Combining Dynamic Heteroleptic Complex Formation with Constitutional Dynamic Synthesis: A Facile Way to M₃LL′ Cage Assemblies

The quantitative preparation of heteroleptic copper(I) complexes arising from a combination of 2,9-diarylphenanthrolines and iminopyridines (Schiff bases) is described. This strategy was applied to construct mono- and binuclear complexes but equally a discrete three-dimensional M3LL′ cage. By means of a constitutional dynamic synthesis, the heteroleptic aggregates were equally prepared from four-component mixtures using the copper(I) center as a catalyst for the in situ generation of the iminopyridine ligands

Metal-Driven and Covalent Synthesis of Supramolecular Grids from Racks: A Convergent Approach to Heterometallic and Heteroleptic Nanostructures

Supramolecular nanogrids were prepared from dynamic supramolecular racks through the coupling of terminal alkynes using either a covalent (with CuCl/O2) or a coordinative (with [trans-(PEt3)2PtCl2]) approach. Because of the rapid equilibration of the racks (as tested by exchange reactions), oligomeric adducts potentially formed in the coupling process will selectively furnish the nanogrids through an entropically driven self-repair mechanism. To ascertain the structural assignment, the nanogrids were also synthesized by an independent strategy

Iridium-Based Lab-on-a-Molecule for Hg²⁺ and ClO^– with Two Distinct Light-Up Emissions

The nonemissive iridium complex 2 is a lab-on-a-molecule for the highly selective detection of Hg2+ and ClO– among 33 analytes using its oxime residues as reactive units. At pH 5, chemodosimeter 2 responds to Hg2+ by dehydration, whereas at pH 8, it is oxidized by ClO–, resulting in 450- and 235-fold emission increases, respectively, at two distinct wavelengths

Combining Dynamic Heteroleptic Complex Formation with Constitutional Dynamic Synthesis: A Facile Way to M₃LL′ Cage Assemblies

The quantitative preparation of heteroleptic copper(I) complexes arising from a combination of 2,9-diarylphenanthrolines and iminopyridines (Schiff bases) is described. This strategy was applied to construct mono- and binuclear complexes but equally a discrete three-dimensional M3LL′ cage. By means of a constitutional dynamic synthesis, the heteroleptic aggregates were equally prepared from four-component mixtures using the copper(I) center as a catalyst for the in situ generation of the iminopyridine ligands

Two Closely Related Iridium(III) Complexes as Colorimetric and Fluorometric Chemodosimeters for Nitrite in Aqueous Solution Operating along Different Modes of Action

Two closely related dual-channel chemodosimeters for nitrite in buffered aqueous acetonitrile were developed using [(pq)2IrCl]2 (1) and [(ppy)2IrCl]2 (2). In the UV–vis channel, the addition of nitrite caused visibly distinct color changes with both probes as a result of sizable absorption intensity enhancements. In the photoluminescence channel, the probes behaved oppositely upon the addition of nitrite. The emission was increased with 1, while it was quenched with 2. NMR and X-ray studies indicated that structurally very different η1-nitrito-N and η2-nitrito-O,O′ complexes were formed. Linear relationships for the quantification were obtained in both channels, allowing one to analyze for NO2– in a range from 5 × 10–5 to 2 × 10–2 M

Metal-Driven and Covalent Synthesis of Supramolecular Grids from Racks: A Convergent Approach to Heterometallic and Heteroleptic Nanostructures

Supramolecular nanogrids were prepared from dynamic supramolecular racks through the coupling of terminal alkynes using either a covalent (with CuCl/O2) or a coordinative (with [trans-(PEt3)2PtCl2]) approach. Because of the rapid equilibration of the racks (as tested by exchange reactions), oligomeric adducts potentially formed in the coupling process will selectively furnish the nanogrids through an entropically driven self-repair mechanism. To ascertain the structural assignment, the nanogrids were also synthesized by an independent strategy

Two Closely Related Iridium(III) Complexes as Colorimetric and Fluorometric Chemodosimeters for Nitrite in Aqueous Solution Operating along Different Modes of Action

Two closely related dual-channel chemodosimeters for nitrite in buffered aqueous acetonitrile were developed using [(pq)2IrCl]2 (1) and [(ppy)2IrCl]2 (2). In the UV–vis channel, the addition of nitrite caused visibly distinct color changes with both probes as a result of sizable absorption intensity enhancements. In the photoluminescence channel, the probes behaved oppositely upon the addition of nitrite. The emission was increased with 1, while it was quenched with 2. NMR and X-ray studies indicated that structurally very different η1-nitrito-N and η2-nitrito-O,O′ complexes were formed. Linear relationships for the quantification were obtained in both channels, allowing one to analyze for NO2– in a range from 5 × 10–5 to 2 × 10–2 M

Iridium-Based Lab-on-a-Molecule for Hg²⁺ and ClO^– with Two Distinct Light-Up Emissions

The nonemissive iridium complex <b>2</b> is a lab-on-a-molecule for the highly selective detection of Hg²⁺ and ClO^– among 33 analytes using its oxime residues as reactive units. At pH 5, chemodosimeter <b>2</b> responds to Hg²⁺ by dehydration, whereas at pH 8, it is oxidized by ClO^–, resulting in 450- and 235-fold emission increases, respectively, at two distinct wavelengths

Two Closely Related Iridium(III) Complexes as Colorimetric and Fluorometric Chemodosimeters for Nitrite in Aqueous Solution Operating along Different Modes of Action

Two closely related dual-channel chemodosimeters for nitrite in buffered aqueous acetonitrile were developed using [(pq)2IrCl]2 (1) and [(ppy)2IrCl]2 (2). In the UV–vis channel, the addition of nitrite caused visibly distinct color changes with both probes as a result of sizable absorption intensity enhancements. In the photoluminescence channel, the probes behaved oppositely upon the addition of nitrite. The emission was increased with 1, while it was quenched with 2. NMR and X-ray studies indicated that structurally very different η1-nitrito-N and η2-nitrito-O,O′ complexes were formed. Linear relationships for the quantification were obtained in both channels, allowing one to analyze for NO2– in a range from 5 × 10–5 to 2 × 10–2 M

Stereocontrolled Synthesis of a Nonracemic Vitamin B₁₂ A−B-Semicorrin

The first synthesis of a vitamin B12 A−B-semicorrin 44 is described. Both A and B rings were prepared from the same precursor, enamide 40, which is obtained by a sequence of sigmatropic rearrangements and a biomimetic oxylactonization. The coupling has been achieved via Eschenmoser sulfide contraction. A−B-semicorrin 44 allows a new approach toward vitamin B12 and other uroporphinoids