Making an order: the concerted alignment of [MOF5]2- (M = Nb and Ta) dipolar anions in one-dimensional coordination chains sustained by tris(3,4,5-trimethyl-1H-pyrazole)copper(II).
Making an order: the concerted alignment of [MOF5]2- (M = Nb and Ta) dipolar anions in one-dimensional coordination chains sustained by tris(3,4,5-trimethyl-1H-pyrazole)copper(II).
复制标题
下订单：三(3,4,5-三甲基-1H-吡唑)铜(II)维持的一维配位链中[MOF5]2-（M = Nb和Ta）偶极阴离子的协同排列
DOI：
10.1107/s2053229618009853
复制
发表时间：
2018
期刊：
影响因子：
--
通讯作者：
K. V. Domasevitch
中科院分区：
文献类型：
--
作者：
A. V. Sharko;O. Erhart;H. Krautscheid;K. V. Domasevitch
氟氧化物阴离子[MOF5] 2 −（M = Nb和Ta）中固有的电子畸变为开发新的极性二次谐波产生材料、压电材料、热电材料和铁电材料提供了极性分子排列的起源。将这种方法扩展到金属有机聚合物领域仍然是一个挑战，而对[MOF5] 2 −单元的环境控制不足会导致它们的取向无序和极性丧失。链状聚[[三甲基]吡啶]的结构（3，4，5-三甲基-1H-吡唑-κ N2）铜（II）]-μ-氧化-[四氟铌（V）]-μ-氟代]，[CuNbF5O（C6H10N2）3] n，（I）及其同构五氟氧化钽酸盐（V）类似物，链状聚[[三（3，4，5-三甲基-1H-吡唑-κ N2）铜（II）]-μ-氧化-[四氟钽（V）]-μ-氟代]，[CuTaF5O（C6H10N2）3] n，（II），是[MOF5] 2 −（M = Nb和Ta）在一维配位链中严格取向顺序的第一个例子。准确区分阴离子的一个方向的主要因素是[MOF5] 2 −与固有的无中心CuL32+平台的强烈和形状选择性的多重相互作用，具有一组两个配位和三个N-H F氢键。在（I）和（II）中，Cu~（2+）离子表现出由三个吡唑N原子和氧化物O原子形成的扭曲四方锥五重配位，定义了赤道平面，阴离子桥连F原子（相对于M-O键为反式）位于顶端位置。无机桥连接CuL32+部分成极性锯齿形链;通过单个链的反平行排列消除结构的体极性。这些链通过C-H <$F氢键和有机配体的非常弱的C-H <$π相互作用进一步连接。
Electronic distortions, which are inherent in the oxide fluoride anions [MOF5]2− (M = Nb and Ta), provide an origin of polar molecular arrangements for the development of new polar second-harmonic-generating, piezo-, pyro- and ferroelectric materials. It is still a challenge to expand this approach to the realm of metal–organic polymers, while insufficient control over the environment of the [MOF5]2− units results in their orientational disorder and loss of polarity. The structures of catena-poly[[tris(3,4,5-trimethyl-1H-pyrazole-κN2)copper(II)]-μ-oxido-[tetrafluoridoniobium(V)]-μ-fluorido], [CuNbF5O(C6H10N2)3]n, (I), and its isostructural pentafluoridooxidotantalate(V) analogue, catena-poly[[tris(3,4,5-trimethyl-1H-pyrazole-κN2)copper(II)]-μ-oxido-[tetrafluoridotantalum(V)]-μ-fluorido], [CuTaF5O(C6H10N2)3]n, (II), are the first examples of the strict orientational order of [MOF5]2− (M = Nb and Ta) in one-dimensional coordination chains. A primary factor for the exact discrimination of one orientation of the anion over the other is strong and shape-selective multiple interactions of [MOF5]2− with the inherently acentric CuL32+ platform, with a set of two coordination and three N—H⋯F hydrogen bonds. In (I) and (II), the Cu2+ ions exhibit distorted square-pyramidal fivefold coordination formed by three pyrazole N atoms and the oxide O atom, defining the equatorial plane, and the anionic bridging F atom (which is trans with respect to the M—O bond) residing in the apical position. The inorganic bridges connect CuL32+ moieties into polar zigzag chains; the bulk polarity of the structure is eliminated by an antiparallel alignment of the individual chains. These chains are further connected through C—H⋯F hydrogen bonding and very weak C—H⋯π interactions of the organic ligands.
登录
查看更多内容
双(甘氨酸)五氟氧化铌酸(V)和双(β-丙氨酸)五氟氧化铌酸(V)二水合物中[NbOF5]2-复合阴离子的紊乱。
DOI：
--
发表时间：
2008
期刊：
Acta Crystallographica Section C: Crystal Structure Communications
影响因子：
--
作者：
A. Gerasimenko;M. A. Pushilin;R. Davidovich
通讯作者：
R. Davidovich
[VOF 5 ] 2- 和 [NbOF 5 ] 2- 极性单元在链中的取向顺序
DOI：
--
发表时间：
2012
期刊：
影响因子：
--
作者：
R. Gautier;Martin D. Donakowski;K. Poeppelmeier
通讯作者：
K. Poeppelmeier
影响因子：
3.8
作者：
Gautier, Romain;Poeppelmeier, Kenneth R.
通讯作者：
Poeppelmeier, Kenneth R.
二价金属氟铌酸盐和氟钽酸盐的合成及性能
DOI：
--
发表时间：
1972
期刊：
影响因子：
--
作者：
R. Davidovich;T. F. Levchishina;T. Kaidalova;V. Sergienko
通讯作者：
V. Sergienko
晶体中内部扭转运动与整体分子运动的相关性
DOI：
10.1107/s0108768198003243
发表时间：
1998
期刊：
Acta Crystallographica Section B-structural Science
影响因子：
--
作者：
V. Schomaker;K. Trueblood
通讯作者：
K. Trueblood