Hydrogen-bond supported intercalation compounds constructed from three types of two-dimensional layers and common guests, {(Hha)[Cu(CA)(EtOH)]} (1), {(Hha)[Cu(CA)(EtOH)]} (2), and {(Hha)[Cu(CA)]} (3) (ha = hexylamine), have been synthesized and characterized. The hexylaminium cations are introduced between the anionic layers of the metal-chloranilate by not only electrostatic interactions but also hydrogen bonding interactions. These compounds show reversible EtOH adsorption and desorption accompanied by a structural transformation. With a change in the interaction between the mononuclear complexes of the host layer, the interaction between the host layer and the intercalated guest cations also changes. Moreover, the mobility and flexibility of the intercalated Hha cations enable the rearrangement of the mononuclear complexes while maintaining their layer structure. Thus, these compounds have flexibilities both in the inter- and intra-layers.
We herein report the synthesis, single-crystal structures of coordination polymers, and structural transformations of complexes employing 1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazinedicarbonitrile (tdpd2−) and pyrazine (pyz) as bridging ligands. {[M(H2O)4(pyz)][M(tdpd)2(pyz)]·6(H2O)}n, [1·10H2O and 2·10H2O where M = Co (1) and Zn (2)], consists of two types of crystallographically independent one-dimensional (1D) structures packed together. One motif, [M(tdpd)2(pyz)]2− (A), is an anionic infinite pyz bridged 1D array with chelating tdpd2− ligands, and the other motif is a cationic chain, [M(H2O)4(pyz)]2+ (B), which is decorated with four terminal water molecules. The 1D arrays (A) and (B) are arranged in parallel by multi-point hydrogen-bonding interactions in an alternate (A)(B)(A)(B) sequence extending along the c-axis. Both compounds exhibit structural transformations driven by thermal dehydration processes around 350 K to give partially dehydrated forms, 1·2H2O and 2·2H2O. The structural determination of the partially dehydrated form, 2·2H2O, reveals a solid-state structural transformation from a 1D chain structure to a two-dimensional (2D) coordination sheet structure, [Zn2(tdpd)2(H2O)2(pyz)]n (2·2H2O). Further heating to 500 K yields the anhydrous form 2. While the virgin samples of 1·10H2O and 2·10H2O crystallize in different crystal systems, powder X-ray diffraction (PXRD) measurements of the dehydrated forms, 1·2H2O and 2·2H2O, are indicative of the same structure. The structural transformation is irreversible for 1·10H2O at ambient conditions. On the other hand, compound 2·10H2O shows a reversible structural change. The solid-state structural transformation for 1·10H2O was also confirmed by monitoring in-situ magnetic susceptibility, which is consistent with other thermally-induced measurements.
Reaction of M(OAc)2·xH2O (M, x = Zn, 2 and Co, 4), 1,4-dihydro-5,6-dicyano-2,3-pyrazinedione (H2CN2pyzdione), and pyrazine (pyz) affords two compounds of the same molecular formula {[M(H2O)6][M(CN2pyzdione)2(pyz)]·6H2O}n (M = Zn for 1 and Co for 2) in which discrete units of [M(H2O)6]2+ are linked to one-dimensional chains of [M(CN2pyzdione)2(pyz)]2– via multiple O–H···O hydrogen-bonding interactions and M2+-bound H2O molecules in [M(H2O)6]2+ also serve as linkers of hydrogen-bonded interstitial H2O molecules. Remarkably, 1 crystallizes in the monoclinic crystal system, the similar crystal system and unit cell parameters as 2, but with a space group distinct from 1 and 2, i.e., 1 is the noncentrosymmetric space group C2, whereas 2 is the centrosymmetric space group C2/m. This polar structure for 1 is induced by the presence of alternating arrangements of distinguishable two axial Zn–N bonds within [Zn(CN2pyzdione)2(pyz)]2– chains. Indeed, solid-state circular dichroism spectra of 1 exhibit significant Cotton effects, as evidenced by the polar space group C2. Moreover, these Cotton effects show clear temperature-dependence depending on contents of H2O molecules of 1.
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