The aromatic PO2 complexes of meso-triaryl-25-oxasmaragdyrins were synthesized by treating the free base 25-oxasmaragdyrins with POCl 3 in toluene/triethylamine at refluxing temperature. The complexes are stable and characterized by X-ray and different spectroscopic techniques. In these complexes, the phosphorus(V) ion was bound to two pyrrolic nitrogen atoms of the smaragdyrin macrocycle and two oxygen atoms in tetrahedral geometry. The X-ray structure revealed that the smaragdyrin macrocycle showed significant distortion upon insertion of a PO2 unit, and the phosphorus atom lies 1.339 Å above the mean plane defined by three meso-carbon atoms of the macrocycle. These complexes absorb strongly in the visible region and are 2.5 times more strongly fluorescent than free base 25-oxasmaragdyrins. The smaragdyrin macrocycle becomes electron-deficient upon complexation with a PO2 unit because these complexes are easier to reduce but difficult to oxidize compared to free base smaragdyrins. We designed and synthesized a covalently linked BODIPY-PO2-smaragdyrin dyad and demonstrated efficient energy transfer from the BODIPY unit to the PO2-smaragdyrin unit.
|頁（從 - 到）||9431-9438|
|出版狀態||已發佈 - 2014 9月 2|
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指紋深入研究「Phosphorus complexes of meso -triaryl-25-oxasmaragdyrins」主題。共同形成了獨特的指紋。
CCDC 975030: Experimental Crystal Structure Determination
Kalita, H. (Creator), Lee, W. (Creator) & Ravikanth, M. (Creator), Unknown Publisher, 2014
DOI: 10.5517/cc11qlly, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc11qlly&sid=DataCite