Enhancing the Photochemical Stability of N,C-Chelate Boryl Compounds: C-C Bond Formation versus C=C Bond cis,trans-Isomerization

被引:74
作者
Baik, Chul [1 ]
Hudson, Zachary M. [1 ]
Amarne, Hazem [1 ]
Wang, Suning [1 ]
机构
[1] Queens Univ, Dept Chem, Kingston, ON K7L 3N6, Canada
基金
加拿大自然科学与工程研究理事会;
关键词
3-COORDINATE ORGANOBORON COMPOUNDS; POLYMER SOLAR-CELLS; OPTICAL-PROPERTIES; LUMINESCENT PROPERTIES; METAL-COMPLEXES; BORON; ELECTROLUMINESCENCE; BLUE;
D O I
10.1021/ja906430s
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
N,C-Chelate boron compounds such as B(ppy)Mes(2) (ppy = 2-phenylpyridyl, Mes = mesityl) have been recently shown to undergo a facile and reversible C-C/C-B bond rearrangement upon irradiation with UV-light, quenching the emission of the sample and limiting their use in optoelectronic devices. To address this problem, four molecules have been synthesized in which the pi-conjugation is extended using either vinyl or acetylene linkers. These compounds, (ph-C C-ppy)BMes(2) (B1A), (ph-CH=CH-ppy)BMes(2) (B1), [p-bis(ppy-CH=CH)benzone](BMes(2))(2) (B2), and [1,3,5-tris(ppy-CH=CH)benzene](BMes(2))(3) (B3) have been fully characterized by NMR and single-crystal X-ray diffraction analyses. All four compounds are light yellow and emit blue or blue-green light upon UV irradiation. The acetylene compound B1 A has been found to exhibit photochemical instability the same as that of the parent chromophore B(ppy)Mes(2). In contrast, all of the olefin-substituted compounds are photochemically stable, instead undergoing cis-trans isomerization exclusively upon exposure to UV light. Experimental and TD-DFT computational results establish that the presence of the olefinic bond in B1-B3 provides an alternate energy dissipation pathway for the B(ppy)Mes(2) chromophore, stabilizing the molecule toward photochromic switching via cis-trans isomerization. Furthermore, the incorporation of a cis-trans isomerization pathway may prove to be a useful strategy for the stabilization of photochemically unstable chromophores in other pi-systems as well.
引用
收藏
页码:14549 / 14559
页数:11
相关论文
共 77 条
[51]   Influence of Molecular Structure And Film Properties on the Water-Stability and Sensor Characteristics of Organic Transistors [J].
Roberts, Mark E. ;
Mannsfeld, Stefan C. B. ;
Tang, Ming Lee ;
Bao, Zhenan .
CHEMISTRY OF MATERIALS, 2008, 20 (23) :7332-7338
[52]   Visible-light photochromism of triarylamine- or ferrocene-bound diethynylethenes that switches electronic communication between redox sites and luminescence [J].
Sakamoto, Ryota ;
Kume, Shoko ;
Nishihara, Hiroshi .
CHEMISTRY-A EUROPEAN JOURNAL, 2008, 14 (23) :6978-6986
[53]  
Saltiel J., 1973, ORG PHOTOCHEM, V3, P1
[54]  
Sheldrick G.M., 2003, SHELXTL 6 14
[55]   Organic materials for electronic and optoelectronic devices [J].
Shirota, Y .
JOURNAL OF MATERIALS CHEMISTRY, 2000, 10 (01) :1-25
[56]  
Smith M. B., 2001, ADV ORGANIC CHEM REA
[57]   AB-INITIO CALCULATION OF VIBRATIONAL ABSORPTION AND CIRCULAR-DICHROISM SPECTRA USING DENSITY-FUNCTIONAL FORCE-FIELDS [J].
STEPHENS, PJ ;
DEVLIN, FJ ;
CHABALOWSKI, CF ;
FRISCH, MJ .
JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (45) :11623-11627
[58]   Enhancing electron accepting ability of triarylboron via π-conjugation with 2,2′-bipy and metal chelation:: 5,5′-bis(BMes2)-2,2′-bipy and its metal complexes [J].
Sun, Yi ;
Ross, Nicole ;
Zhao, Shu-Bin ;
Huszarik, Krista ;
Jia, Wen-Li ;
Wang, Rui-Yao ;
Macartney, Donal ;
Wang, Suning .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (24) :7510-+
[59]   ELECTROLUMINESCENCE OF DOPED ORGANIC THIN-FILMS [J].
TANG, CW ;
VANSLYKE, SA ;
CHEN, CH .
JOURNAL OF APPLIED PHYSICS, 1989, 65 (09) :3610-3616
[60]   ORGANIC ELECTROLUMINESCENT DIODES [J].
TANG, CW ;
VANSLYKE, SA .
APPLIED PHYSICS LETTERS, 1987, 51 (12) :913-915