An Isolable Radical Anion of an Organosilicon Cluster Containing Only σ Bonds

Abstract

The radical anion of octa-tert-butyloctasilacubane was generated and isolated. The EPR spectrum showed the satellites due to the tertiary 13 Cn uclei of the eight tert-butyl groups.T he X-rayc rystallographic analysis showed that the SiÀSi bonds are shortened and the SiÀCb onds are elongated compared with those of octa-tert-butyloctasilacubane.T hese results are well explained by the distribution of an unpaired electron in the singly occupied molecular orbital (SOMO).

Facile Synthesis of an Octagermacubane with Two Three‐Coordinate Germanium(0) Atoms and its Unique Radical Anion

“…In contrast, a matrix‐isolation EPR study of [C 8 F 8 ]⋅ − ( 27 ), [28] revealed that the unpaired electron is located predominantly inside the cubane cage, unlike in 26 . An anionic cubic germanium‐iron cluster {Ge 8 [Fe(CO) 4 ] 8 } 7− ( 28 ) featuring an unpaired electron, [29] and a [Si 8 (tBu) 8 ]⋅ − radical anion ( 29 ) were also isolated [30] . However, in both 28 and 29 , the SOMO is highly delocalized over the σ bonds of their cubane framework, [29, 30] in contrast to 26 .…”

“…An anionic cubic germanium‐iron cluster {Ge 8 [Fe(CO) 4 ] 8 } 7− ( 28 ) featuring an unpaired electron, [29] and a [Si 8 (tBu) 8 ]⋅ − radical anion ( 29 ) were also isolated [30] . However, in both 28 and 29 , the SOMO is highly delocalized over the σ bonds of their cubane framework, [29, 30] in contrast to 26 . Therefore, radical anions 26 represent a new type of group 14 cluster radical anions, in which the spin is evenly distributed between two symmetric 3‐coordinate Ge atoms, with very little spin density on the other Ge atoms .…”

Triple‐chain segments regulation enable shape memory and photo deformation of smart polyimide

“…Much progress has been made in this field, but it is still a challenge to synthesize polymers with multiple functions or reactions simultaneously, with the few exceptions being based on supramolecular chemistry or gels. 4,5 Meanwhile, most of these materials are poorly stabilized and susceptible to heat and solvents.…”

“…Compared with inorganic transition metal oxides with photo striction, photo strictive organic molecules with reversible conformational changes, such as isopropyl pyran, diary benzene, and azobenzene, have been widely used in the fields of controllable liquid transmission, information storage, sensors, and anti‐counterfeiting. Much progress has been made in this field, but it is still a challenge to synthesize polymers with multiple functions or reactions simultaneously, with the few exceptions being based on supramolecular chemistry or gels 4,5 . Meanwhile, most of these materials are poorly stabilized and susceptible to heat and solvents.…”

{Ge8[Fe(CO)4]8}7−: an anionic cubic germanium-iron-cluster featuring an unpaired electron

“…Kyushin and co-workers reported on the compound [Si 8 t Bu 8 ]˙ − ( 4 ) which is obtained by chemical reduction of Si 8 t Bu 8 with a potassium mirror. 25 Compound 4 can be crystallized as a separated ion pair via addition of [2.2.2]cryptand. The EPR spectrum of compound 4 shows a single isotropic signal which is persistent in a sealed tube for at least half a year, the authors tell.…”