A Series of Isopropyl-Substituted Oligogermanes Prⁱ₃Ge(GePh₂)_nGePrⁱ₃ (n = 0–3) Featuring a Luminescent and Dichroic Pentagermane Prⁱ₃Ge(GePh₂)₃GePrⁱ₃

Abstract

The series of oligogermanes Pr i 3 Ge-(GePh 2 ) n GePr i 3 (n = 0, 2; n = 1, 3; n = 2, 4; n = 3, 5) were prepared by the hydrogermolysis reaction. All four species were characterized by NMR ( 1 H and 13 C) and UV/visible spectroscopy as well by cyclic voltammetry and differential pulse voltammetry. The oligogermanes exhibited a successive red shift in their absorbance maxima as the length of the Ge−Ge chain was increased, and these molecules also became easier to oxidize as the chain length was increased. The X-ray crystal structures of 4 and 5 as well as the trigermane HPh 2 GeGePh 2 GePh 2 H (6) were determined. The pentagermane 5 was shown to be dichroic in the solid state due to the packing of the individual molecules in a columnar fashion in the crystal. Pentagermane 5 is also luminescent in solution, exhibiting an emission maximum at 380 nm. The physical properties of 5, like the hexagermane Pr i 3 Ge(GePh) 4 GePr i 3 , mimic the properties of the larger polygermane systems.

Donor-acceptor molecular oligogermanes: Novel properties and structural aspects

“…This mechanism may be applicable to the oxidation of alkyl substituted oligogermanes,. [28] [26] In the case of aryl substituted oligogermanes, the intermediate cation and radical should be sufficiently stable to form catenated derivative that could undergo subsequent oxidations as observed by Weinert et al [23] The structure of oligogermanes (especially the nature of the substituents) strongly impacts on the oxidation potential and pathway.…”

“…To the best of our knowledge there are only 3 linear pentagermanes with known molecular solid state structure, Ge5Ph12 (at 295 K: d(Ge-Ge)av 2.460(4) and Ge-Ge-Geav 115.6(2) o ; at 100 K: d(Ge-Ge)av 2.4502(6) and Ge-Ge-Geav 115.52(2) o [11a, 25] ), (Me3Ge)3GeGeMe2Ge(GeMe3)3 (d(Ge-Ge)av 2.4425 (9) and Ge-Ge-Geav 111.68(4) o ) [9b] and (i-Pr)3Ge[GePh2]3Ge(i-Pr)3 (d(Ge-Ge)av 2.4710 (8) and Ge-Ge-Geav 117.01(3) o ) [26] . Compound 4 crystallizes in a triclinic P-1 (Z = 2) space group, without any symmetry element.…”

Exploring the Versatility of the Amidation of Aryl Acid Fluorides using the Germylamines R3GeNMe2

“…The germylamines R 3 GeNMe 2 (R = Ph (1), [40] Bu n (2), [40] Pr i (3) [41] ) were synthesized by the metathesis reaction between the corresponding chlorogermane R 3 GeCl and LiNMe 2 as previously reported (Scheme 3). Distillation of Ph 3 GeNMe 2 in a Kugelrohr oven resulted in crystals that were suitable for X-ray analysis.…”

Substituent Control of σ-interference Effects in the Transmission of Saturated Molecules

“…Although alkyl and phenyl substituents are quite benign from a chemical point of view, they are particularly promising because they are realistic synthetical targets for silicon and germanium based molecular cores. [49][50][51][52][53][54][55][56][57] We hope these results will motivate studies of the properties of substituted cyclic and bicyclic silanes and germanes. The transmission suppression is less clear in the C222 systems than for the silanes and germanes.…”