Direct Visualization of Homogeneous Chemical Distribution in Functional Polyradical Microspheres.

It is demonstrated that the postfunctionalization of solid polymeric microspheres can generate fully and throughout functionalized materials, contrary to the expectation that core-shell structures are generated. The full functionalization is illustrated on the example of photochemically generated microspheres, which are subsequently transformed into polyradical systems. Given the all-organic nature of the functionalized microspheres, characterization methods with high analytical sensitivity and spatial resolution are pioneered by directly visualizing the inner chemical distribution of the postfunctionalized microspheres based on characteristic electron energy loss signals in transmission electron microscopy (TEM). Specifically, ultrasonic ultramicrotomy is combined successfully with electron energy loss spectroscopy (EELS) and electron spectroscopic imaging (ESI) during TEM. These findings open a key avenue for analyzing all-organic low-contrast soft-matter material structures, while the specifically investigated system concomitantly holds promise as an all-radical solid-state functional material.