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Postsynthetic Modification of Metal-Organic Frameworks for Selective C-H Functionalization and Acetylene Adsorption /

Record Type:	Electronic resources : Monograph/item
Title/Author:	Postsynthetic Modification of Metal-Organic Frameworks for Selective C-H Functionalization and Acetylene Adsorption // Aidan Flannery Greene.
Author:	Greene, Aidan Flannery,
Description:	1 electronic resource (137 pages)
Notes:	Source: Dissertations Abstracts International, Volume: 87-05, Section: B.
Contained By:	Dissertations Abstracts International87-05B.
Subject:	Chemistry. -
Online resource:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=32384486
ISBN:	9798297963177

Postsynthetic Modification of Metal-Organic Frameworks for Selective C-H Functionalization and Acetylene Adsorption /
Greene, Aidan Flannery,

Postsynthetic Modification of Metal-Organic Frameworks for Selective C-H Functionalization and Acetylene Adsorption /Aidan Flannery Greene. - 1 electronic resource (137 pages)

Source: Dissertations Abstracts International, Volume: 87-05, Section: B.

Metal-organic frameworks (MOFs) are constructed from inorganic clusters linked by organic struts to self-assemble into a three-dimensional framework. These porous crystalline materials have immense tunability owing to the facile modulation of their components, and their high porosity and good thermal and chemical robusticity making them ideal platforms for a wide array of applications. In particular, MOFs have achieved great interest for the design of heterogeneous catalysts and selective gas adsorbents.The versatility of MOF platforms may be extended via postsynthetic modification (PSM), wherein the linkers or nodes are altered after traditional solvothermal synthesis of the framework. This approach typically preserves the overall topological profile and porosity of the MOF while permitting the immobilization of new species to impart novel reactivity. Additionally, site isolation of transition metal complexes within heterogeneous platforms has been demonstrated to promote improved catalyst activity and stability compared to the homogeneous analogue. This thesis describes the PSM of MOFs to design heterogeneous catalysts for C-H functionalization and adsorbent materials for selective chemisorption of acetylene.Amine-functionalized MOFs MIL-101(Al)-NH2 and IRMOF-3 have been previously demonstrated to undergo facile PSM at their linkers to install novel reactive species within the framework. In Chapter 2, both frameworks are subjected to postsynthetic phospha-Mannich condensation using hydroxymethyl- and bis(hydroxymethyl)phosphine precursors to readily append phosphine moieties within the frameworks. The connectivity of the resulting solid-state phosphine ligands is dependent on the precursor used, and intra-framework crosslinking is observed for the bis(hydroxymethyl)phosphines. Following postsynthetic metalation with iridium, these materials were screened for C-H borylation of mono-functionalized arene substrates, and only the MIL-derived crosslinked materials proved competent for this transformation, demonstrating near quantitative turnover but no observed selectivity. The pendant phosphines were immediately cleaved upon exposure to the reaction conditions, and the IRMOF-derived materials suffered from minimal iridium incorporation owing to the tight pore windows hindering diffusion of the iridium precursor.Traditional C-H borylation catalysts employ iridium-bipyridine (bpy) or - phenthroline (phen) complexes, which exhibit extremely high activity but generate a statistical distribution of borylated arene concordant with the steric profile of the arene substituent. Modification of these ligands to impart selective functionalization via the formation of noncovalent interactions and/or steric hindrance with the substrate have been reported. In Chapter 3, MIL-101(Al)-NH2 is subjected to amide condensation at its amine sites to append bpy ligands within the framework at variable concentrations. The ancillary amine sites and coordinatively unsaturated aluminum-oxo nodes of the MOF were expected to induce noncovalent interactions with polar substrates and impart selectivity to the system. Following postsynthetic metalation with iridium, these materials were screened for C-H borylation of mono-functionalized arenes, but no selectivity was observed despite modest turnover. A dual PSM approach was then examined, in which urea groups and bpy ligands were sequentially condensed at the amine sites of MIL-101(Al)-NH2. Despite the drastic increase of the concentration of hydrogen bond donors within the framework, statistical product distribution was preserved.MOFs have been explored as platforms for selective adsorption of acetylene and other unsaturated hydrocarbons from industrial gas mixtures. The Plasma Pyrolysis Assembly (PPA) has been designed to recycle metabolic carbon dioxide for extended space missions, but necessitates the purification of a hydrogen stream via selective adsorption of acetylene and carbon monoxide. The postsynthetic metal incorporation (PSMI) of CuCl at the bpy ligands of UiO-67-bpy has been previously demonstrated to produce a material that strongly chemisorbs CO. Chapter 4 details the PSMI of UiO-67-bpy and MFU-4l-bpy with Cu(I) salts. Several of the materials exhibited improved acetylene adsorption relative to the parent materials, with the UiO materials outperforming their MFU-bpy counterparts, and the counteranion did not seem to have a large impact on the adsorption capacity. The majority of the copper is expected to bind at the bpy ligands, with several materials also exhibiting copper oversaturation attributed to the formation of [CuX2]- counteranions, or chelation of copper at defect sites within the framework. Unexpectedly, the parent MFU-4l was also found to undergo PSMI with CuCl, resulting in significant increases in acetylene and CO adsorption. The MOF is hypothesized to chelate CuI at the peripheral Zn-Cl sites of the metal nodes, suggesting that bpy ligands are not necessary for the development of these CuI adsorbents.

