Search

Metal-organic frameworks (MOFs) form a unique platform for operation with data using ReRAM technology. Here we report on a large-scale fabrication of a MOF-based ReRAM array with 6 × 6 cells, demonstrating 50% variation in their electronic parameters. Despite this inhomogeneity, such a "non-ideal" ReRAM array is used for recording binary information followed by deep learning processes to achieve 95% accuracy of reading. Next, the same ReRAM array is used to record numbers (from 0 to 15) followed by the operation of addition. For the correct performance of such an analogue algorithm, we determine a set of unique coefficients for each ReRAM cell, allowing us to use this set as an encrypted key to get access to logical operations. The obtained results, thereby, demonstrate the possibility of "non-ideal" MOF-based ReRAM for low error reading of information coupled with encrypted logical operations.

A new "bicycle helmet"-like copper(ii),sodiumphenylsilsesquioxane Ph12Si12O12(OH)(O-)11Cu5Na(bipy)3(H2O) exhibited high catalytic efficiency in two homogeneous reactions: (i) functionalization of C-H compounds; (ii) formation of benzamides from alcohols.

The first Ni(ii)-based metallagermaniumsesquioxane cage compound [(PhGeO1.5)10(NiO)4(NaO0.5)2] presents a sandwich-like structure where two germsesquioxane cages are linked through an {NiO}4 core and exhibits slow dynamics of the magnetization.

Herein, the effect of replacement of the surrounding solvent and/or the partial substitution of sodium ions in the cage-like copper, sodium phenylsilsesquioxane [(PhSiO 1.5 ) 12 (CuO) 4 (NaO 0.5 ) 4 (n-BuOH) 6 ] 1 with a globular structure was investigated; the synthesis of ten new derivatives of complex 1 was performed, and their crystal structures were determined. Solvate replacement of n-butanol in 1 with dimethyl sulfoxide, acetonitrile, 1,4-dioxane/EtOH, and 1,4-dioxane/PhCN afforded the complexes [(PhSiO 1.5 ) 12 (CuO) 4 (NaO 0.5 ) 4 (DMSO) 8 ] (2), [(PhSiO 1.5 ) 12 (CuO) 4 (NaO 0.5 ) 4 (MeCN) 6 (H 2 O) 2 ]·2MeCN (3), [(PhSiO 1.5 ) 12 (CuO) 4 (NaO 0.5 ) 4 (C 4 H 8 O 2 )(EtOH) 4 ]·0.5EtOH (4), and [(PhSiO 1.5 ) 12 (CuO) 4 (NaO 0.5 ) 4 (C 4 H 8 O 2 ) 4 (H 2 O) 3 ]·2PhCN·2C 4 H 8 O 2 ·H 2 O (5). In an aqueous solution of EtOH, a rearrangement reaction occurred instead of substitution, which resulted in a new complex, [(PhSiO 1.5 ) 10 (CuO) 2 (NaO 0.5 ) 2 (H 2 O) 6 ] (6), with a cooling tower molecular structure. Transmetalation reactions of 1 with KCl or CsF resulted in the formation of the trimetallic complexes [(PhSiO 1.5 ) 12 (CuO) 4 (NaO 0.5 ) 2 (KO 0.5 ) 2 (DMF) 6 ] (7), [(PhSiO 1.5 ) 12 (CuO) 4 (NaO 0.5 )(CsO 0.5 ) 3 (DMF) 4 (DMSO)(H 2 O)]·1.5DMF (8), [(PhSiO 1.5 ) 12 (CuO) 4 (NaO 0.5 ) 2 (CsO 0.5 ) 2 (DMF) 8 ]·0.5H 2 O (9), and [(PhSiO 1.5 ) 12 (CuO) 4 (NaO 0.5 ) 3 (CsO 0.5 )(DMF) 4 ] (10). The replacement of sodium ions of 1 by the bulky non-metallic cation PhMe 3 N + upon the interaction of 1 with PhMe 3 NCl in a MeCN medium afforded the complex (PhNMe 3 ) 2 [(PhSiO 1.5 ) 12 (CuO) 4 (NaO 0.5 ) 2 (O)(MeCN) 4 ]·4MeCN (11). X-ray analysis confirmed the successful replacement of terminal butanol molecules in all complexes and the stability of the globular cage of the parent complex under the reaction conditions, with the exceptions of complexes 6 and 9 that underwent an unprecedented reorganization of cage metallasilsesquioxane (CLMS) units into the cooling tower and sandwich-like cages, respectively. The stability of the cage during substitution reactions provides the first experimental evidence that polynuclear cage metallasilsesquioxanes can act as building blocks for the construction of coordination polymers, opening new ways for the synthesis of hybrid CLMS-based frameworks. In particular, the compounds 4, 6, 7, 9, and 10 are one-dimensional coordination polymers, and 5 and 8 are two-dimensional coordination polymers with a square lattice topology. A magnetism study of the coordination polymer compounds 5, 6, 8, and 9 showed antiferromagnetic behavior between copper centers.