Department of Chemistry, University of Basel, Spitalstrassse 51, CH-4056 Basel, Switzerland.
Dalton Trans. 2011 Dec 7;40(45):12146-52. doi: 10.1039/c1dt10618j. Epub 2011 Jul 19.
In solution, (E) to (Z)-isomerism is facile both in 3-(9-anthracenyl)-1-(pyridin-4-yl)propenone, 2, and in its silver(I) complex Ag(2)(2). The crystal structures of (E)-2, (Z)-2 and [Ag{(E)-2}(2)][SbF(6)] are presented, and the roles of edge-to-face and face-to-face π-interactions in the lattice are discussed. Solution NMR spectroscopic data suggest that the driving force for (E) to (Z) isomerization is intramolecular π-stacking of the pyridine and anthracene domains. The reversed enone 3-(9-anthracenyl)-1-(pyridin-4-yl)propen-3-one, (E)-3, and the silver(I) complex [Ag{(E)-3}(2)][SbF(6)] have been prepared and characterized, including a single crystal X-ray determination of the latter. Surprisingly, no π-stacking between anthracene or pyridine domains is observed in the solid state, and the crystal packing is dominated by Ag···F, CH(anthracene)···π-pyridine and CH···F interactions. In contrast to (E)-2 and Ag{(E)-2}(2), neither (E)-3 nor Ag{(E)-3}(2) undergoes photoisomerization in solution.
在溶液中，3-(9-蒽基)-1-(吡啶-4-基)丙烯酮 2 及其银(I)配合物[Ag(2)(2)]+都很容易发生(E)到(Z)顺反异构。本文呈现了(E)-2、(Z)-2 和 [Ag{(E)-2}(2)][SbF(6)]的晶体结构，并讨论了边缘到面和面对面π-相互作用在晶格中的作用。溶液 NMR 光谱数据表明，(E)到(Z)异构化的驱动力是吡啶和蒽环结构域的分子内π堆积。还制备和表征了反式烯酮 3-(9-蒽基)-1-(吡啶-4-基)丙烯-3-酮 (E)-3 和银(I)配合物 [Ag{(E)-3}(2)][SbF(6)]，包括后者的单晶 X 射线测定。令人惊讶的是，在固态中未观察到蒽或吡啶结构域之间的π堆积，晶体堆积主要由 Ag···F、CH(anthracene)···π-吡啶和 CH···F 相互作用主导。与 (E)-2 和 [Ag{(E)-2}(2)]+不同，(E)-3 和 [Ag{(E)-3}(2)]+在溶液中均不会发生光异构化。