English

ISBN: 9798297963177Subjects--Topical Terms:

516420
Chemistry.
Subjects--Index Terms:

Metal-organic frameworks

Postsynthetic Modification of Metal-Organic Frameworks for Selective C-H Functionalization and Acetylene Adsorption /
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Additionally, site isolation of transition metal complexes within heterogeneous platforms has been demonstrated to promote improved catalyst activity and stability compared to the homogeneous analogue. This thesis describes the PSM of MOFs to design heterogeneous catalysts for C-H functionalization and adsorbent materials for selective chemisorption of acetylene.Amine-functionalized MOFs MIL-101(Al)-NH2 and IRMOF-3 have been previously demonstrated to undergo facile PSM at their linkers to install novel reactive species within the framework. In Chapter 2, both frameworks are subjected to postsynthetic phospha-Mannich condensation using hydroxymethyl- and bis(hydroxymethyl)phosphine precursors to readily append phosphine moieties within the frameworks. The connectivity of the resulting solid-state phosphine ligands is dependent on the precursor used, and intra-framework crosslinking is observed for the bis(hydroxymethyl)phosphines. Following postsynthetic metalation with iridium, these materials were screened for C-H borylation of mono-functionalized arene substrates, and only the MIL-derived crosslinked materials proved competent for this transformation, demonstrating near quantitative turnover but no observed selectivity. The pendant phosphines were immediately cleaved upon exposure to the reaction conditions, and the IRMOF-derived materials suffered from minimal iridium incorporation owing to the tight pore windows hindering diffusion of the iridium precursor.Traditional C-H borylation catalysts employ iridium-bipyridine (bpy) or - phenthroline (phen) complexes, which exhibit extremely high activity but generate a statistical distribution of borylated arene concordant with the steric profile of the arene substituent. Modification of these ligands to impart selective functionalization via the formation of noncovalent interactions and/or steric hindrance with the substrate have been reported. In Chapter 3, MIL-101(Al)-NH2 is subjected to amide condensation at its amine sites to append bpy ligands within the framework at variable concentrations. The ancillary amine sites and coordinatively unsaturated aluminum-oxo nodes of the MOF were expected to induce noncovalent interactions with polar substrates and impart selectivity to the system. Following postsynthetic metalation with iridium, these materials were screened for C-H borylation of mono-functionalized arenes, but no selectivity was observed despite modest turnover. A dual PSM approach was then examined, in which urea groups and bpy ligands were sequentially condensed at the amine sites of MIL-101(Al)-NH2. Despite the drastic increase of the concentration of hydrogen bond donors within the framework, statistical product distribution was preserved.MOFs have been explored as platforms for selective adsorption of acetylene and other unsaturated hydrocarbons from industrial gas mixtures. The Plasma Pyrolysis Assembly (PPA) has been designed to recycle metabolic carbon dioxide for extended space missions, but necessitates the purification of a hydrogen stream via selective adsorption of acetylene and carbon monoxide. The postsynthetic metal incorporation (PSMI) of CuCl at the bpy ligands of UiO-67-bpy has been previously demonstrated to produce a material that strongly chemisorbs CO. Chapter 4 details the PSMI of UiO-67-bpy and MFU-4l-bpy with Cu(I) salts. Several of the materials exhibited improved acetylene adsorption relative to the parent materials, with the UiO materials outperforming their MFU-bpy counterparts, and the counteranion did not seem to have a large impact on the adsorption capacity. The majority of the copper is expected to bind at the bpy ligands, with several materials also exhibiting copper oversaturation attributed to the formation of [CuX2]- counteranions, or chelation of copper at defect sites within the framework. Unexpectedly, the parent MFU-4l was also found to undergo PSMI with CuCl, resulting in significant increases in acetylene and CO adsorption. The MOF is hypothesized to chelate CuI at the peripheral Zn-Cl sites of the metal nodes, suggesting that bpy ligands are not necessary for the development of these CuI adsorbents.
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