This critical review is devoted to semiconducting and high spin polymers which are of great scientific interest in view of further development of the organic electronics and the emerging organic spintronic fields. Diversified synthetic strategies are discussed in detail leading to high molecular mass compounds showing appropriate redox (ionization potential (IP), electron affinity (EA)), electronic (charge carrier mobility, conductivity), optoelectronic (electroluminescence, photoconductivity) and magnetic (magnetization, ferromagnetic spin interactions) properties and used as active components of devices such as n- and p-channel field effect transistors, ambipolar light emitting transistors, light emitting diodes, photovoltaic cells, photodiodes, magnetic photoswitches, etc. Solution processing procedures developed with the goal of depositing highly ordered and oriented films of these polymers are also described. This is completed by the description of principal methods that are used for characterizing these macromolecular compounds both in solution and in the solid state. These involve various spectroscopic methods (UV-vis-NIR, UPS, pulse EPR), electrochemistry and spectroelectrochemistry, magnetic measurements (SQUID), and structural and morphological investigations (X-ray diffraction, STM, AFM). Finally, four classes of polymers are discussed in detail with special emphasis on the results obtained in the past three years: (i) high IP, (ii) high |EA|, (iii) low band gap and (iv) high spin ones.

This review gives an overview of the synthesis, photophysical properties, surface characterization/functionalization and some applications of chalcopyrite-type nanocrystals.

Cu-Fe-S nanocrystals exhibiting a strong localized surface plasmon resonance (LSPR) effect were synthesized for the first time. The elaborated reproducible preparation procedure involved copper(II) oleate, iron(III) stearate, and sulfur powder dissolved in oleylamine (OLA) as precursors. The wavelength of the plasmonic resonance maximum could be tuned by changing the Cu/Fe ratio in the resulting nanocrystals, being the most energetic for the 1:1 ratio (486 nm) and undergoing a bathochromic shift to ca. 1200 nm with an increase to 6:1. LSPR could also be observed in nanocrystals prepared from the same metal precursors and sulfur powder dissolved in 1-octadecene (ODE), provided that the sulfur precursor was taken in excess. Detailed analysis of the reaction mixture by chromatographic techniques, supplemented by mass spectrometry and (1)H NMR spectroscopy enabled the identification of the true chemical nature of the sulfur precursor in S/OLA, namely, (C18H35NH3(+))(C18H35NH-S8(-)), a reactive product of the reduction of elemental sulfur by the amine groups of OLA. In the case of the S/ODE precursor, the true precursors are much less reactive primary or secondary thioethers and dialkyl polysulfides.