Skip to Main Content
 

Global Search Box

 
 
 
 

Files

File List


LAB-Thesis.pdf (46.5 MB)

ETD Abstract Container

Abstract Header

Synthesis of Dehydrobenzoannulene-Based Covalent Organic Frameworks

Baldwin, Luke Adam
http://orcid.org/0000-0002-7787-238X
http://rave.ohiolink.edu/etdc/view?acc_num=osu1491561788473597

Abstract Details

2017, Doctor of Philosophy, Ohio State University, Chemistry.
Our group is interested in covalent organic frameworks (COFs), a class of highly crystalline, well-ordered 2D and 3D polymers with predictable pore sizes, photophysical properties, and well-defined structures. Other materials that interested our group include graphyne and graphdiyne, as well as substructures of these carbon allotropes. Our research centers on the design and synthesis of novel, functional, 2D and 3D COFs with macrocycles for post-synthetic alterations Specifically, the incorporation of DBA[12] and DBA[18] macrocycles into crystalline materials intrigued our group. We first started by synthesizing two DBA based COFs with a mixture of alternating triangular and hexagonal pores using a C2-symmetric diboronic acid linker. After synthesis we found that these COFs were extremely thermally stable, highly porous, and crystalline. Incorporation of DBA into the polymers also allowed for highly fluorescent materials that had micropores (0.4 to 0.5 nm) from the DBA units, and mesopores (3.2 to 3.6 nm) from the hexagonal pore of the COF. Turning our attention to three component COFs we reported the synthesis of three novel COFs that contained a homogeneous and heterogeneous distribution of DBA vertex units. The COFs were synthesized using different ratios of DBA[12], DBA[18], and diboronic acid to yield three COFs with high crystallinity, and interesting luminescent properties. This protocol showed that the pore size of COFs can be altered by incorporating different mixtures of DBA vertex units in the polymer. After our success in 2D COFs we turned our attention to constructing metalated three-dimensional COFs. We synthesized a highly porous DBA based 3D COF with a record high surface area (SABET = 5083 m2g-1) and record low density (0.13 g/cm3) for a COF material. Metalation of the DBA-3D COF with Ni resulted in minimal reduction to the surface area, and retention of crystallinity. We explored these COFs for the uptake of ethane and ethylene gas to determine whether the incorporation of metal had any impact on the storage capacity.
Psaras McGrier (Advisor)
199 p.
Chemistry; Materials Science; Organic Chemistry; Polymer Chemistry
COFs; porous; crystalline; metalation; framework; annulene

Recommended Citations

Citations

  • Baldwin, L. A. (2017). Synthesis of Dehydrobenzoannulene-Based Covalent Organic Frameworks [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1491561788473597

    APA Style (7th edition)

  • Baldwin, Luke . Synthesis of Dehydrobenzoannulene-Based Covalent Organic Frameworks. 2017. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1491561788473597.

    MLA Style (8th edition)

  • Baldwin, Luke . "Synthesis of Dehydrobenzoannulene-Based Covalent Organic Frameworks." Doctoral dissertation, Ohio State University, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=osu1491561788473597

    Chicago Manual of Style (17th edition)

osu1491561788473597
337
© 2017, all rights reserved.
This open access ETD is published by The Ohio State University and OhioLINK.