Formation of Coordination Polymers or Discrete Adducts via Reactions of Gadolinium(III)–Copper(II) 15-Metallacrown-5 Complexes with Polycarboxylates: Synthesis, Structures and Magnetic Properties

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• 作者：Anna V. Pavlishchuk ; Sergey V. Kolotilov ; Matthias Zeller ; Laurence K. Thompson ; Anthony W. Addison
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：February 3, 2014
• 年：2014
• 卷：53
• 期：3
• 页码：1320-1330
• 全文大小：543K
• ISSN：1520-510X

文摘

Reactions of the copper(II)鈥揼adolinium(III) 15-metallacrown-5 complex [GdCub>5b>(Glyha)b>5b>(NOb>3b>)b>2b>(Hb>2b>O)b>6b>](NOb>3b>) (Glyha^{2鈥?/sup> = dianion of glycinehydroxamic acid) with different di/tricarboxylates (1,3-phthalate, 1,4-phthalate, biphenyl-4,4鈥?dicarboxylate, citrate) resulted in formation of different types of products: {[(GdCub>5b>(Glyha)b>5b>(Hb>2b>O)b>2b>)(GdCub>5b>(Glyha)b>5b>(Hb>2b>O)b>3b>)(1,3-bdc)b>3b>]路16Hb>2b>O}b>nb> (<b>1b>), {[(GdCub>5b>(Glyha)b>5b>(Hb>2b>O)b>3b>)b>2b>(1,4-bdc)b>2b>](1,4-bdc)路8Hb>2b>O}b>nb> (<b>2b>), {[(GdCub>5b>(Glyha)b>5b>(Hb>2b>O)b>4b>)b>2b>(1,4-bdc)b>3b>]路8Hb>2b>O}b>nb> (<b>3b>), [GdCub>5b>(Glyha)b>5b>(Citr)(Hb>2b>O)b>4b>]路7Hb>2b>O (<b>4b>), {[GdCub>5b>(Glyha)b>5b>(Hb>2b>O)b>5b>](渭b>2b>-COb>3b>)[Cu(Fgg)]}路7Hb>2b>O (<b>5b>) and [Cu(Gly)b>2b>(Hb>2b>O)]b>nb> (<b>6b>) (where bdc2鈥?/sup> is the corresponding phthalate (benzenedicarboxylate), Citr3鈥?/sup> is citrate, Fgg3鈥?/sup> is the trianion of [(N-formylaminoacetyl)amino]acetic acid and Gly鈥?/sup> is glycinate). Complexes <b>1b>鈥?b>5b> contain the [GdCub>5b>(Glyha)b>5b>]3+ cation. Complexes <b>2b> and <b>3b> possess the same composition but differ by the mode of p-phthalate coordination to the [GdCub>5b>(Glyha)b>5b>]3+ unit. In compounds <b>1b>鈥?b>3b>, metallacrown cations are linked by the corresponding phthalates in 1D, 1D and 2D polymers, respectively, whereas <b>4b> and <b>5b> are discrete molecules. Compound <b>5b> is the product of a multistep reaction, which finally involves atmospheric COb>2b> capture. Hydrolysis of hydroxamate in this reaction is confirmed by isolation of a mononuclear copper glycine complex 6. The 蠂b>Mb>T vs T data for <b>1b> were fitted using a model based on the Hamiltonian <b>膜b> (GdCub>5b>) = 鈭?Jb>1b>(Sb>1b> 脳 Sb>Gdb> + Sb>2b> 脳 Sb>Gdb> + Sb>3b> 脳 Sb>Gdb> + Sb>4b> 脳 Sb>Gdb> + Sb>5b> 脳 Sb>Gdb>) 鈥?2Jb>2b>(Sb>1b> 脳 Sb>2b> + Sb>2b> 脳 Sb>3b> + Sb>3b> 脳 Sb>4b> + Sb>4b> 脳 Sb>1b> + Sb>5b> 脳 Sb>1b>. The best fit corresponded to Jb>1b> = +0.60(2) cm鈥?, Jb>2b> = 鈭?1.0(5) cm鈥? and zJ鈥?/i> = 鈭?.035(4) cm鈥?. Complex <b>1b> is the first example of a 15-metallacrown-5 system, for which numerical values of exchange parameters have been reported. The isotherm for methanol absorption by compound <b>1b> at 293 K was typical for microporous sorbents, whereas ethanol sorption was negligibly small.}