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  1. A longstanding challenge in the field of optoelectronic materials, the effects of solid-state arrangement and morphology are still a prominent factor associated with small-molecule and polymer-based device performance. Here, mixed heterocyclic aromatic oligomers containing thiophene, furan and pyrazine are prepared alongside their methylated congeners. Their solution and solid-phase properties were studied via spectroscopic, electrochemical and single-crystal X-ray diffraction (XRD) analysis. Comparative analysis between solid-state packing arrangements and photophysical properties revealed optical band gaps as low as 1.7 eV with Stokes-shifts up to 130 nm and quantum yields of 12%. Results of the study aid in further understanding the effects of molecular and solid-state arrangements that give rise to unique optical and photophysical properties critical to enhancing optoelectronic behavior. 
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  2. Abstract

    The ever‐expanding need for renewable energy can be addressed in part by photocatalytic CO2reduction to give fuels via an artificial photosynthetic process driven by sunlight. A series of rhenium photocatalysts are evaluated in the photocatalytic CO2reduction reaction and via photophysical, electrochemical, and computational studies. The impact of various electron withdrawing substituents on the aryl group of the pyNHC‐aryl ligand along with the impact of extending conjugation along the backbone of the ligand is analyzed. A strong correlation between excited‐state lifetimes, photocatalytic rates, and computationally determined dissociation energy of the labile ligand of these complexes is observed. Additionally, computed orbital analysis provides an added understanding, which allows for prediction of the potential impact of an electron withdrawing substituent on photocatalysis.

     
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