Ionic aggregation of the solvated electron with lithium cation in tetrahydrofuran solution

Abstract

Aggregation of the solvated electron with lithium cation in tetraC hydrofuran forms ionic species which .have been investigated by the pulse radiolysis method. The ion pair (Li ,ei) has a·near infra-red absorption band with X = 1175 nm and a molar extinction coefficient of 2.28 x 104 max M-icm-1 at the maximum. A higher aggregate, suggested to be the dilithium cation-electron triple ion, {(Li )2,ei} has an optical absorption band with k = 890 nm and an extinction coefficient of 5400 M-icm-1 at the max maximum. Absolute rate constants have been determined for reactions of these species with anthracene, biphenyl and dibenzylmercury. The reactivities of these two species are compared a.long wi.th the reactivities of (Na ,es) and es in THF solution.

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

“…As mentioned above, a transient absorption of a solvated electron in thf or cation-electron contact pairs has been found at 870 nm and beyond with lifetimes exceeding 1 ns. [29][30][31] Hence, inspection of the NIR spectral range is essential. In contrast to the reference system, the LiGe 9 -compound, 28 40 In such a scenario, the relatively long lifetime (τ 3 ∼ 150 ps) of this charge-transfer-complex can be explained by the low electron withdrawing effect of the Ge 9 0 -entity, i.e.…”

“…around 1180 nm for [Li, e − ]. 31 The newly synthesized cluster compound was investigated by broadband fs-transient absorption spectroscopy in the visible and NIR spectral region to explore the influence of a transition metal substituent on the excited state dynamics of such a cluster using [Ge 9 (Hyp) 3 ] − as a reference system. 32 The Ge 9 core in 1 is best described as a distorted monocapped square antiprismatic arrangement of nine germanium atoms, where the capping germanium atom (Ge8) is bound to a Hyp substituent via a Ge-Si single bond of 236.9 pm.…”

UV photoexcitation of a dissolved metalloid Ge9 cluster compound and its extensive ultrafast response

“…21 According to our knowledge, no timeresolved studies exist for the latter system, but extensive investigations have been performed for charge transfer of NaI to THF [22][23][24][25][26][27][28][29] that show a similar signature of so-called tight-contact pairs of the form (Na + , e À ) THF peaking around 870 nm 30 (full squares in Fig. We further speculate that additional channels such as ligand elimination are also energetically accessible 11 or they are related to trapped states like (Li + ,e À ) THF contact pairs that peak around 1180 nm.…”

Correlation of optical and electron spin resonance spectra for alkali metal solutions in ethylamine and tetrahydrofuran

“…Electron spin resonance (esr) spectra of most pulse radioiysis (25)(26)(27)(28)(29)(30)(31) techniques have demonalkali metal solutions in amines and ethers con-strated the existence of distinct optical bands sist of a singlet and a set of hyperfine lines assigned to e,-, (M+, es-) and M-. In et.hylamine assigned to solvated electrons, e,-, and a (EA) (25,26) and tetrahydrofuran (TMF) (27-'monomer' or solvated alkali atom species (1-1 I), respectively.…”