Magnetic Response Properties of Coinage Metal Macrocyles. Insights into the Induced Magnetic Field through the Analysis of [Cu5(Mes)5], [Ag4(Mes)4], and [Au

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• 作者：Alvaro Mu帽oz-Castro
• 刊名：The Journal of Physical Chemistry C
• 出版年：2012
• 出版时间：August 16, 2012
• 年：2012
• 卷：116
• 期：32
• 页码：17197-17203
• 全文大小：401K
• 年卷期：v.116,no.32(August 16, 2012)
• ISSN：1932-7455

文摘

The complexity of the magnetic response of coinage metal macrocycles supporting closed-shell d¹⁰鈥揹¹⁰ interaction has been studied through the analysis of [Cu₅(Mes)₅], [Ag₄(Mes)₄], and [Au₅(Mes)₅] (Mes = 2,4,6-Me₃C₆H₂) by means of relativistic DFT methods. Our effort relies on the description of the overall shielding tensor (未) surrounding the molecular space in terms of its components (未_ij, i, j = x, y, z) by using chemical shift tensor maps to unravel the magnetic complexity of such molecular arrays. Additionally, the diamagnetic, paramagnetic, and spin鈥搊rbit contributions to the through the space chemical shift tensor are depicted for the first time in order to gain more insight into the variation of the magnetic response according to the atomic number (Z) of the metallic core involved. Our results show a strong axis-dependent (orientation-dependent) behavior of the coinage macrocycles indicating that the magneto-responsive properties increase according to Z with the core electrons mainly contributing to diamagnetic term of the shielding tensor.