Hybrid polymeric iodoplumbates constructed from morpholine and its derivatives: structures and properties

Abstract

Three hybrid polymeric iodoplumbates constructed from morpholine and its derivatives, {(Pb(4)I(15))[(Mph·H)(3)(Mph·1.5H)(2)]}(n)(1), {(edm-H(2))(Pb(3)I(8))]·2DMF}(n)(2), {(edm-H(2))[(dmp)(Pb(4)I(12))]˙2DMF}(n) (3) (Mph = morpholine, edm = ethylenedimorpholine, dmp(2+) = N,N'- dispiromorpholinopiperazonium) have been synthesized and structurally determined. In these compounds, morpholine and its derivatives weakly interact with or covalently bond to polymeric iodoplumbates. In 1, hydrogen bonds between (Pb(4)I(15))(7-) clusters and protonized Mph contribute to the formation of a 1-D hybrid chain. In 2, the 1-D [(Pb(3)I(8))](n)(2n-) chain is extended to be a 2-D layer via the edm(2+) ligand by means of Pb-O covalent bonds. Interestingly, the 2-D [(Pb(4)I(12))](n)(4n-) inorganic layer in 3 is concertedly templated by two kinds of organic cations. The above compounds exhibit a semiconductor nature, and third-order nonlinear optical (NLO) activities can be detected in 1 and 3.