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Here we present the synthesis and characterization of a hybrid vanadium-organic coordination polymer with robust magnetic order, a Curie temperature T C of ∼110 K, a coercive field of ∼5 Oe at 5 K, and a maximum mass magnetization of about half that of the benchmark ferrimagnetic vanadium(tetracyanoethylene) ∼2 (V·(TCNE) ∼2 ). This material was prepared using a new tetracyano-substituted quinoidal organic small molecule 7 based on a tricyclic heterocycle 4-hexyl-4 H -pyrrolo[2,3- d :5,4- d ′]bis(thiazole) ( C6-PBTz ). Single crystal X-ray diffraction of the 2,6-diiodo derivative of the parent C6-PBTz , showed a disordered hexyl chain and a nearly linear arrangement of the substituents in positions 2 and 6 of the tricyclic core. Density functional theory (DFT) calculations indicate that C6-PBTz -based ligand 7 is a strong acceptor with an electron affinity larger than that of TCNE and several other ligands previously used in molecular magnets. This effect is due in part to the electron-deficient thiazole rings and extended delocalization of the frontier molecular orbitals. The ligand detailed in this study, a representative example of fused heterocycle aromatic cores with extended π conjugation, introduces new opportunities for structure–magnetic-property correlation studies where the chemistry of the tricyclic heterocycles can modulate the electronic properties and the substituent at the central N -position can vary the spatial characteristics of the magnetic polymer. 

Hydrogen bonding (HB) interactions are well known to impact the properties of water in the bulk and within hydrated materials. A series of Ni( ii ) complexes based on chelates containing N -(2-aminoethyl)-1-methylimidazole-2-carboxamide have been synthesized and fully characterized by single crystal X-ray diffraction, spectroscopic methods, and thermal analysis. The complexes reveal a variety of water cluster motifs dependent on the packing arrangement in the solid state. A key feature is the orientation of the carboxamide moiety, which leads to the formation of void spaces that accommodate water through HB interactions. The water motifs contain 1D water chains (streams), 2D tapes of infused rings (cascades), and isolated water dimers (pools). The HB motifs in the hydrated structures vary as a function of the crystal packing of the host molecules. Thermal analyses show a correlation between the HB motif in the hydrated crystals and the temperature range of the dehydration process. The conductivity of the hydrated crystals varies as a function of the crystal packing interactions between metal complexes.