Thermally induced structural transitions between single-crystalline states in the first hybrid compound combining Keggin-type clusters with metal-cyclam complexes: From two-dimensional covalent assemblies to discrete molecular species

A hydrothermal reaction between the monolacunary polyoxometalate [SiW11O39]8–, a copper(II) salt, and 1,4,8,11-tetraazacyclotetradecane (cyclam) affords the first example of a hybrid compound combining metal complexes of such an N4-tetradentate macrocyclic ligand and Keggin-type clusters, namely, [Cu(cyclam)(H2O)][{Cu(cyclam)}2SiW11O39Cu(H2O)]·5H2O (1). This compound has been characterized by infrared spectroscopy and thermal and elemental analyses. Single-crystal X-ray diffraction (scXRD) reveals a layered crystal packing made of corrugated two-dimensional covalent grids in which four octahedral {Cu(cyclam)}2+ bridging moieties connect copper(II)-monosubstituted {SiW11O39Cu(H2O)}6– polyanions to four adjacent clusters, and additional [Cu(cyclam)(H2O)]2+ square-pyramidal counterions are embedded into square-like grid voids. Thermostructural analyses confirm the presence in the 130–250 °C temperature range of a stable and crystalline anhydrous phase, which displays a diffraction pattern different from that of 1. This thermally triggered phase transition proceeds through a single-crystal to single-crystal transformation pathway, which according to scXRD, involves not only the release of water molecules, but also the cleavage and formation of Cu–O bonds induced by the rotation of Keggin-type anions. These modifications fully dismantle the parent two-dimensional covalent assembly to result in the neutral, discrete [{Cu(cyclam)}3SiW11O39Cu] hybrid species (2), in which the cluster exhibits three square-pyramidal {Cu(cyclam)}2+ decorating moieties grafted at its surface. This species must display a five-coordinated copper(II) center in the Keggin skeleton, and therefore, it constitutes one of the scarce examples of such type of coordinatively unsaturated substituted cluster observed in the solid state. The irreversibility of the phase transition has been confirmed by combined thermal and diffractometric analyses, which evidenced also the great flexibility of the supramolecular framework of 2, as this anhydrous phase is able to adsorb up to six water molecules per cluster to lead to the hydrated derivative [{Cu(cyclam)}3SiW11O39Cu(H2O)]·5H2O (2h) without any significant alteration in its cell parameters, nor in its crystalline structure.This work was funded by Eusko Jaurlaritza/Gobierno Vasco (EJ/GV, Grants IT1291-19 and PIBA2018-59) and Ministerio de Ciencia, Innovacion y Universidades (Grant MAT2017- 89553-P). L.F.N. and E.R.B. are indebted to EJ/GV for their predoctoral fellowships (PRE_2019_1_0106 and PRE_2018_1_0143).Peer reviewe