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首页> 外文期刊>RSC Advances >Low pH constructed Co(ii) and Ni(ii) 1D coordination polymers based on Cα-substituted analogues of zoledronic acid: structural characterization, and spectroscopic and magnetic properties
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Low pH constructed Co(ii) and Ni(ii) 1D coordination polymers based on Cα-substituted analogues of zoledronic acid: structural characterization, and spectroscopic and magnetic properties

机译：基于唑来膦酸的Cα取代类似物的低pH构造的Co（ii）和Ni（ii）一维配位聚合物：结构表征，光谱和磁性

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摘要

Three novel coordination compounds based on α,α-disubstituted analogues of zoledronic acid with a cyclopropane (cpp) or cyclobutane (cbt) ring on the C _(α) carbon, isomorphous [Co(H _(2) cppZol)(H _(2) O)]·H _(2) O ( 1a ), [Ni(H _(2) cppZol)(H _(2) O)]·H _(2) O ( 1b ) and [Co(H _(2) cbtZol)(H _(2) O)]·H _(2) O ( 2a ), were synthesized under hydrothermal conditions at low pH. Single-crystal X-ray diffraction analysis revealed that all the compounds had a 1D double zig–zag chain architecture with an 8 + 8 ring motif formed by alternately arranged symmetrical (–O–P–O–) _(2) bridges linking equivalent octahedral metal centres. Both the ligand coordination mode and chain architecture displayed by 1a , 1b and 2a are unique among 1D [M(H _(2) L)(H _(2) O) _( x ) ]· y H _(2) O coordination polymers based on nitrogen-containing bisphosphonates reported so far. All the compounds exhibit similar decomposition pathways upon heating with thermal stabilities decreasing in the order 1b > 1a > 2a . The IR spectra revealed that lattice water release above 227, 178 and 97 °C, respectively, does not change the chain architecture leaving them intact up to ca. 320, 280 and 240 °C. Magnetic behaviour investigations indicated that 1a , 2a and 1b exhibit weak alternating antiferromagnetic–ferromagnetic exchange interactions propagated between the magnetic centres through double (–O–P–O–) _(2) bridges. The boundary between antiferro- and ferromagnetic couplings for the Co–O?O–Co angle in 1a and 2a was estimated to be ca. 80°. This value is also applicable for recently reported [M _(3) (HL) _(2) (H _(2) O) _(6) ]·6H _(2) O (M = Co, Ni) complexes based on α,α-disubstituted analogues of zoledronic acid and can be used to the explain magnetic behaviour of 1b .
机译：三种新颖的配位化合物，它们基于唑来膦酸的α，α-二取代类似物，并在C _（α）碳上同构[Co（H _（2）cppZol）（H _）形成环丙烷（cpp）或环丁烷（cbt）环（2）O）]·H _（2）O（1a），[Ni（H _（2）cppZol）（H _（2）O）]·H _（2）O（1b）和[Co（在低pH的水热条件下合成了H_（2）cbtZol）（H_（2）O）] H_（2）O（2a）。单晶X射线衍射分析表明，所有化合物均具有一维双曲折链结构，具有交替排列的对称（–O–P–O–）_（2）桥连接等价物而形成的8 + 8环基序八面体金属中心。在1D [M（H _（2）L）（H _（2）O）_（x）] y H _（2）O中，由1a，1b和2a显示的配体配位模式和链结构均是唯一的。迄今为止，已经报道了基于含氮双膦酸酯的配位聚合物。所有化合物在加热时均表现出相似的分解途径，热稳定性按1b> 1a> 2a的顺序降低。红外光谱表明，分别在227、178和97°C以上释放的晶格水不会改变链的结构，从而使它们完整地保留至大约120℃。 320、280和240°C。磁行为研究表明1a，2a和1b表现出通过双（–O–P–O–）_（2）桥在磁中心之间传播的弱交替反铁磁-铁磁交换相互作用。估计1a和2a中Co–O→O–Co角的反铁磁耦合和铁磁耦合之间的边界约为。 80°。此值也适用于基于[M _（3）（HL）_（2）（H _（2）O）_（6）]·6H（2）O（M = Co，Ni）络合物在唑来膦酸的α，α-二取代类似物上的合成，可用于解释1b的磁性。

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