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Searching for a connection between the two-electron redox behavior of Group-14 elements and their possible use as platforms for the photoreductive elimination of chlorine, we have studied the photochemistry of [(o-(Ph 2 P)C 6 H 4 ) 2 Ge IV Cl 2 ]Pt II Cl 2 and [(o-(Ph 2 P)C 6 H 4 ) 2 ClGe III ]Pt III Cl 3 , two newly isolated isomeric complexes. These studies show that, in the presence of a chlorine trap, both isomers convert cleanly into the platinum germyl complex [(o-(Ph 2 P)C 6 H 4 ) 2 ClGe III ]Pt I Cl with quantum yields of 1.7 % and 3.2 % for the Ge IV -Pt II and Ge III -Pt III isomers, respectively. Conversion of the Ge IV -Pt II isomer into the platinum germyl complex is a rare example of a light-induced transition-metal/main-group-element bond-forming process. Finally, transient-absorption-spectroscopy studies carried out on the Ge III -Pt III isomer point to a ligand arene-Cl . charge-transfer complex as an intermediate., (© 2021 Wiley-VCH GmbH.)

A series of metal-organic chromophores containing Ru(II) or Ir(III) were studied for the luminometric detection of nitroaromatic compounds, including trinitrotoluene (TNT). These complexes display long-lived, intense photoluminescence in the visible region and are demonstrated to serve as luminescent sensors for nitroaromatics. The solution-based behavior of these photoluminescent molecules has been studied in detail in order to identify the mechanism responsible for metal-to-ligand charge-transfer (MLCT) excited state quenching upon addition of TNT and 2,4-dinitrotoluene (2,4-DNT). A combination of static and dynamic spectroscopic measurements unequivocally confirmed that the quenching was due to a photoinduced electron transfer (PET) process. Ultrafast transient absorption experiments confirmed the formation of the TNT radical anion product following excited state electron transfer from these metal complexes. Reported for the first time, photoluminescence quenching realized through ink-jet printing and solid-state titrations was used for the solid-state detection of TNT; achieving a limit-of-quantitation (LOQ) as low as 5.6 ng cm(-2). The combined effect of a long-lived excited state and an energetically favorable driving force for the PET process makes the Ru(II) and Ir(III) MLCT complexes discussed here particularly appealing for the detection of nitroaromatic volatiles and related high-energy compounds., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)