Self-Assembled Supramolecular Complexes with 鈥淩ods-in-Belt鈥?Architecture in the Light of Soft X-rays

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• 作者：Anna A. Makarova ; Elena V. Grachova ; Dmitry V. Krupenya ; Oleg Vilkov ; Alexander Fedorov ; Dmitry Usachov ; Alexander Generalov ; Igor O. Koshevoy ; Sergey P. Tunik ; Eckart R眉hl ; Clemens Laubschat ; Denis V. Vyalikh
• 刊名：The Journal of Physical Chemistry C
• 出版年：2013
• 出版时间：June 13, 2013
• 年：2013
• 卷：117
• 期：23
• 页码：12385-12392
• 全文大小：442K
• 年卷期：v.117,no.23(June 13, 2013)
• ISSN：1932-7455

文摘

One of the most important properties of the recently discovered 鈥渞ods-in-belt鈥?supramolecular complexes containing Au鈥揅u or Au鈥揂g cluster cores is the possibility of tuning their electronic and photophysical properties through modification of the ligand environment. This opens great perspectives for their applications in light-emitting devices and bioimaging. The high structural ordering and self-assembly properties of these unique objects may be used to design artificial nanostructures with complex topologies that could become ideal building blocks for next-generation electronics. Here we present a detailed experimental study of the electronic structure of 鈥渞ods-in-belt鈥?supramolecular complexes. Applying X-ray photoemission and absorption spectroscopy, we systematically unraveled the structure of their occupied and unoccupied electronic states near the Fermi level. The major contribution to the highest occupied molecular orbitals is made by the triple-bonded carbons hosted in the dialkynylgold 鈥渞ods鈥?and the copper (silver) atoms from the central cluster core of the heterometallic Au鈥揅u (Au鈥揂g) molecules. The lowest unoccupied molecular orbitals are located on the carbon skeleton of the complexes, including 鈭扖鈮鈥?and 鈭扖鈺怌鈥?aromatic orbitals. The onset of the valence band in the Au鈥揂g systems is 0.3 eV lower than that in the Au鈥揅u complexes, implying a slightly larger energy gap for the silver-based molecules. With increasing size, the complexes become more and more sensitive to X-ray damage.