Polynuclear architectures with cadmium and lithium ions based on the {Li2Cd2(O2CCMe3)6} fragment

Molecular [Li2Cd2(L)2(Piv)6]·Solv (Piv ​= ​trimethylacetate anion, L ​= ​2,4-lutidine (1), 2,2′-bipyrdine (2), 2,2’:6′,2″-terpyridine (3),·Solv ​= ​4MeCN (2)), chain [Li3Cd(MeCN)(THF)(Piv)5]n (4) and three-dimensional polymer [Li4Cd5(H2O)4(Piv)14]n.4H2O (5) complexes were synthesized and structurally characterized. All the new molecules contain the basic moiety {Li2Cd2(Piv)6} with the two central Li atoms connected with periphery CdII by bridging carboxylate anions. Molecular compounds 1–3 are stabilized by terminal N-donor ligands. In the chain of polymer 4 each CdII atom simultaneously belongs to the neighboring {Li2Cd2(Piv)4} moiety. The core in 5 is formed by connection the {Li2Cd2} units by the {Cd(Piv)2(H2O)4} tetradentate bridging moiety. The vaporization processes, thermodynamic characteristics of complex 2 and related dissociation products in condensed and gas phases were determined by mass spectrometry. Stability of 2 in the processes of hypothetical dissociation was additionally estimated by DFT-calculations. A series of new complexes with stable core {Li2Cd2(Piv)6} were synthesized. Polymers rearrange to molecular {Li2Cd2} complexes in the presence of stabilizing N-donor. Vaporization, dissociation, thermodynamics for {Li2Cd2} complex were characterized by mass spectrometry. Stability of {Li2Cd2(Piv)6} fragment in the dissociation was estimated by DFT-calculations. [Display omitted] •A series of new complexes with stable core {Li2Cd2(Piv)6} were synthesized.•Polymers rearrange to molecular {Li2Cd2} complexes in the presence of N-donor.•Vaporization, dissociation, thermodynamics were characterized by mass spectrometry.•Stability of {Li2Cd2(Piv)6} in the dissociation was estimated by DFT-calculations.