Abstract
Four analogous platinum stilbene- and stilbazole-based complexes exhibit unusual long-range heteronuclear spin-spin coupling in solution. Single crystal analysis and NMR experiments show that the 19F, 31P, and 195Pt nuclei communicate over large distances (0.9-1.3 nm) through bond rather than through space. Spin-spin couplings between 195Pt and 19F over seven bonds and between 31P and 19F over eight bonds are observed with 7JPtF = 2.9 Hz and 8JPF = 11.8 Hz. Remarkably, a very large spin coupling between 195Pt and 19F over six bonds (6J PtF = 40.1 Hz) is also observed in a structurally related pyridinium complex. Experimental and gNMR (version 5.0) simulated 19F{ 1H}, 31P{1H}, and 195Pt{ 1H} spectra of the complexes reveal a three-spin AMY system (A = 31P, M = 31P, Y = 19F) or a five-spin AMY3 flanked by a four-spin AMXY or a six-spin AMXY3 system (X = 195Pt), respectively. Density functional theory calculations at the PBE0/SDD level of theory show a π-conjugated metal-ligand network, which may contribute to the experimentally observed spin-spin interactions.
| Original language | English |
|---|---|
| Pages (from-to) | 4021-4030 |
| Number of pages | 10 |
| Journal | Inorganic Chemistry |
| Volume | 48 |
| Issue number | 9 |
| DOIs | |
| Publication status | Published - May 4 2009 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Physical and Theoretical Chemistry
Cite this
Long-range through-bond heteronuclear communication in platinum complexes. / Zenkina, Olena V.; Konstantinovski, Leonid E.; Shimon, Linda J W; Diskin-Posner, Yael; Iron, Mark A.; van der Boom, Milko.
In: Inorganic Chemistry, Vol. 48, No. 9, 04.05.2009, p. 4021-4030.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Long-range through-bond heteronuclear communication in platinum complexes
AU - Zenkina, Olena V.
AU - Konstantinovski, Leonid E.
AU - Shimon, Linda J W
AU - Diskin-Posner, Yael
AU - Iron, Mark A.
AU - van der Boom, Milko
PY - 2009/5/4
Y1 - 2009/5/4
N2 - Four analogous platinum stilbene- and stilbazole-based complexes exhibit unusual long-range heteronuclear spin-spin coupling in solution. Single crystal analysis and NMR experiments show that the 19F, 31P, and 195Pt nuclei communicate over large distances (0.9-1.3 nm) through bond rather than through space. Spin-spin couplings between 195Pt and 19F over seven bonds and between 31P and 19F over eight bonds are observed with 7JPtF = 2.9 Hz and 8JPF = 11.8 Hz. Remarkably, a very large spin coupling between 195Pt and 19F over six bonds (6J PtF = 40.1 Hz) is also observed in a structurally related pyridinium complex. Experimental and gNMR (version 5.0) simulated 19F{ 1H}, 31P{1H}, and 195Pt{ 1H} spectra of the complexes reveal a three-spin AMY system (A = 31P, M = 31P, Y = 19F) or a five-spin AMY3 flanked by a four-spin AMXY or a six-spin AMXY3 system (X = 195Pt), respectively. Density functional theory calculations at the PBE0/SDD level of theory show a π-conjugated metal-ligand network, which may contribute to the experimentally observed spin-spin interactions.
AB - Four analogous platinum stilbene- and stilbazole-based complexes exhibit unusual long-range heteronuclear spin-spin coupling in solution. Single crystal analysis and NMR experiments show that the 19F, 31P, and 195Pt nuclei communicate over large distances (0.9-1.3 nm) through bond rather than through space. Spin-spin couplings between 195Pt and 19F over seven bonds and between 31P and 19F over eight bonds are observed with 7JPtF = 2.9 Hz and 8JPF = 11.8 Hz. Remarkably, a very large spin coupling between 195Pt and 19F over six bonds (6J PtF = 40.1 Hz) is also observed in a structurally related pyridinium complex. Experimental and gNMR (version 5.0) simulated 19F{ 1H}, 31P{1H}, and 195Pt{ 1H} spectra of the complexes reveal a three-spin AMY system (A = 31P, M = 31P, Y = 19F) or a five-spin AMY3 flanked by a four-spin AMXY or a six-spin AMXY3 system (X = 195Pt), respectively. Density functional theory calculations at the PBE0/SDD level of theory show a π-conjugated metal-ligand network, which may contribute to the experimentally observed spin-spin interactions.
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U2 - 10.1021/ic801940h
DO - 10.1021/ic801940h
M3 - Article
VL - 48
SP - 4021
EP - 4030
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 9
ER -