• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Crystal growth & design >Significant Role of Supramolecular Interactions on Conformational Modulation of Flexible Organic Cation Receptors in a Metal-Bis(dithiolate) Coordination Complex Matrix
【24h】

Significant Role of Supramolecular Interactions on Conformational Modulation of Flexible Organic Cation Receptors in a Metal-Bis(dithiolate) Coordination Complex Matrix

机译：超分子相互作用对金属双（二硫代）配合物基质中柔性有机阳离子受体的构象调制的重要作用。

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

A series of new ion-pair complexes [Bz,R-BzBimy](2)[M(mnt)(2)] {[Bz,R-BzBimy](+) = 1-benzy1-3-(4-R-benzyl)benzimidazolium; M = Cu, R = H (1a), NO2 (1b) and Br (1c); M = Ni, R = H (2a), NO2 (2b) and Br (2c) and mnt(2-) = maleonitriledithiolate} have been prepared and characterized by routine spectral analyses including single crystal X-ray crystallography. Due to the flexible nature of aryl groups (-CH2-Ar) in benzimidazolium cations, [Bz,H-BzBimy](1+) and [Bz,NO2-BzBimy](1+) if of compounds [Bz,H-BzBimy]BF4 (a) and [Bz,NO2-BzBimy]BF4 (b), respectively, the conformational change of the aryl groups have been observed in their respective metal-dithiolate compounds 1a, 1b, 2a, and 2b. However, no change in orientation of the associated phenyl groups is observed between the cationic organic receptor [Bz,Br-BzBimy](1+) of compound [Bz,Br-BzBimy](2)BF4 (c) and that in resulting ion pair compounds 1c and 2c. Fluxional behavior of the aryl groups in the cationic organic receptor (benzimidazolium moiety, [Bz,R-BzBimy](+)), when it is ion-paired with different counteranions, e.g., tetrafluoroborate (BF4-) and [M(mnt)(2)](2-), is mainly dependent on the supramolecular interactions (for example, S center dot center dot center dot H, N center dot center dot center dot H, O center dot center dot center dot H, Br center dot center dot center dot Br, etc., weak contacts) between the relevant cation and anion. The p-substituents (H, NO, and Br) of one of the phenyl rings in benzimidazolium moiety (cationic part) are found to be responsible for the structural diversities, observed in the crystal structures of metal-dithiolate ion pair compounds 1a, 1b, 1c, 2a, 2h, and 2c. In this context, it is worth mentioning that the nickel containing ion pair compounds 2a, 2b, and 2c are isomorphous with corresponding copper analogues 1a, 1b, and 1c. The near-IR absorbance bands at around 1210 nm, observed for the copper compounds (1a-1c), have been attributed to the charge transfer from the copper dithiolate anion [Cu(mnt)(2)](2-) to the benzimidazolium cation [Bz,R-BzBimy](+). The absorption bands, observed at around 862 nm for nickel compounds (2a-2c), can be assigned to combined transitions consisting of d-d, MLCT, pi -> pi* electronic transitions. DFT calculations have been carried out to determine stability of bare organic molecules, used in this study, in the perspective of their apparent stability (energy consideration) in the matrix of metal dithiolate coordination complex. Hirshfeld surface analyses have been performed to assess additional supramolecular perceptions into crystal structure features. The relevant fingerprint plot areas portray the percentages of different intermolecular interactions in the crystal structures. Copper compounds 1a-1c are additionally characterized by electron spin resonance (ESR) studies.
机译：一系列新的离子对络合物[Bz，R-BzBimy]（2）[M（mnt）（2）] {[Bz，R-BzBimy]（+）= 1-benzy1-3-（4-R-苄基）苯并咪唑鎓; M = Cu，R = H（1a），NO2（1b）和Br（1c）; M = Ni，R = H（2a），NO2（2b）和Br（2c）以及mnt（2-）=顺丁烯二硫代马来酸三价}已制备并通过常规光谱分析（包括单晶X射线晶体学）进行了表征。由于苯并咪唑鎓阳离子中芳基（-CH2-Ar）的柔性性质，如果为化合物[Bz，H-BzBimy]，则[Bz，H-BzBimy]（1+）和[Bz，NO2-BzBimy]（1+）分别在] BF 4（a）和[Bz，NO 2 -BzBimy] BF 4（b）中观察到芳基的构象变化在它们各自的金属二硫醇盐化合物1a，1b，2a和2b中。但是，在化合物[Bz，Br-BzBimy]（2）BF4（c）的阳离子有机受体[Bz，Br-BzBimy]（1+）与所得离子之间未观察到相关苯基的取向变化配对化合物1c和2c。当与不同的抗衡离子（例如四氟硼酸根（BF4-）和[M（mnt））离子配对时，阳离子有机受体（苯并咪唑部分，[Bz，R-BzBimy]（+））中芳基的流动行为（2）]（2-），主要取决于超分子相互作用（例如，S中心点中心点中心点H，N中心点中心点中心点H，O中心点中心点中心点H，Br中心点阳离子和阴离子之间的弱点）。在金属-二硫代盐离子对化合物1a，1b的晶体结构中观察到，发现苯并咪唑鎓部分（阳离子部分）中一个苯环的p-取代基（H，NO和Br）是造成结构多样性的原因。 ，1c，2a，2h和2c。在这方面，值得一提的是，含镍的离子对化合物2a，2b和2c与相应的铜类似物1a，1b和1c是同构的。对于铜化合物（1a-1c）观察到的在约1210 nm处的近红外吸收带归因于电荷从二硫代铜酸阴离子[Cu（mnt）（2）]（2-）转移至苯并咪唑鎓阳离子[Bz，R-BzBimy]（+）。对于镍化合物（2a-2c），在约862 nm处观察到的吸收带可以分配给由d-d，MLCT，pi-> pi *电子跃迁组成的组合跃迁。 DFT计算已经确定了本研究中使用的裸露有机分子的稳定性，从其在金属二硫醇盐配位化合物基质中的表观稳定性（能量考虑）出发。已经进行了赫希菲尔德表面分析，以评估对晶体结构特征的其他超分子感知。相关的指纹图谱区域描绘了晶体结构中不同分子间相互作用的百分比。铜化合物1a-1c的特征还在于电子自旋共振（ESR）研究。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号