Identification of Ge≡O Triple Bond in Ge₆O^– Cluster: Anion Photoelectron Spectroscopy and Theoretical Calculations

Abstract

Unlike CO, which is common in coordination chemistry and organometallic chemistry, little is known about SiO or GeO compounds. Here we report a Ge6O– cluster featuring a GeO triple bond. The structural and chemical bonding properties of Ge6O–/0 are investigated using anion photoelectron spectroscopy and theoretical calculations. Two nearly degenerate isomers have been found for Ge6O–. The lowest-energy structure (6A) can be viewed as an O atom bonding with a tetragonal bipyramidal Ge6. The second one (6B) can be considered as an O atom interacting with a capped trigonal bipyramidal Ge6. Chemical bonding analyses reveal that Ge6O– (6A) can be viewed as a GeO unit interacting with a σ antiaromatic C 2v symmetric tetragonal pyramidal Ge5 3– moiety. Comparisons of the chemical bonding in Ge6O– (6A) with that in Ge5CO– and Ge5MnO– indicate the similar behavior of GeO to CO and MnO in its bonding to the Ge5 3– and Ge5 4– moieties.

Anion Photoelectron Spectroscopy and Theoretical Studies of Ge3n+1O (n = 1–3) Clusters with the C3v Symmetric Ge3 Structural Unit

“…Several metal-doped silicon and germanium clusters have been found with the potential to construct silicon and germanium nanomaterials, such as VSi 12 , CoSi 12 , V 2 Si 20 , and Mn 2 Ge 7 . In addition, GeO 2 nanowires and nanofibers as well as GeO x nanowires are usually considered as model materials for nanoscale optical and memory devices. , In this work, the structures of Ge 4 O, Ge 7 O, and Ge 10 O could be obtained by inserting one, two, and three C 3v symmetric Ge 3 units into the diatomic GeO molecule, in which the Ge 3 units are antiparallel in Ge 7 O and Ge 10 O. In order to investigate the possibility of the construction of 1D nanostructures by extending the Ge 3 units, we conducted preliminary calculations for Ge 13 O at the B3LYP/6-311++G­(d,p) level.…”

“…Moreover, the chemical bonding analyses of germanium oxide clusters could provide further insights into the germanium–germanium and germanium–oxygen interactions which in turn are helpful to realize the assemblies of nanostructures. In the last decades, a number of anionic and neutral germanium oxide clusters including GeO, − GeO 2 –/0 , ,− GeO 4 – , Ge 2 O 2 –/0 , ,,, Ge 2 O 3 –/0 , Ge 3 O –/0 , , Ge 3 O 2 – , Ge 3 O 3 –/0 , ,,, Ge 3 O 4 – , Ge 3 O 5 – , Ge 4 O 4 –/0 , ,,, Ge 5 O 5 – , and Ge 6 O –/0 have been investigated using spectroscopic experiments and theoretical calculations.…”

Structures and Properties of Planar Ge3O3 Cluster and Its Buckled Honeycomb Two-Dimensional Nanostructure

“…Many experimental and theoretical studies have been conducted on germanium oxide clusters. − The IR and Raman spectra of Ge 3 O 3 were measured in a nitrogen matrix and solid Ar, respectively. , The Gibbs free energy and enthalpy of formation of Ge 3 O 3 were calculated by theory . The vibrational frequencies of Ge 3 O 3 were analyzed using theoretical methods. , The photoelectron spectrum of Ge 3 O 3 – was recorded in experiments .…”