Hybrid Polymeric Iodoplumbates Constructed from Morpholine and Its Derivatives: Structures and Properties

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Abstract
Three hybrid polymeric iodoplumbates constructed from morpholine and its derivatives, {(Pb4I15)[(Mph·H)3(Mph·1.5H)2]}n(1), {(edm-H2)(Pb3I8)]·2DMF}n(2), {(edm-H2)[(dmp)(Pb4I12)]˙2DMF}n (3) (Mph = morpholine, edm = ethylenedimorpholine, dmp2+ = 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 (Pb4I15)7− clusters and protonized Mph contribute to the formation of a 1-D hybrid chain. In 2, the 1-D [(Pb3I8)]n 2n− chain is extended to be a 2-D layer via the edm2+ ligand by means of Pb–O covalent bonds. Interestingly, the 2-D [(Pb4I12)]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.