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Heteroatom functionalization of phenalenyl: synthesis, structures, and properties of hexa‐substituted phenalenyliums
Author(s) -
Ueda Akira,
Yoshida Kenta,
Suzuki Shuichi,
Fukui Kozo,
Nakasuji Kazuhiro,
Morita Yasushi
Publication year - 2011
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1916
Subject(s) - heteroatom , chemistry , hexa , density functional theory , tetraphenylborate , electrochemistry , cinnoline , cyclic voltammetry , crystal structure , photochemistry , crystallography , computational chemistry , organic chemistry , ring (chemistry) , ion , electrode
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.