Tethered Blatter Radical for Molecular Grafting: Synthesis of 6-Hydroxyhexyloxy, Hydroxymethyl, and Bis(hydroxymethyl) Derivatives and Their Functionalization

Abstract

Synthetic access to 7-CF3-1,4-dihydrobenzo[e][1,2,4]triazin-4-yl radicals containing 4-(6-hydroxyhexyloxy)phenyl, 4-hydroxymethylphenyl or 3,5-bis(hydroxymethyl)phenyl groups at the C(3) position and their conversion to tosylates and phosphates are described. The tosylates were used to obtain disulfides and an azide with good yields. The Blatter radical containing the azido group underwent a copper(I)-catalyzed azide–alkyne cycloaddition with phenylacetylene under mild conditions, giving the [1,2,3]triazole product in 84% yield. This indicates the suitability of the azido derivative for grafting Blatter radical onto other molecular objects via the CuAAC “click” reaction. The presented derivatives are promising for accessing surfaces and macromolecules spin-labeled with the Blatter radical.

Thermally induced dimensionality changes in derivatives of a “super stable” Blatter radical

“…These radicals constitute a class of exceptionally stable organic radicals, which have been explored 26 as active elements in a number of fields of contemporary science and technology, such as spintronics, [27][28][29] sensors, 30,31 organic batteries, [32][33][34] metalorganic frameworks, 30 thermoelectric systems, 35 and photoconductive liquid crystals. [36][37][38][39][40] In this context, a Blatter radical was substituted with the CF 3 group in the C(3) 2,22,[41][42][43] or C(7) [21][22][23][33][34][35][43][44][45][46][47][48][49] (e.g. 1a, Fig.…”