2017
DOI: 10.1021/acs.inorgchem.7b00698
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Gas–Solid Chemisorption/Adsorption and Mechanochemical Selectivity in Dynamic Nonporous Hybrid Metal Organic Materials

Abstract: Gas-solid chemisorption of HCl and adsorption of MeOH/EtOH by nonporous chiral copper(II) coordination complexes 1·MeOH and 1″·MeOH occur in a cooperative and dynamic manner to give solvated second sphere adducts 1'·MeOH/EtOH. The chemisorption process involves dramatic atomic rearrangements in the crystalline state upon cleavage and formation of H-Cl, N-H, Cu-N, and Cu-Cl coordination and covalent bonds from the gas and solid state, respectively. Using mechanochemistry, the chloride-bridged coordination compl… Show more

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Cited by 34 publications
(16 citation statements)
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“…The exposure of 1 to HCl vapors is accompanied by a change of color of the crystals, that starts in seconds, from blue (compound 1 , see Figure a) to yellow (compound 2 , see Figure a), indicative of a change in the coordination environment of the Cu centers, as previously observed . The process is completed in 0.5 h. Despite the many structural modifications that occur upon the adsorption of the gas molecules, we have been able to isolate a single‐crystal and solve the structure by X‐ray single‐crystal diffraction, revealing that 2 is composed of distorted tetrahedral [CuCl 4 ] 2− anions and [imH 2 ] + cations, resulting in a nonporous molecular material of formula (imH 2 ) 2 [CuCl 4 ], also accessible through conventional synthetic routes .…”
Section: Resultssupporting
confidence: 62%
“…The exposure of 1 to HCl vapors is accompanied by a change of color of the crystals, that starts in seconds, from blue (compound 1 , see Figure a) to yellow (compound 2 , see Figure a), indicative of a change in the coordination environment of the Cu centers, as previously observed . The process is completed in 0.5 h. Despite the many structural modifications that occur upon the adsorption of the gas molecules, we have been able to isolate a single‐crystal and solve the structure by X‐ray single‐crystal diffraction, revealing that 2 is composed of distorted tetrahedral [CuCl 4 ] 2− anions and [imH 2 ] + cations, resulting in a nonporous molecular material of formula (imH 2 ) 2 [CuCl 4 ], also accessible through conventional synthetic routes .…”
Section: Resultssupporting
confidence: 62%
“…[29,30] The Cu The exposure of 1 to HCl vapors is accompanied by a change of color of the crystals, that starts in seconds, from blue (compound 1, see Figure 1a) to yellow (compound 2, see Figure 2a), indicative of a change in the coordination environment of the Cu centres, as previously observed. [15,17,[31][32][33][34][35][36][37] The process is completed in 0.5 hours. Despite the many structural modifications that occur upon the adsorption of the gas molecules, we have been able to isolate a single-crystal and solve the structure by X-ray single-crystal diffraction, revealing that 2 is composed by distorted tetrahedral [CuCl4] 2-anions and [imH2] + cations, resulting in a nonporous molecular material of formula (imH2)2[CuCl4], also accessible through conventional synthetic routes.…”
Section: Resultsmentioning
confidence: 99%
“…The exposure of 1 to HCl vapors is accompanied by a change of color of the crystals, that starts in seconds, from blue (compound 1,s ee Figure 1a)t oy ellow (compound 2,s ee Figure 2a), indicative of ac hange in the coordination environment of the Cu centers, as previously observed. [15,17,[31][32][33][34][35][36][37] The processi sc ompleted in 0.5 h. Despite the many structural modifications that occur upon the adsorption of the gas molecules, we have been able to isolate as ingle-crystal and solve the structure by X-ray single-crystal diffraction, revealing that 2 is composed of distorted tetrahedral [CuCl 4 ] 2À anions and [imH 2 ] + cations,r esulting in an onporous molecular material of formula (imH 2 ) 2 [CuCl 4 ], also accessible through conventional synthetic routes. [38] Three molecules of HCl are incorporated to the crystal structure of 1,w hereas one imidazole ligand is released as amorphous imidazolium chloride ( Figure S1, Supporting Information).…”
Section: Resultsmentioning
confidence: 99%