylenediamine,p-(NH_2)_2C_6H_4,pi perazine,HN(C_2H_4)_2NH,trans-1,4-cy-clohexanediamine,p-(NH_2)_2C_6H_10,and guanidinium carbonate[(NH_2)_3C]_2[CO_3],generates quantitatively the corresponding adducts,[HC_6H_12N_2][Fe(eta~5C_5H_4-COOH)(eta~5-C_5H_4COO)](1),[HC_6H_8N_2]-[Fe(eta~5-C_5H_4COOH)(eta~5C_5H_4COO)](2),[H_2C_4H_10N_2][Fe(eta~5-C_5H_4COO)_2](3),[H_2C_6H_14N_2][Fe(eta~5-C_5H_4COO)_2].2H_2O,(4.2H_2O),and[C(NH_2)_3]_2[Fe(eta~5-C_5H_4COO)_2].2H_2O,(5.2H_2O),respectively.Crystallization from methanol in the presence of seeds of the ground sample allows the growth of single crystals of these adducts;therefore we were able to determine the structures of the adducts by single-crystal X-ray diffraction.This information was used in turn to identify and characterize the polycrystalline materials obtained by the grinding process.In the case of[HC_6N_2H_12][Fe(eta~5-C_5H_4COOH)(eta~5-C_5H_4COO)](1),the base can be removed by mild treatment regenerating the starting dicarboxylic acid,which in all other cases decomposition is observed.The solid-solid processes described herein imply molecular diffusion through the lattice,breaking and reassembling of hydrogen-bonded networks,and proton transfer from acid to base.
机译:手动研磨带有许多固体碱的有机金属配合物[Fe(eta〜5-C_5H_4COOH)_2],即1,4-二氮杂双环[2.2.2]辛烷,C_6H_12N_2,1,4-苯二胺,p-(NH_2) _2C_6H_4,哌嗪,HN(C_2H_4)_2NH,反式-1,4-环己二胺,对-(NH_2)_2C_6H_10和碳酸胍[(NH_2)_3C] _2 [CO_3]定量生成相应的加合物[HC_6H_12N_2 ] [Fe(eta〜5C_5H_4-COOH)(eta〜5-C_5H_4COO)] [1),[HC_6H_8N_2]-[Fe(eta〜5-C_5H_4COOH)(eta〜5C_5H_4COO)] [2),[H_2C_4H_10N_2] [Fe (eta〜5-C_5H_4COO)_2](3),[H_2C_6H_14N_2] [Fe(eta〜5-C_5H_4COO)_2] .2H_2O,(4.2H_2O)和[C(NH_2)_3] _2 [Fe(eta〜5) -C_5H_4COO)_2] .2H_2O,(5.2H_2O)。在存在地面样品种子的情况下从甲醇中结晶可以使这些加合物形成单晶;因此,我们能够通过单个晶体确定加合物的结构晶体X射线衍射。该信息依次用于鉴定和表征通过研磨过程获得的多晶材料。 [HC_6N_2H_12] [Fe(eta〜5-C_5H_4COOH)(eta〜5-C_5H_4COO)](1)的e中,可通过温和处理将起始二元羧酸再生除去碱,在所有其他情况下均会观察到分解。本文所述的固-固过程暗示分子通过晶格扩散,氢键网络的断裂和重新组装以及质子从酸到碱的转移。

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