Phosphorus complexes of meso-triaryl-25-oxasmaragdyrins

Kalita, Hemanta ; Lee, Way-Zen ; Ravikanth, Mangalampalli (2014) Phosphorus complexes of meso-triaryl-25-oxasmaragdyrins Inorganic Chemistry, 53 (17). pp. 9431-9438. ISSN 0020-1669

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The aromatic PO2 complexes of meso-triaryl-25-oxasmaragdyrins were synthesized by treating the free base 25-oxasmaragdyrins with POCl3 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.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:104915
Deposited On:30 Nov 2017 12:31
Last Modified:30 Nov 2017 12:31

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