The Structures of s<sup>2</sup>Metal Complexes in the Ground and sp Excited States

Vogler, Arnd; Nikol, Hans

doi:10.1080/02603599308048663

Cited by 100 publications

(105 citation statements)

References 32 publications

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“…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.…”

Section: Discussionsupporting

confidence: 64%

“…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].…”

Section: Discussionmentioning

confidence: 73%

“…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.…”

Section: Discussionmentioning

confidence: 99%

“…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.…”

Section: Introductionmentioning

confidence: 99%

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Photoluminescence of tetrachloroarsenate(III)

Kunkely

Pawlowski

Vogler

1994

Chemical Physics Letters

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Section: Discussionsupporting

confidence: 64%

Section: Discussionmentioning

confidence: 73%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Photoluminescence of tetrachloroarsenate(III)

Kunkely

Pawlowski

Vogler

1994

Chemical Physics Letters

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“…Spectroscopic data on lone-pair systems are numerous as well -see the reviews of G. Blasse [8] and A.Vogler and H. Nikol [9].We will analyse some representative examples for the CN=3 (SnCl 3 -), CN=4 (SbCl 4 -) and CN=6 (SbCl 6 3-, SeCl 6 2-, TeCl 6 2-) by applying respective AOM approaches and in comparison with the results of many electron DFT calculations.…”

Section: Introductionmentioning

confidence: 99%

The Angular Overlap Model and Vibronic Coupling in Treating s-p and d-s Mixing – a DFT Study

Reinen

Atanasov

2004

Structure and Bonding

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The steric and energetic lone pair effect induced by s-p mixing can be parameterised within the angular overlap model (AOM), as is shown for a series of halide molecules and complexes mainly of the fifth main group (oxidation state +III) with the coordination numbers 3 to 6. The derived effective AOM parameters e sp eff , defined for the average bond lengths of the distorted structures, decrease the softer the considered entity is, and seem to be transferable within groups of chemically related species.We base the analysis on results of DFT calculations, using specifically Kohn-Sham MO diagrams in comparison to corresponding many-electron energies. There is definite experimental evidence for s-p and for d-s mixing as well, as is demonstrated by the DFT analysis of spectral data for some model complexes. The equivalence of the vibronic coupling approach on the MO level with the AOM is emphasized; the advantage of the AOM is, however, that angular and radial (bond length) contributions can be cleanly separated.

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Bromoplumbate mit kettenförmigen und isolierten Anionen: (Bzl4P)2[Pb3Br8], (Bzl4P)2[Pb3Br8(dmf)2], (Bzl4P)[PbBr3], (Bzl4P)2[PbBr4] und (Bzl4P)4[Pb2Br6][PbBr4]

Gröger

Lode

Vollmer

et al. 2002

Z. anorg. allg. Chem.

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Professor Lothar Beyer zum 65. Geburtstag gewidmet Inhaltsu È bersicht. PbBr 2 bildet mit LiBr und (Bzl 4 P)(PF 6 ) (Bzl = CH 2 C 6 H 5 ) in Aceton eine Reihe von Bromoplumbatkomplexen, deren Zusammensetzungen und Strukturen von den Reaktions-und Kristallisationsbedingungen abha È ngen. In den eindimensional polymeren Anionen (Bzl 4 P) 2 [Pb 3 Br 8 ] (1 a) und (Bzl 4 P)[PbBr 3 ] (2) sind die Pb-Atome fu È nf-und sechsfach koordiniert. Dagegen binden in den diskreten einbzw. zweikernigen Anionen von (Bzl 4 P) 2 [PbBr 4 ]´2Aceton (3´2Aceton) und (Bzl 4 P) 4 [Pb 2 Br 6 ][PbBr 4 ] (4) die Pb-Atome an jeweils vier Bromoliganden. Aus DMF als Lo È sungsmittel kristallisiert (Bzl 4 P) 2 [Pb 3 Br 8 (dmf) 2 ] (1 b) mit dem gleichen Bromoplumbatgeru È st wie in 1 a, wobei die Koordinationslu È cken in 1 a durch Lo È sungsmittelmoleku È le belegt sind. Verbindung 3 zeigt bei Anregung mit ultraviolettem Licht gru È n-gelbe Lumineszenz mit einem Emissionsmaximum bei 547 nm.(Bzl 4 P) 2 [Pb 3 Br 8 ] (1 a): a = 907,93(6), b = 1305,39(9), c = 1367,04(9), a = 91,929(6), b = 104,527(6), c = 103,589(6), V = 1517,1(2)´10 6 pm 3 , Raumgruppe P1; (Bzl 4 P) 2 [Pb 3 Br 8 (dmf) 2 ] (1 b): Abstract. PbBr 2 reacts with LiBr and (Bzl 4 P)(PF 6 ) (Bzl = CH 2 C 6 H 5 ) in acetone to form a series of bromoplumbate complexes with compositions and structures depending on the conditions of reaction and crystallization. While the anions in (Bzl 4 P) 2 [Pb 3 Br 8 ] (1) and (Bzl 4 P)[PbBr 3 ] (2) are onedimensional polymers with penta-and hexacoordinated Pb atoms, the metal atoms in the mono-and dinuclear complex anions of (Bzl 4 P) 2 [PbBr 4 ]´2acetone (3´2acetone) and (Bzl 4 P) 4 [Pb 2 Br 6 ][PbBr 4 ] (4) bind to four bromo ligands. From DMF as a solvent (Bzl 4 P) 2 [Pb 3 Br 8 (dmf) 2 ] (1 b) crystal-lizes with the same bromoplumbate structure as in 1 a, but with dmf ligands occupying the coordination sites vacant in 1 a. Upon radiation of compound 3 with ultraviolet light greenish yellow photoluminescence (emssion maximum at 547 nm) is observed. Crystallographic details see ªInhaltsu È bersichtº.

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The Structures of s²Metal Complexes in the Ground and sp Excited States

Cited by 100 publications

References 32 publications

Photoluminescence of tetrachloroarsenate(III)

Photoluminescence of tetrachloroarsenate(III)

The Angular Overlap Model and Vibronic Coupling in Treating s-p and d-s Mixing – a DFT Study

Bromoplumbate mit kettenförmigen und isolierten Anionen: (Bzl4P)2[Pb3Br8], (Bzl4P)2[Pb3Br8(dmf)2], (Bzl4P)[PbBr3], (Bzl4P)2[PbBr4] und (Bzl4P)4[Pb2Br6][PbBr4]

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The Structures of s2Metal Complexes in the Ground and sp Excited States

Cited by 100 publications

References 32 publications

Photoluminescence of tetrachloroarsenate(III)

Photoluminescence of tetrachloroarsenate(III)

The Angular Overlap Model and Vibronic Coupling in Treating s-p and d-s Mixing – a DFT Study

Bromoplumbate mit kettenförmigen und isolierten Anionen: (Bzl4P)2[Pb3Br8], (Bzl4P)2[Pb3Br8(dmf)2], (Bzl4P)[PbBr3], (Bzl4P)2[PbBr4] und (Bzl4P)4[Pb2Br6][PbBr4]

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The Structures of s²Metal Complexes in the Ground and sp Excited States