Syntheses, crystal structures, lone pair functionality and electrospray ionization mass spectral properties of trinuclear, dimer of trinuclear and trinuclear-based one-dimensional systems of copper(II) and lead(II)

Add time:08/08/2019    Source:sciencedirect.com

This work presents the syntheses, crystal structures, lone pair functionality and electrospray ionization spectra in positive mode (ESI-MS positive) of two trinuclear CuIIPbIICuII compounds [(CuIIL1)2PbII(ClO4)2] (1) and [(CuIIL2)2PbII(NO3)2] (2), one dimer of trinuclear (CuIIPbIICuII)2 compound [{(CuIIL2)2PbII}2(μ-adipate)](ClO4)2·2H2O (3) and one trinuclear CuIIPbIICuII–based one-dimensional (1D) compound [(CuIIL2)2PbII(μ1,5-dicyanamide)2]n (4), where H2L1 and H2L2 are the [2+1] condensation products of salicylaldehyde and, respectively, 1,3-diaminopropane and 2,2′-dimethyl-1,3-diaminopropane. The four compounds have been synthesized by treating the corresponding copper(II) metallo-ligand with a PbII salt (for 1 and 2) or with a PbII salt and a secondary bridging ligand (adipic acid for 3 and sodium dicyanamide for 4). In the trinuclear CuIIPbIICuII moiety in all of 1–4, the PbII center resides in between two [CuIIL1]/[CuIIL2] moieties and copper(II) and lead(II) for each of the two CuIIPbII pairs are diphenoxo bridged. Two trinuclear units are interlinked by an adipate to form the dimeric hexanuclear compound 3. The neighbouring trinuclear units are interlinked by two dicyanamides, forming one-dimensional coordination polymer 4. ESI-MS positive spectra reveal the existence of mono/di/trinuclear and even unusual tetranuclear star type gaseous positive ions; the observed and simulated isotopic distribution patterns are nicely matched. The existence of stereochemically active/inactive lone pair of electrons of lead(II) has been explored. Salient and interesting features in the structures and ESI-MS have been discussed.

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