Publication Date:
2011-08-23
Description:
Two kinds of heteroatom-functionalized phenalenyl derivatives, 1,4,7-trimethoxy-3,6,9-tris( n -propylamino)phenalenylium 1 + and 3,4,6,7-tetramethoxy-1,9-dithiophenalenylium 2 + , have been synthesized and isolated as air-stable tetraphenylborate (BPh 4 − ) salts. The structural and electronic features of these phenalenyliums, which are rare examples of the phenalenyl derivatives where all of the six α-carbons are substituted by heteroatom functional groups, were experimentally investigated by using X-ray crystal structure analysis, cyclic voltammetry, and ultraviolet-visible and fluorescence measurements with the help of density functional theory calculations. On the basis of these results, we evaluated the heteroatom effects in the phenalenylium systems by detailed comparison of the structure and physical properties of 1 + and 2 + with those of 2,5,8-tri- tert -butyl phenalenylium 3 + without heteroatoms. These molecular-level investigations demonstrated that the electrochemical and optical properties and solid-state packing structures of the phenalenylium systems can be easily tuned by the heteroatom substituents. Copyright © 2011 John Wiley & Sons, Ltd. Two kinds of heteroatom-functionalized phenalenyl derivatives, 1,4,7-trimethoxy-3,6,9-tris( n -propylamino)phenalenylium 1 + and 3,4,6,7-tetramethoxy-1,9-dithiophenalenylium 2 + , have been synthesized and isolated as air-stable tetraphenylborate salts (see Figure). The structural and electronic features were experimentally investigated by X-ray crystal structure analysis, cyclic voltammetry, and UV-vis and fluorescence measurements with the help of DFT calculations. Furthermore, the heteroatom effects attributable to the electron-donating alkoxy, amino, or thio groups introduced at all of the α-carbons in the phenalenylium skeleton were evaluated in detail.
Print ISSN:
0894-3230
Electronic ISSN:
1099-1395
Topics:
Chemistry and Pharmacology
,
Physics
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