Synthesis and characterization of conjugated materials with phosphorus

<p>In this work, the synthesis and characterization of three series of conjugated compounds, 2,6-di-R-benzo[1,2-d:4,5-d’]bisoxaphospholes (R2-BBOPs), 2-R-naphtho(2,3-d)oxaphospholes (R-NOPs) and 2,7-di-R-naphtho[1,2-d:5,6-d’]bisoxaphospholes (R2-NBOPs) are reported. The investigation of BBOPs, NOPs and NBOPs extensively developed research of ¿¿-conjugated materials with P=C bonds. </p><p>These materials were fully characterized via: multi-nuclear magnetic resonance spectroscopy (NMR), melting points (MP), elemental analyses (EA) or high resolution mass spectroscopy (HRMS), ultraviolet-visible spectroscopy (UV-vis) and fluorescence spectroscopy. Some materials were characterized by cyclic voltammetry experiments (CV), and the solid state structures of selected materials were also determined by single-crystal X-ray diffraction analysis (X-ray). Density functional theory (DFT) calculations were employed as well. The comparisons of three series of compounds each other, as well as the relative compounds 2-R-benzo(1,3-d)oxaphospholes (R-BOPs) will also be discussed in this work. </p><p>Single-crystal structures of these conjugated materials, especially containing aryl substituents, display a coplanar configuration with almost 180¿¿ torsion angle . </p><p>The UV-vis absorption spectra of these conjugated compounds display absorption maxima peaks, featuring the ¿¿-¿¿* transition between 304 nm to 387 nm, while the fluorescence emission spectra of these materials exhibit emission maxima peaks between 367 nm to 470 nm. Red shifts of both absorption and emission maxima were observed between alkyl and aryl substituted oxaphospholes (OPs). It demonstrates that aryl substituted compounds performed smaller HOMO/LUMO gaps than alkyl substituted counterparts.</p><p>Cyclic voltammetry experiments display initial reduction waves (Epc, V vs. SCE, conc. is 0.001 M in THF) at -1.90 (Ph2-NBOP), -1.92 (Ph-NOPs), -2.02 (Ph-BOPs), and -2.12 ((2,4,6-Me3-C6H2)2-BBOPs), respectively. It reveals that initial reduction of Ph2-NBOP occurred more readily than counterparts of NOP, BBOP and BOP, which is attributed to its lower ¿¿* orbital.</p>

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Chemistry

Grantor dc:publisher

Case Western Reserve University School of Graduate Studies

Year dc:date

2013

Author dc:creator

• Laughlin, Feng Li

Contributors dc:contributor

• Thomas, Gray
• Protasiewicz, John

• Chemistry
• benzobisoxaphosphole
• naphthoxaphosphole
• naphthobisoxaphosphole
• conjugated material
• fluorescence

Statement dc:rights

• unrestricted
• This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws.

Language dc:language

English

Repository record dc:identifier

http://rave.ohiolink.edu/etdc/view?acc_num=case1345483824

OAI identifier oai:identifier

oai:etd.ohiolink.edu:case1345483824