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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >A theoretical study of luminescent vapochromic compounds including an AuCu_2(NHC)_2 core
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A theoretical study of luminescent vapochromic compounds including an AuCu_2(NHC)_2 core

机译：含AuCu_2（NHC）_2核的发光气相致变色化合物的理论研究

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Vapochromic complexes [Au(im(CH_2py)_2) _2(Cu(MeCN)_2)_2]~(3+)1, [Au(im(CH _2py)_2)_2(Cu(MeOH))_2]~(3+)2 and [Au(im(CH_2py)_2)_2(Cu(H_2O)) _2])~(3+)3 were theoretically investigated. The Au-Cu distances of 1 and 2 (4.631 ? and 2.767 ?, respectively) optimized by the SCS-MP2 method in this work agree with the literature experimental values (4.591 ? and 2.792 ?). Their structural features are explained by computational results: (i) in 1, two MeCN molecules coordinate with the Cu center, because of the strong coordination ability of MeCN, to afford a four-coordinate tetrahedral-like Cu center. This geometry needs a long Au-Cu distance. (ii) In 2 and 3, only one MeOH or H_2O molecule coordinates with the Cu center because of their weak coordination abilities, to afford a three-coordinate planar Cu center. Because the three-coordinate Cu center is flexible, the Au-Cu distance becomes short due to the Au-Cu metallophilic interaction, the strength of which is 5.3 kcal mol~(-1) at the SCS-MP2 level. The emission energies of 1, 2 and 3 (2.62, 2.40 and 2.38 eV, respectively) calculated here by the B3PW91 agree with their literature experimental values (2.68, 2.47, and 2.39 eV). The lowest energy triplet excited state (T_1) is assigned as the excitation from the Cu d to the pyridine π* orbital in 1 and that from the Au-Cu 5d-3d anti-bonding MO to the Au-Cu 6p-4sp bonding MO in 2 and 3. As a result, the emission energy from the T_1 to the ground state is different between these compounds. The difference in Au-Cu distance is one of the important factors for the differences in emission energy and assignment between 1 and others (2 and 3). The vapochromism of these compounds arises from the difference in Au-Cu distance which is determined by the balance between the strengths of the coordination of a gas molecule and the Au-Cu metallophilic interaction; in other words, the Au-Cu heterometallophilic interaction is important for the vapochromic activity of the complex.
机译：气相致变色络合物[Au（im（CH_2py）_2）_2（Cu（MeCN）_2）_2]〜（3+）1，[Au（im（CH _2py）_2）_2（Cu（MeOH））_ 2]〜（3理论上研究了+）2和[Au（im（CH_2py）_2）_2（Cu（H_2O）_2]）〜（3+）3。通过SCS-MP2方法优化的Au-Cu距离为1和2（分别为4.631Ω和2.767Ω），与文献中的实验值（4.591Ω和2.792Ω）一致。计算结果解释了它们的结构特征：（i）在1中，由于MeCN的强配位能力，两个MeCN分子与Cu中心配位，从而形成了四坐标四面体状的Cu中心。这种几何形状需要很长的Au-Cu距离。 （ii）在2和3中，由于它们的弱配位能力，只有一个MeOH或H_2O分子与Cu中心配位，从而得到三坐标平面Cu中心。由于三坐标的Cu中心是柔性的，因此由于Au-Cu的亲金属相互作用，Au-Cu的距离变短，在CSS-MP2水平下其强度为5.3 kcal mol〜（-1）。 B3PW91在此计算出的1、2和3的发射能量（分别为2.62、2.40和2.38 eV）与其文献实验值（2.68、2.47和2.39 eV）相符。最低能量的三重态激发态（T_1）被指定为从Cu d到1中的吡啶π*轨道的激发以及从Au-Cu 5d-3d反键MO到Au-Cu 6p-4sp键MO的激发结果，这些化合物之间从T_1到基态的发射能量不同。 Au-Cu距离的差异是1与其他（2和3）之间的发射能量和分配差异的重要因素之一。这些化合物的气相致变色是由Au-Cu距离的差异引起的，Au-Cu距离的差异是由气体分子的配位强度和Au-Cu嗜金属相互作用之间的平衡决定的。换句话说，Au-Cu杂金属相互作用对于复合物的气相致变色活性很重要。

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