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Unusual nitro-coordination of Eu(III) and Tb(III) with pyridinyl ligands
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A new ligand family based on picoline, bipyridine and terpyridine containing a nitro moiety has been synthesized and its coordination and sensitization ability for lanthanide ions has been studied. Three new complexes were characterized by X-ray single crystal diffraction and all three show uncommon coordination of the nitro moiety to the lanthanide ion. 5cTb, a terpyridine-nitro derivative with Tb(NO3)3, crystallizes in the orthorhombic space group Pbca with a = 15.125(3), b = 13.776(3), c = 18.716(4) �, and V = 3899.8(13) �and is isostructural with its Eu(III) analog (5cEu) with cell parameters a = 15.1341(4), b = 13.7070(4), c = 18.8277(5) �. 6Eu, a tripodal amine with a nitro-derivatized pyridine with Eu(CF3SO3)3, crystallizes in the triclinic space group P[1 with combining macron] with a = 11.067(2), b = 11.633(2), c = 12.772(3) �, ? = 110.94(3), ? = 97.49(3), ? = 91.42(3)� and V = 1518.1(5) � Finally, ligand 5a, a bipyridine-nitro derivative, crystallizes in the orthorhombic space group P21/n with a = 3.7128(3), b = 11.7806(8), c = 19.9856(14) �, ? = 92.925(2)� and V = 873.01(11) � All four ligands show sensitization of Eu(III) and Tb(III) luminescence.