Crystal Structures and Melting Behaviors of 2D and 3D Anionic Coordination Polymers Containing Organometallic Ionic Liquid Components

Abstract

Although coordination polymers generally do not melt, several that do melt have been synthesized recently and have drawn much attention. In this study, two‐ and three‐dimensional coordination polymers that melt were synthesized, [Ru(Cp)(C6H5R)][M{C(CN)3}2] (R=H, Me, Et; M=K, Rb; Cp=C5H5), which are complex salts comprising M[C(CN)3] and organometallic ionic liquids [Ru(Cp)(C6H5R)][C(CN)3]. They have anionic [M{C(CN)3}2]n− coordination polymer frameworks, whose dimensionalities depend on the size of the organometallic cation inside. Their melting points decreased with increasing cation substituent length and size of the alkali metal ion (Tm=102–239 °C), and these low‐melting‐point coordination polymers exhibited incongruent melting, forming mixtures of solid M[C(CN)3] and ionic liquid upon melting. Using the same method, coordination polymers were synthesized with various bridging ligands, [Co(Cp)2][MX2] (X=B(CN)4, C(CN)3, N(CN)2; M=K, Na), as well as a paramagnetic coordination polymer, [Fe(Cp)2][K{C(CN)3}2].

Synthesis and Properties of a Compositional Series of MIL-53(Al) Metal–Organic Framework Crystal-Glass Composites

“…Further studies of specific interest are as follows: (i) the diffusion of various guest species into the composite material, (ii) predicting optimum loading limits, (iii) the effects of crystallite size, and (iv) attempts at shaping the bulk products formed. We believe that this may open routes to further functional MOF-CGCs and take advantage of many recent reports of MOF and coordination polymer glass formation. − …”

Synthesis and Properties of a Compositional Series of MIL-53(Al) Metal-Organic Framework Crystal-Glass Composites

“…We believe that this may open routes to further functional MOF--CGCs and take advantage of many recent reports of MOF and coordination polymer glass formation. [28][29][30][31]…”

Two-Dimensional Metal-Organic Framework Materials: Synthesis, Structures, Properties and Applications

“…Topological view with kgd net in complex [Ru­(Cp)­(C 6 H 6 )]­[K­{C­(CN) 3 } 2 ]. Adapted with permission from ref . Copyright 2019 John Wiley & Sons.…”

“…Further H 2 and CO 2 uptake has been measured as 209.9 cm 3 (STP) g −1 and 106.8 cm 3 (STP) g 50). 377 [Zn 5 (bpib) 2 (L) 4 (OH) 2 (H 2 O) 2 ] (bpib = 1,4-bis(2-(pyridin-2-yl)-1H-imidazol-1-yl)butane; H 2 L = 3,3′-methylenebis(oxy)dibenzoic acid) provides a highly corrugated kgd net which is two-fold parallel interpenetrated (Figure 51). 378 Matzger et al reported a unique non-interpenetrated clusterbased 2D MOF [Zr 6 (μ 3 -O) 4 (μ 3 -OH) 4 (BTB) 2 (OH) 6 (H 2 O) 6 ], derived from a tritopic linker BTB (1,3,5-(4-carboxylphenyl)benzene) in the presence of concentrated HCl and exhibits kgd topology net (Figure 52).…”