Utilizing an N-annulated perylene diimide (NPDI) organic building block, this thesis reports on the design and synthesis of dimeric and tetrameric NPDI materials using a sustainable direct (hetero)arylation (DHA) cross coupling synthetic method. Ultimately, these materials are designed for n-type organic field effect transistor (OFET) devices to use in smart packaging, intended for temperature sensing technology. Chapter one surveys important progress in the design, synthesis, and solution processing of NPDI-type materials to fabricate printed organic electronics in a more sustainable and eco-friendly manner. Following an optimization of the sustainable DHA synthetic method to streamline a series of dimeric NPDIs (chapter two) and tetrameric NPDIs (chapter three) that increase solubility in solvents that encourage greener processing. All compounds are characterized through physical analysis (e.g., 1H NMR and 13C NMR spectroscopy, MALDI-TOF mass spectrometry, CHN elemental analysis), optoelectronic analysis using UV-Vis spectroscopy (UV-Vis), electrochemical analysis using cyclic voltammetry (CV), and finally, a solvent solubility determination.