Effect of a weak donor on the intramolecular charge transfer of molecules containing two neighboring silicon atoms

Comparison between SiMe2and CMe2Spacers as σ-Bridges for Photoinduced Charge Transfer

“…13 These properties find their origin in the occurrence of σ-conjugation along the silicon backbone, 1,14,15 the presence of polarizable valence electrons, 16 low ionization potentials, 3,14 and σ-π interactions. [17][18][19] Because of these features Zyss and co-workers [20][21][22][23][24][25] investigated the second-order nonlinear optical activity, which is strongly related to the presence of intramolecular CT interactions, of donoracceptor substituted silanes. Although moderate second-order nonlinear optical responses were found, it remained obscure whether CT between donors and acceptors takes place in oligoand especially monosilylene-bridged compounds.…”

“…They exhibit intense σ−σ* electronic transitions in the near-UV region, − intermolecular charge transfer (CT) complexes involving permethylated oligosilanes have been reported, , and in photoexcited arylsilanes intramolecular CT emission originating from a 1 (σ,π*) charge transfer state has been observed. − Furthermore, rapid electron transfer between chromophores connected by silicon catenates was proposed . These properties find their origin in the occurrence of σ-conjugation along the silicon backbone, ,, the presence of polarizable valence electrons, low ionization potentials, , and σ−π interactions. − Because of these features Zyss and co-workers − investigated the second-order nonlinear optical activity, which is strongly related to the presence of intramolecular CT interactions, of donor−acceptor substituted silanes. Although moderate second-order nonlinear optical responses were found, it remained obscure whether CT between donors and acceptors takes place in oligo- and especially monosilylene-bridged compounds.…”

Stepwise Introduction of Different Substituents to α-Chloro-ω-hydrooligosilanes: Convenient Synthesis of Unsymmetrically Substituted Oligosilanes

“…Recently, various functionalized oligosilanes have attracted growing interests due to their unique photophysical and electronic properties [1][2][3][4][5][6][7][8][9][10][11][12][13]. In the synthesis of such compounds, introduction of functionality to oligosilanes is an important process.…”

Nonlinear Optical Properties of Organosilicons: Intramolecular Charge Transfer in Pyridyldisilanes with a Donor‐Acceptor Linker

“…The increasing interest in diphenyldisilane compounds for NLO leads to various kinds of materials related to the intramolecular CT in conjugated systems ,. It has been reported that properties of organosilicon compounds with NLO responses are expected to depend on three features: increasing polarzability of the Si backbone via σ delocalization as compared to the saturated carbon chain, p‐d orbital bonding, and σ‐π interactions …”

“…Some diphenyldisilane molecules were synthesized by Mignani, and the first order hyperpolarizability value is up to 16×10 −30 esu for 1‐(4‐(2,2‐Dicyanoethenyl)phenyl)‐2‐(4‐(dimethylamino)phenyl) tetramethyldisilane ,. Nishihara et al .…”