Antenna Effect by Organometallic Chromophores in Bimetallic d鈥揻 Complexes

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• 作者：Franklin Ferraro ; Dayan P谩ez-Hern谩ndez ; Juliana A. Murillo-L贸pez ; Alvaro Mu帽oz-Castro ; Ramiro Arratia-P茅rez
• 刊名：The Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：August 22, 2013
• 年：2013
• 卷：117
• 期：33
• 页码：7847-7854
• 全文大小：343K
• 年卷期：v.117,no.33(August 22, 2013)
• ISSN：1520-5215

文摘

The nature of the intermetallic bond in a series of complexes of the type [Cp₂鈥揟M鈥揗鈥揅p₂] (where TM = Re and M = Y, La, Lu, Yb, Ac; also TM = Os and M = Th; Cp = cyclopentadienyl ligand) have been studied by relativistic two-component density functional theory (DFT) calculations. The results obtained in this work show that the interaction between the transition metal and lanthanide atoms is mainly ionic in all cases, while for the case of actinide atoms this interaction becomes significantly more covalent. The effective direction of the electron transfer between the Re鈫扐c or Os鈫扵h centers allows us to propose that the [Cp₂ReAcCp₂] and [Cp₂OsThCp₂] complexes are ideal candidates for near-infrared (NIR) technologies since their absorption spectra show some transitions over 600 nm. We also observed a shifting of the absorption spectrum of around 100 nm of the [Cp₂Re] fragment when is compared against the absorption spectrum of the entire complex. This behavior allows us to argue that the [Cp₂Re] fragment is a good antenna chromophore due to the possibility of charge transfer transitions from this fragment to the f shell in lanthanide or actinide elements studied here.