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The molecular transport and intercal...

Hogan, Greg Anthony.

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The molecular transport and intercalation of guest molecules into hydrogen-bonded metal-organic frameworks (HMOFs).

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	The molecular transport and intercalation of guest molecules into hydrogen-bonded metal-organic frameworks (HMOFs)./
作者:	Hogan, Greg Anthony.
出版者:	Ann Arbor : ProQuest Dissertations & Theses, : 2010,
面頁冊數:	445 p.
附註:	Source: Dissertation Abstracts International, Volume: 71-12, Section: B, page: 7429.
Contained By:	Dissertation Abstracts International71-12B.
標題:	Inorganic chemistry. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3427634
ISBN:	9781124321936

The molecular transport and intercalation of guest molecules into hydrogen-bonded metal-organic frameworks (HMOFs).
Hogan, Greg Anthony.

The molecular transport and intercalation of guest molecules into hydrogen-bonded metal-organic frameworks (HMOFs). - Ann Arbor : ProQuest Dissertations & Theses, 2010 - 445 p.

Source: Dissertation Abstracts International, Volume: 71-12, Section: B, page: 7429.

Thesis (Ph.D.)--University of Missouri - Saint Louis, 2010.

The process of molecular transport and intercalation has been widely studied for many years, resulting in the discovery of molecular frameworks that are capable of hosting guest molecules or ions. Layered and porous metal-organic frameworks (MOFs) have been found to have applications in the field of catalysis, storage, separations, and ion-exchange. More recently, molecular components with peripheral hydrogen-bonding moieties have been used to affect the synthesis of hydrogen-bonded metal-organic frameworks (HMOFs) as an alternative to MOFs, which are interconnected via coordinate-covalent bonds. While MOFs are perhaps stronger materials, HMOFs have the advantage of being easily modifiable and more flexible. Because HMOFs have not been extensively studied for their ability to host molecules, and because their ability to withstand guest loss and guest exchange is essentially unknown, here we report the synthesis and molecular transport properties of both close-packed and porous HMOFs.

ISBN: 9781124321936Subjects--Topical Terms:

3173556
Inorganic chemistry.

The molecular transport and intercalation of guest molecules into hydrogen-bonded metal-organic frameworks (HMOFs).
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245 1 4 $a The molecular transport and intercalation of guest molecules into hydrogen-bonded metal-organic frameworks (HMOFs).
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500 $a Source: Dissertation Abstracts International, Volume: 71-12, Section: B, page: 7429.
500 $a Adviser: Alicia M. Beatty.
502 $a Thesis (Ph.D.)--University of Missouri - Saint Louis, 2010.
520 $a The process of molecular transport and intercalation has been widely studied for many years, resulting in the discovery of molecular frameworks that are capable of hosting guest molecules or ions. Layered and porous metal-organic frameworks (MOFs) have been found to have applications in the field of catalysis, storage, separations, and ion-exchange. More recently, molecular components with peripheral hydrogen-bonding moieties have been used to affect the synthesis of hydrogen-bonded metal-organic frameworks (HMOFs) as an alternative to MOFs, which are interconnected via coordinate-covalent bonds. While MOFs are perhaps stronger materials, HMOFs have the advantage of being easily modifiable and more flexible. Because HMOFs have not been extensively studied for their ability to host molecules, and because their ability to withstand guest loss and guest exchange is essentially unknown, here we report the synthesis and molecular transport properties of both close-packed and porous HMOFs.
520 $a Layered materials can mimic the behavior of naturally occurring clays, where guest molecules are absorbed and the layer will expand to accommodate the entering guest molecule. We have created a clay mimic composed of a metal pyridine-dicarboxylates and ammonium counterions (a layered HMOF), which is suitable for studying the ability of such materials to absorb guest molecules. We can control the distance of the interlayer region, as well as the chemical nature (hydrophobic or hydrophilic) by varying the organic amine. The metal complex contains axial water ligands that are replaceable, and such ligand exchange has precedence in coordination polymer (MOF) systems, and has been termed "coordinative intercalation". Using the synthesized layered material we examined the process of intercalation, having chosen a variety of guest molecules ranging from alkyl to aryl molecules, each of which have substituents varying in size, shape and electronics. The first set of guest molecules are non-coordinating and are theoretically capable of entering the layer and anchoring freely through the use of non-covalent interactions. The second set of guest molecules contain a pyridine moiety that can exchange with the coordinated water ligand through coordinative-intercalation. The products have been characterized by TGA, DSC, UV-Vis, and powder XRD.
520 $a Further work was dedicated to examining porous materials, which were created using organic diamines, rather than simple primary amines, as starting materials. The resulting diammonium cations act as pillars, forming open channels. The predefined channel dimensions allow the insertion of specific sized guest molecules. The walls of the channel are close-packed, so that in theory guest molecules can travel in one direction through the solid. Using the synthesized pillared structure we investigated guest inclusion and selectivity through the process of co-crystallization. The stability of the pillared structure in the absence of guests is also reported, as well as the potential for the empty pillared structure to withstand guest re-insertion and removal.
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