On the Affinity between Fullerenes and Deltahedral Zintl Ions: A UV/Vis Spectroscopic Investigation

Abstract

The close relationship of C60 and deltahedral tetrel element cluster anions has been pointed out before. We report herein on UV/Vis spectra of the Zintl anions and compounds [Ge9]2–, [(CH2=CH)2Ge9]2–, [{(Me3Si)3Si}3Ge9]–, {(Me3Si)3Si}3Ge9CH2CH3, {(Me3Si)3Si}3Ge9(CH2)2CH3, {(Me3Si)3Si}3Ge9(CH2)3CH=CH2, and [{(Me3Si)3Si}3Ge9CH2CH3]Pt(PPh3). The spectra are compared to those of the C60 fullerene, which were recorded under the same conditions. The UV/Vis spectrum of pristine [Ge9]2– resembles that of C60 and at higher concentration hint at the known trimeric [(Ge9)3]6–. The influence of ligand substitution at the Ge9 cluster‐core is highlighted. For this, the synthesis of the specifically functionalized deltahedral Ge9 clusters {(Me3Si)3Si}3Ge9(CH2)2CH3, {(Me3Si)3Si}3Ge9(CH2)2CH=CH2, and {(Me3Si)3Si}3Ge9(CH2)3C6H5 are reported for the first time and is achieved by the reaction of K[{(Me3Si)3Si}3Ge9] with the respective alkyl halides in acetonitrile. The newly synthesized products were characterized by NMR spectroscopy.

The influence of the FeCp(CO)2+moiety on the dynamics of the metalloid [Ge9(Si(SiMe3)3)3]−cluster in thf: synthesis and characterization by time-resolved absorption spectroscopy

“…The UV-Vis part is dominated by a band, which extends from the UV to the visible range with shoulders at 340 and 560 nm while in the NIR region no noticeable absorption can be found. It is similar to the spectrum of the metalloid cluster [Ge 9 Hyp 3 ] − , 20,28 which shows a comparable UV bandwith one shoulder at 260 nmthat extends to visible but without − clusters 20 reveal UV absorption similar to the one found here which is evidence for the assignment to the Ge 9 − entity.…”

“…On the other hand, transitions in the Vis range were assigned to originate from the Ge 9 2− -cluster in ref. 20, which is not present in our case. Therefore, we assign the band peaking around 560 nm (Fig.…”

Intermetalloid Clusters: Molecules and Solids in a Dialogue

“…[141] Due to their discrete energy levels,s mall metal clusters are prone to show fluorescence behavior and highly fluorescent clusters of Cu, Ag and Au were prepared in solution by wet-chemical methods. [146] [143] Theu se of nanoclusters as luminescent emitters for biomedical purposes has found large scientific interest, such as use as bioimaging,b iosensing or as anticancer agents.…”

Intermetalloide Cluster: Moleküle und Festkörper im Dialog

“…0.5 nm fürA u). [146] [139,140] Nach diesem allgemeinen Kontext ist die Anionen-Photoelektronen-Spektroskopie in Kombination mit UV/Vis-Messungen und rechnerischen Methoden ein leistungsfähiges Werkzeug,umdie elektronische Struktur von Clustern zu bestimmen.…”

“…[145] Der Einfluss von aggregiertem [Ge 9 ] 2À auf die optischen Eigenschaften wurde durch konzentrationsabhängige UV/Vis-Messungen gezeigt:W ährend in verdünnten Lçsungen die Spektren von [Ge 9 ] 2À denen von C 60 ähneln, tauchen bei hçheren Konzentrationen Banden bei niedrigerer Energie auf, welche von Oligomeren wie {[Ge 9 ] 3 } 6À stammen. [146]…”