Isomeric Ionic Lithium Isonicotinate Three-Dimensional Networks and Single-Crystal-to-Single-Crystal Rearrangements Generating Microporous Materials

Abstract

Reaction between LiOH and isonicotinic acid (inicH) in the appropriate solvent or mixture of solvents affords a family of variously solvated forms of a simple ionic lithium salt, viz., Li(+)inic(-)·S (where S = 0.5 morpholine, 0.5 dioxane, 0.25 n-hexanol, 0.5 N-methylpyrrolidinone, 0.5 N,N-dimethylformamide, 0.5 n-propanol, 0.5 cyclohexanol, 0.5 pyridine, 0.5 t-butanol, 0.5 ethanol, and 0.5 methanol). Three-dimensional Li(+)inic(-) frameworks containing solvent-filled channels are present in all of these except for the MeOH and EtOH solvates. The nondirectional character of the electrostatic interactions between the Li(+) and inic(-) ions bestows an element of "plasticity" upon the framework, manifested in the observation of no less than five different framework structures within the family. Unusual single-crystal-to-single-crystal transformations accompany desolvation of Li(+)inic(-)·S in which the Li(+)inic(-) framework undergoes a major rearrangement (from a structure containing "8484 chains" to one with "6666 chains"). The "before and after" structures are strongly suggestive of the mechanism and the driving force for these solid state framework rearrangements: processes which further demonstrate the "plasticity" of the ionic Li(inic) framework. A solid-state mechanism for these desolvation processes that accounts very satisfactorily for the formation of the channels and for the diverse geometrical/topological aspects of the transformation is proposed. The reverse process allows the regeneration of the solvated 8484 form. When the 6666 Li(+)inic(-) form is immersed in carbon disulfide, a single-crystal-to-single-crystal transformation occurs to generate Li(+)inic(-)·0.25CS2. The hydrate, Li(+)inic(-)·2H2O which consists of discrete Li(inic)·H2O chains obtained by recrystallizing the salt from water, can also be obtained by hydration of the 6666 form. A dense 3D network with the formula, Li(inic) can be obtained in a reversible process by the removal of the water from the hydrated form and also by crystallization from a t-amyl alcohol solution.

New s‐Block Metal Pyridinedicarboxylate Network Structures through Gas‐Phase Thin‐Film Synthesis

“…This is in line with the general observation that the s‐block metal‐based CP structures are more prone to absorb guest water molecules than, for example, the transition‐metal‐based structures . Furthermore, due to the ionic network, they are more flexible to rearrange their crystal structures from one crystal structure to another, for example, upon intercalation/deintercalation of coordinated water/solvent molecules …”

“…[24][25][26][27] Furthermore, due to the ionic network, they are more flexible to rearrange their crystal structures from one crystals tructure to another,f or example, upon intercalation/deintercalation of coordinated water/solvent molecules. [12,28] Av iable assumption is that solvent-free conditions could promotet he synthesis of anhydrous metal pyridinedicarboxylate network structures, and in this work, we demonstratet hat this is indeed true. We employ the strongly emerginga tomic/ molecular layer deposition (ALD/MLD) thin-filmt echnique [29,30] for the direct single-step synthesis of novel alkali and alkaline earth metal pyridinedicarboxylate materials.…”

“…GIXRD patterns for thin films depositedat2 20 8Cw ith the Li(thd)+ +TPA( for comparison)a nd Li(thd)+ +3,5-PDC processes. The calculatedpatterns below the measured ones were produced from the reported crystal structures by using the VESTA [28] software. [15,17] sorptiono ft he hybridf ilm.…”

A lithium‐organic framework as a fluorescent sensor for detecting aluminum (III) ion

“…In general, the lightweight elements feature lighter atomic mass and smaller atomic size as compared with other metal elements . Therefore, those MOFs consisting Li centers possess relatively low framework density, which is favorable to the gas adsorption. For example, some Li‐MOFs show great potential in H 2 storage .…”

Metal–Organic Frameworks Constructed from Group 1 Metals (Li, Na) and Silicon-Centered Linkers

“…10 Since then, Li + -based MOFs have been reported using linkers as varied as amino acids, thiophenedicarboxylates, and anthraquinones. [11][12][13][14][15][16] These Li + -based MOFs have been shown to display properties such as luminescence, [17][18][19] gas uptake, [20][21] and even have potential applications as electrodes in Li batteries. 13 Some Na + -based MOFs have also been reported to possess similar properties to their Li + analogs such as gas sorption, luminescence, and anodes for Na batteries.…”