Phosphonate Chelators for Medicinal Metal Ions

A family of phosphonate-bearing chelators was synthesized to study their potential in metal-based (radio)- pharmaceuticals. Three ligands (H6phospa, H6dipedpa, H6eppy; structures illustrated in manuscript) were fully characterized, including X-ray crystallographic structures of H6phospa and H6dipedpa. NMR spectroscopy techniques were used to confirm the complexation of each ligand with selected trivalent metal ions. These methods were particularly useful in discerning structural information for Sc3+ and La3+ complexes. Solution studies were conducted to evaluate the complex stability of 15 metal complexes. As a general trend, H6phospa was noted to form the most stable complexes, and H6eppy associated with the least stable complexes. Moreover, In3+ complexes were determined to be the most stable, and complexes with La3+ were the least stable, across all metals. Density functional theory (DFT) was employed to calculate structures of H6phospa and H6dipedpa complexes with La3+ and Sc3+. A comparison of experimental 1 H NMR spectra with calculated 1 H NMR spectra using DFT-optimized structures was used as a method of structure validation. It was noted that theoretical NMR spectra were very sensitive to a number of variables, such as ligand configuration, protonation state, and the number/orientation of explicit water molecules. In general, the inclusion of an explicit second shell of water molecules qualitatively improved the agreement between theoretical and experimental NMR spectra versus a polarizable continuum solvent model alone. Formation constants were also calculated from DFT results using potential-energy optimized structures. Strong dependence of molecular free energies on explicit water molecule number, water molecule configuration, and protonation state was observed, highlighting the need for dynamic data in accurate first-principles calculations of metal−ligand stability constants

Color‐Selective Printed Organic Photodiodes for Filterless Multichannel Visible Light Communication

Future lightweight, flexible, and wearable electronics will employ visible-lightcommunication schemes to interact within indoor environments. Organic photodiodes are particularly well suited for such technologies as they enable chemically tailored optoelectronic performance and fabrication by printing techniques on thin and flexible substrates. However, previous methods have failed to address versatile functionality regarding wavelength selectivity without increasing fabrication complexity. This work introduces a general solution for printing wavelength-selective bulk-heterojunction photodetectors through engineering of the ink formulation. Nonfullerene acceptors are incorporated in a transparent polymer donor matrix to narrow and tune the response in the visible range without optical filters or light-management techniques. This approach effectively decouples the optical response from the viscoelastic ink properties, simplifying process development. A thorough morphological and spectroscopic investigation finds excellent charge-carrier dynamics enabling state-of-the-art responsivities >10² mA W⁻¹ and cutoff frequencies >1.5 MHz. Finally, the color selectivity and high performance are demonstrated in a filterless visible-light-communication system capable of demultiplexing intermixed optical signals

Color‐Selective Printed Organic Photodiodes for Filterless Multichannel Visible Light Communication

Future lightweight, flexible, and wearable electronics will employ visible-light- communication schemes to interact within indoor environments. Organic photodiodes are particularly well suited for such technologies as they enable chemically tailored optoelectronic performance and fabrication by printing techniques on thin and flexible substrates. However, previous methods have failed to address versatile functionality regarding wavelength selectivity without increasing fabrication complexity. This work introduces a general solution for printing wavelength-selective bulk-heterojunction photodetectors through engineering of the ink formulation. Nonfullerene acceptors are incorporated in a transparent polymer donor matrix to narrow and tune the response in the visible range without optical filters or light-management techniques. This approach effectively decouples the optical response from the viscoelastic ink properties, simplifying process development. A thorough morphological and spectroscopic investigation finds excellent charge-carrier dynamics enabling state-of-the-art responsivities >102 mA W−1 and cutoff frequencies >1.5 MHz. Finally, the color selectivity and high performance are demonstrated in a filterless visible-light-communication system capable of demultiplexing intermixed optical signals