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首页> 外文期刊>Chemistry: A European journal >The Nature of the Ag~I centre dot centre dot centre dot Ag~I Interaction in Different Ag(NH3)2 Dimers Embedded in Supramolecular Solids
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The Nature of the Ag~I centre dot centre dot centre dot Ag~I Interaction in Different Ag(NH3)2 Dimers Embedded in Supramolecular Solids

机译：嵌入超分子固体中的不同Ag（NH3）2二聚体的Ag〜I中心点中心点中心点Ag〜I相互作用的性质

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摘要

An isolated silver(I) ammonia monomer, a dimer, and a novel dimer containing an intercalated water molecule have been embedded as guests in supramolecular frameworks, [Ag(NH3)2][(H2thpe)(H3thpe)]centre dot MeCN (1), [{Ag(NH3)2}2][(H2thpe)2]centre dot 4.25H2O (2), and [{Ag(NH3)2}-H2O-{Ag(NH3)2}]-[(H2thpe)_2] centre dot benzene (3) (H3THPE = tris(hydroxyphenyl)ethane). The [{Ag-(NH3)2}2]~(2+) dimer is not stable as an isolated entity, but is stabilized by hydrogen bonding in the supramolecular framework. The water-intercalated silver(I) ammonia dimer, which constitutes a novel species, is also subject by hydrogen bonding in concentrated solutions. The destabilization energy of the dimer relative to isolated monomers is calculated to be approx=300kJ mol~(-1) by both perturbation methods and DFT theory. For the water-intercalateddimer it is calculated to be approx= 200 kJ mol~(-1) according to the BSSE-corrected MP2 calculation. The different aggregate states show a dramatic variation of absorption and emission properties, in accordance with the concentration dependent red-shift observed in solutions. Natural-bond-orbital analysis shows that the disilver-am-monium-aquo "sandwich" cation in 3 is stabilized by interaction between the pi lone pair orbital on the oxygen atom of the water molecule and Ag~I-N sigma anti-bonding molecular orbital.
机译：分离的银（I）氨单体，二聚体和包含嵌入水分子的新型二聚体已作为来宾嵌入了超分子框架[Ag（NH3）2] [（H2thpe）（H3thpe）]中心MeCN（1 ），[{Ag（NH3）2} 2] [（H2thpe）2]中心点4.25H2O（2）和[{Ag（NH3）2} -H2O- {Ag（NH3）2}]-[（H2thpe ）_2]中心点苯（3）（H3THPE =三（羟苯基）乙烷）。 [{Ag-（NH3）2} 2]〜（2+）二聚体作为分离的实体不稳定，但通过超分子框架中的氢键稳定。构成新颖物质的水嵌入的银（I）氨二聚体也受到浓缩溶液中氢键的影响。通过扰动法和DFT理论计算，相对于分离的单体，二聚体的去稳定能约为= 300kJ mol〜（-1）。对于水嵌入的二聚体，根据BSSE校正的MP2计算，其计算为约= 200 kJ mol〜（-1）。根据在溶液中观察到的浓度依赖性红移，不同的聚集态显示出吸收和发射特性的巨大变化。自然键轨道分析表明，水分子中氧原子上的π孤对与Ag〜IN sigma反键分子轨道之间的相互作用使3中的二铵-铵-水基“三明治”阳离子稳定。 。

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