Photoluminescence of antimony(III) and bismuth(III) chloride complexes in solution

Abstract

The search of an ideal host for the formation and detection of trapped electrons in organic single crystals has lead us to a large family of clathrate hydrates containing peralkylammonium hydroxide guests. The presence of trapped electrons has been detected by pulse radiolysis at room temperature in a large number of the clathrates.1-2 Two compounds were chosen for this initial study of electron stabilization: tetramethylammonium hydroxide pentahydrate,

Photoluminescence of tetrachloroarsenate(III)

“…Its spin-forbidden character is in accordance with the observation that this emission appears only at low temperatures while the luminescence of SbCl; and BiCl; can be clearly seen in solution at room temperature [ 2,3]. A rough estimate of the radiative lifetime of AsCl; based on the emission quantum yield (@x 1 0m4) and lifetime (T= 0.46 us) yields a reasonable value of approximately 10 ms which compares with 2.5 ms for As3+ in Cs2NaScCl 6.…”

“…Stokes shifts of this magnitude were also observed for SbClb and Sic&. It is suggested that this shift is caused by a structural change from disphenoidal (C,,) [6] in the ground state toward a tetrahedral geometry in the 'P1 excited state [ 2,3]. It is quite interesting that the Stokes shift of AsCl,-is comparable to that of As3+ in Cs$IaScCl, (Ati= 12200 cm-') [ I].…”

“…In analogy to SbCl; and BiClh [2,3] the longwavelength absorptions of AsCl; are assigned to sp transitions of the central s2 ion. The A band ( 'So+3PI transition) of AsClh at A,_= 359 nm is much weaker than those of SbClh and BiCl, since the spin-selection rule is largely valid for arsenic which belongs to the fourth period of the periodic table.…”

“…We explored this possibility and selected the complex anion AsCl; for the present investigation. This choice was based on our previous study of the emission behavior of the complexes MC12 and MCI:-with M = Sb and Bi [ 2,3]. We expected to see distinct differences in the luminescence properties between the heavy metal complexes SbCl, and BiCI; and the corresponding chloro complex of the lighter congener arsenic which as a number of the fourth period of the periodic table is characterized by a smaller spinorbit coupling constant.…”

Photochemistry and photophysics of coordination compounds of the main group metals

“…The electronic spectra of SbCl 4~ (Figure 5) 10 may be used to illustrate this emission behavior. We suggest that the ground state distortion of SbCl4" is eliminated in the excited state.…”