TY - JOUR
T1 - Application of 204mPb perturbed angular correlation of ¿-rays spectroscopy in coordination chemistry
AU - Vibenholt, Johan Elias
AU - Schau-Magnussen, Magnus
AU - Stachura, Monika Kinga
AU - Bjerrum, Morten Jannik
AU - Thulstrup, Peter Waaben
AU - Arcisauskaité, Vaida
AU - Hemmingsen, Lars Bo Stegeager
PY - 2012/2/20
Y1 - 2012/2/20
N2 - 204mPb perturbed angular correlation of γ- rays (PAC) spectroscopy has been applied successfully for the first time to detect the nuclear quadrupole interaction in a lead(II) coordination compound in a molecular crystal [tetraphenylarsonium lead(II) isomaleonitriledithiolate ([AsPh 4] 4 [Pb 2 (i-mnt) 4])]. The recorded parameters from a powder crystalline sample are ?Q = 0.178(1) GHz and ν = 0.970(7). The electric field gradient (EFG) was determined at the PW91/QZ4P level including relativistic effects using the two-component zeroth-order regular approximation method for both the [Pb(i-mnt) 2] -2 monomer and the [Pb 2 (i-mnt) 4] 4- dimer. Only the EFG for the latter compares favorably with the experimental data, indicating that the picture of this complex as a prototypical hemidirected coordination geometry with a stereochemically active lone pair on lead(II) is inadequate. Advantages and limitations of 204mPb PAC spectroscopy as a novel technique to elucidate the electronic and molecular structures of lead-containing complexes and biomolecules are presented.
AB - 204mPb perturbed angular correlation of γ- rays (PAC) spectroscopy has been applied successfully for the first time to detect the nuclear quadrupole interaction in a lead(II) coordination compound in a molecular crystal [tetraphenylarsonium lead(II) isomaleonitriledithiolate ([AsPh 4] 4 [Pb 2 (i-mnt) 4])]. The recorded parameters from a powder crystalline sample are ?Q = 0.178(1) GHz and ν = 0.970(7). The electric field gradient (EFG) was determined at the PW91/QZ4P level including relativistic effects using the two-component zeroth-order regular approximation method for both the [Pb(i-mnt) 2] -2 monomer and the [Pb 2 (i-mnt) 4] 4- dimer. Only the EFG for the latter compares favorably with the experimental data, indicating that the picture of this complex as a prototypical hemidirected coordination geometry with a stereochemically active lone pair on lead(II) is inadequate. Advantages and limitations of 204mPb PAC spectroscopy as a novel technique to elucidate the electronic and molecular structures of lead-containing complexes and biomolecules are presented.
U2 - 10.1021/ic202614j
DO - 10.1021/ic202614j
M3 - Journal article
C2 - 22300368
SN - 0020-1669
VL - 51
SP - 1992
EP - 1994
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 4
ER -