Platinum(II) Compounds Containing Cyclometalated Tridentate Ligands: Synthesis, Luminescence Studies, and a Selective Fluoro for Methoxy Substitution

Two series of potentially tridentate ligands of formula ArCHN­(CH₂)₂NMe₂ and ArCHN­(CH₂)₃NMe₂ (Ar = C₆H₅, 2-FC₆H₄, 4-FC₆H₄, 2,3,4-F₃C₆H₂) were used to prepare [C,N,N′]-cyclometalated platinum compounds containing either a chloro or a methyl ancillary ligand. The synthesis of the compounds [PtCl­{Me₂N­(CH₂)_<i>x</i>NCHR}] (<b>3a</b>–<b>h</b>), via the corresponding compounds [PtCl₂{Me₂N­(CH₂)_<i>x</i>NCHAr}] (<b>2</b>), requires drastic conditions and proceeds more easily for ligands derived from <i>N</i>,<i>N</i>-dimethylpropylenediamine (<i>x</i> = 3). Along the process, an unexpected selective nucleophilic substitution of a fluoro for a methoxy substituent took place at the aryl ring for ligands 2,3,4-F₃C₆H₂CHN­(CH₂)_<i>x</i>NMe₂. The syntheses of compounds [PtMe­{Me₂N­(CH₂)_<i>x</i>NCHR}] (<b>4a</b>–<b>h</b>) using [Pt₂Me₄(μ-SMe₂)₂] as a precursor took place for all ligands under relatively mild conditions. All compounds were fully characterized, including molecular structure determination for [PtCl­{Me₂N­(CH₂)₃NCH­(4-FC₆H₃)}] (<b>3b</b>) and [PtCl­{Me₂N­(CH₂)₃NCH­(2-OMe,3,4-F₂C₆H)}] (<b>3g</b>). The absorption and emission spectra were also studied for the [C,N,N′]-cyclometalated platinum­(II) compounds, and all of the compounds were emissive in the solid state and in dichloromethane solution at room temperature (compounds <b>3</b>) or at 77 K (compounds <b>4</b>). The size of the [N,N′]-chelate ring and the number and position of the substituents in the aryl ring modulate the intensity and the energy of the emission

Platinum(II) Compounds Containing Cyclometalated Tridentate Ligands: Synthesis, Luminescence Studies, and a Selective Fluoro for Methoxy Substitution

Two series of potentially tridentate ligands of formula ArCHN­(CH₂)₂NMe₂ and ArCHN­(CH₂)₃NMe₂ (Ar = C₆H₅, 2-FC₆H₄, 4-FC₆H₄, 2,3,4-F₃C₆H₂) were used to prepare [C,N,N′]-cyclometalated platinum compounds containing either a chloro or a methyl ancillary ligand. The synthesis of the compounds [PtCl­{Me₂N­(CH₂)_<i>x</i>NCHR}] (<b>3a</b>–<b>h</b>), via the corresponding compounds [PtCl₂{Me₂N­(CH₂)_<i>x</i>NCHAr}] (<b>2</b>), requires drastic conditions and proceeds more easily for ligands derived from <i>N</i>,<i>N</i>-dimethylpropylenediamine (<i>x</i> = 3). Along the process, an unexpected selective nucleophilic substitution of a fluoro for a methoxy substituent took place at the aryl ring for ligands 2,3,4-F₃C₆H₂CHN­(CH₂)_<i>x</i>NMe₂. The syntheses of compounds [PtMe­{Me₂N­(CH₂)_<i>x</i>NCHR}] (<b>4a</b>–<b>h</b>) using [Pt₂Me₄(μ-SMe₂)₂] as a precursor took place for all ligands under relatively mild conditions. All compounds were fully characterized, including molecular structure determination for [PtCl­{Me₂N­(CH₂)₃NCH­(4-FC₆H₃)}] (<b>3b</b>) and [PtCl­{Me₂N­(CH₂)₃NCH­(2-OMe,3,4-F₂C₆H)}] (<b>3g</b>). The absorption and emission spectra were also studied for the [C,N,N′]-cyclometalated platinum­(II) compounds, and all of the compounds were emissive in the solid state and in dichloromethane solution at room temperature (compounds <b>3</b>) or at 77 K (compounds <b>4</b>). The size of the [N,N′]-chelate ring and the number and position of the substituents in the aryl ring modulate the intensity and the energy of the emission

Priority and emerging organic microcontaminants in three Mediterranean river basins: Occurrence, spatial distribution, and identification of river basin specific pollutants

There is a worldwide growing use of chemicals by our developed, industrialized, and technological society. More than 100,000 chemical substances are thus commonly used both by industry and households. Depending on the amount produced, physical-chemical properties, and mode of use, many of them may reach the environment and, notably, the aquatic receiving systems. This may result in undesirable and harmful side-effects on both the human and the ecosystem's health. Mediterranean rivers are largely different from Northern and Central European rivers in terms of hydrological regime, climate conditions (e.g. air temperature, solar irradiation, precipitation), and socio-economics (e.g. land use, tourism, crop types, etc.), with all these factors leading to differences in the relative importance of the environmental stressors, in the classes and levels of the pollutants found and their environmental fate. Furthermore, water scarcity might be critical in affecting water pollution because of the lowered dilution capacity of chemicals. This work provides raw chemical data from different families of microcontaminants identified in three selected Mediterranean rivers (the Sava, Evrotas, and Adige) collected during two sampling campaigns conducted in 2014 and 2015 in three different matrices, namely, water, sediments, and biota (fish). More than 200 organic micropollutants were analyzed, including relevant groups like pharmaceuticals, personal care products, perfluorinated compounds, pesticides, pyrethroid insecticides, flame retardants, and persistent organic pollutants. Data obtained were summarized with some basic statistics for all compound families and matrices analyzed. Observed occurrence and spatial patterns were interpreted both in terms of compound physical-chemical properties and local environmental pressures. Finally, their spatial distribution was examined and their ecotoxicological risk in the water phase was assessed. This allowed locating, at each basin, the most polluted sites (“hot spots”) and identifying the respective river basin specific pollutants (RBSPs), prioritizing them in terms of the potential ecotoxicological risk posed to the aquatic ecosystems.This work has been supported by the European Communities EU 7th Framework Programme Funding under Grant agreement no. 603629-ENV-2013-6.2.1-Globaqua and partly by the Generalitat de Catalunya (Consolidate Research Group 2017-SGR-01404) and by the Spanish Ministry of Science, Innovation and Universities (Projects CEX2018-000794-S and IBERAQUA-NET RED2018-102737-T). Special thanks are due to all partners of the GLOBAQUA consortium and the peer review panel for ensuring quality results and a fruitful collaboration within the frame of the project.Peer reviewe