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The Construction of Metal-Organic Fr...

Choi, Eunwoo.

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The Construction of Metal-Organic Framework with Active Backbones by the Utilization of Reticular Chemistry.

Record Type:	Language materials, printed : Monograph/item
Title/Author:	The Construction of Metal-Organic Framework with Active Backbones by the Utilization of Reticular Chemistry./
Author:	Choi, Eunwoo.
Description:	134 p.
Notes:	Source: Dissertation Abstracts International, Volume: 73-05, Section: B, page: 2933.
Contained By:	Dissertation Abstracts International73-05B.
Subject:	Chemistry, Organic. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3493446
ISBN:	9781267144829

The Construction of Metal-Organic Framework with Active Backbones by the Utilization of Reticular Chemistry.
Choi, Eunwoo.

The Construction of Metal-Organic Framework with Active Backbones by the Utilization of Reticular Chemistry. - 134 p.

Source: Dissertation Abstracts International, Volume: 73-05, Section: B, page: 2933.

Thesis (Ph.D.)--University of California, Los Angeles, 2011.

With the principles of reticular chemistry, metal-organic frameworks with ultra-high porosity, chiral-recognition unit as a chiral stationary phase, metalloporhyrins for enhanced hydrogen adsorption and an intrinsic conductivity to form porous conductors, have been prepared. This dissertation presents how the principles of reticular chemistry were utilized to achieve in the preparations of metal-organic frameworks with a large surface area and active backbones. Through the simple isoreticular (having the same framework topology) expansion from MOF-177 composed with 1,3,5-tris(4'-carboxyphenyl-)benzene (BTB3-) as the strut; MOF-200 was prepared with 4,4',4"-(benzene-1,3,5-triyl-tris(benzene-4,1-diy1))tribenzoic acid an extension from BTB3- by a phenylene unit to yield one of the most porous MOFs with a Langmuir surface area of 10,400 m2. and the lowest density of 0.22 cm3.g-1.

ISBN: 9781267144829Subjects--Topical Terms:

516206
Chemistry, Organic.

The Construction of Metal-Organic Framework with Active Backbones by the Utilization of Reticular Chemistry.
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020 $a 9781267144829
035 $a (MiAaPQ)AAI3493446
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100 1 $a Choi, Eunwoo. $3 1266203
245 1 4 $a The Construction of Metal-Organic Framework with Active Backbones by the Utilization of Reticular Chemistry.
300 $a 134 p.
500 $a Source: Dissertation Abstracts International, Volume: 73-05, Section: B, page: 2933.
500 $a Adviser: Omar M. Yaghi.
502 $a Thesis (Ph.D.)--University of California, Los Angeles, 2011.
520 $a With the principles of reticular chemistry, metal-organic frameworks with ultra-high porosity, chiral-recognition unit as a chiral stationary phase, metalloporhyrins for enhanced hydrogen adsorption and an intrinsic conductivity to form porous conductors, have been prepared. This dissertation presents how the principles of reticular chemistry were utilized to achieve in the preparations of metal-organic frameworks with a large surface area and active backbones. Through the simple isoreticular (having the same framework topology) expansion from MOF-177 composed with 1,3,5-tris(4'-carboxyphenyl-)benzene (BTB3-) as the strut; MOF-200 was prepared with 4,4',4"-(benzene-1,3,5-triyl-tris(benzene-4,1-diy1))tribenzoic acid an extension from BTB3- by a phenylene unit to yield one of the most porous MOFs with a Langmuir surface area of 10,400 m2. and the lowest density of 0.22 cm3.g-1.
520 $a A successful thermal polymerization reaction at 325 °C inside of the pores of highly porous MOF, MOF-177, was performed and verified the integrity of the MOF structure even after the thermal reaction. 1,4-Diphenylbutadiyne that is known to polymerize upon heating to form a conjugated backbone was impregnated via solution-diffusion into MOF-177 and then subsequently polymerized by heat to form polymer impregnated MOF-177. Characterization was carried out using powder X-ray diffraction and volumetric sorption analyzer.
520 $a MOF-1020 with a linear quaterphenyl dicarboxylate-based strut was designed to contain a chiral bisbinaphthyl crown-ether moiety for alkyl ammonium resolution was precisely placed into a Zn4O(CO2)6-based cubic MOF structure. Unfortunately, the chiral resolution was not achieved due to the sensitivity and the pore environment of MOF-1020. However, an interesting phenomenon was observed, where the loss of crystallinity occurs upon solvent removal while the crystallites remain shiny and crystalline, but it readily is restored upon re-solvation of the crystallites. This rare phenomenon was studied by powder X-ray diffraction and supported by gas adsorption and thermogravimetric analysis.
520 $a Layered MOFs with metalloporphyrins with Zn, Cu, Co and Fe at their +2 oxidation states as struts were prepared to facilitate non-structural metal sites and tested for hydrogen adsorption and the binding enthalpies. Steep uptakes are indeed observed, but rather due to the optimal interlayer distance of 9 A for dihydrogen, and the binding enthalpies are 6.7 -- 7.6 kJ . mo1-1 which are not ·extraordinary. Although the metals did not seem to play a large role, a trend was observed where the binding enthalpies increase as the metals in the metalloporphyrins go from late to early transition metals.
520 $a With the concept of conductive metal oxides, a journey of constructing conductive MOFs was taken by attempting the formation of metal-carbon bonds by linking transition metal ions with conjugated organic struts which are 1,4-benzenediisonitrile, 1,4-benzenediethynylide and p-cyanophenylethynylide. Among the attempted systems, a reaction of Cr(III) and 1,4-benzenediethynylide yielded an amorphous material with a BET (Brunauer-Emmett-Teller) surface area of 80 m2.g-1, hydrogen uptake of 47 cm 3. g-1 and a resistance of 20 MO. Also a crystalline compound was prepared by mimicking Prussian blue by using p-cyanophenylethynylide where one end can bind metal with ethynylic carbon and the other end with the cyano nitrogen by following the similar synthesis of Prussian blue analogues.
520 $a The principles of reticular chemistry are demonstrated through each chapter and show how powerful and beneficial reticular chemistry is by allowing the predetermination of the structure and function. The details of the ways to approach an ideal compound and the synthetic aspects are also described in this dissertation.
590 $a School code: 0031.
650 4 $a Chemistry, Organic. $3 516206
650 4 $a Chemistry, Inorganic. $3 517253
650 4 $a Engineering, Materials Science. $3 1017759
690 $a 0490
690 $a 0488
690 $a 0794
710 2 $a University of California, Los Angeles. $3 626622
773 0 $t Dissertation Abstracts International $g 73-05B.
790 $a 0031
791 $a Ph.D.
792 $a 2011
793 $a English
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3493446