Nanomolar Pyrophosphate Detection in Water and in a Self-Assembled Hydrogel of a Simple Terpyridine-Zn²⁺ Complex

A simple terpyridine-Zn­(II) complex is shown to act as an efficient and highly selective fluorescent sensor for pyrophosphate in water at physiological pH. The sensor complex showed an unprecedented fluorescence response (∼500 fold increase) and a record nanomolar sensitivity (detectable fluorescent response at 20 nM and LOD ∼ 0.8 nM). It has successfully been used to stain and record confocal fluorescence microscopy images of HeLa cells. Moreover, the complex was found to self-assemble into a hydrogel which was subsequently used to coat disposable paper strips for easy, low-cost detection of pyrophosphate

DOSY NMR, X‑ray Structural and Ion-Mobility Mass Spectrometric Studies on Electron-Deficient and Electron-Rich M₆L₄ Coordination Cages

A novel modular approach to electron-deficient and electron-rich M₆L₄ cages is presented. From the same starting compound, via a minor modulation of the synthesis route, two <i>C</i>₃-symmetric ligands <b>L1</b> and <b>L2</b> with different electronic properties are obtained in good yield. The trifluoro-triethynylbenzene-based ligand <b>L1</b> is more electron-deficient than the well-known 2,4,6-tri­(4-pyridyl)-1,3,5-triazine, while the trimethoxy-triethynylbenzene-based ligand <b>L2</b> is more electron-rich than the corresponding benzene analogue. Complexation of the ligands with cis-protected square-planar [(dppp)­Pt­(OTf)₂] or [(dppp)­Pd­(OTf)₂] corner-complexes yields two electron-deficient (<b>1a</b> and <b>1b</b>) and two electron-rich (<b>2a</b> and <b>2b</b>) M₆L₄ cages. The single crystal X-ray diffraction study of <b>1a</b> and <b>2a</b> confirms the expected octahedral shape with a ca. 2000 ų cavity and ca. 11 Å wide apertures. The crystallographically determined diameters of <b>1a</b> and <b>2a</b> are 3.7 and 3.6 nm, respectively. The hydrodynamic diameters obtained from the DOSY NMR in CDCl₃:CD₃OD (4:1), and diameters calculated from collision cross sections (CCS) acquired by ion-mobility mass spectrometry (IM-MS) were for all four cages similar. In solution, the cage structures have diameters between 3.3 to 3.6 nm, while in the gas phase the corresponding diameters varied between 3.4 to 3.6 nm. In addition to the structural information the relative stabilities of the Pt₆L₄ and Pd₆L₄ cages were studied in the gas phase by collision-induced dissociation (CID) experiments, and the photophysical properties of the ligands <b>L1</b> and <b>L2</b> and cages <b>1a</b>, <b>1b</b>, <b>2a</b>, and <b>2b</b> were studied by UV–vis and fluorescence spectroscopy

DOSY NMR, X‑ray Structural and Ion-Mobility Mass Spectrometric Studies on Electron-Deficient and Electron-Rich M₆L₄ Coordination Cages

A novel modular approach to electron-deficient and electron-rich M₆L₄ cages is presented. From the same starting compound, via a minor modulation of the synthesis route, two <i>C</i>₃-symmetric ligands <b>L1</b> and <b>L2</b> with different electronic properties are obtained in good yield. The trifluoro-triethynylbenzene-based ligand <b>L1</b> is more electron-deficient than the well-known 2,4,6-tri­(4-pyridyl)-1,3,5-triazine, while the trimethoxy-triethynylbenzene-based ligand <b>L2</b> is more electron-rich than the corresponding benzene analogue. Complexation of the ligands with cis-protected square-planar [(dppp)­Pt­(OTf)₂] or [(dppp)­Pd­(OTf)₂] corner-complexes yields two electron-deficient (<b>1a</b> and <b>1b</b>) and two electron-rich (<b>2a</b> and <b>2b</b>) M₆L₄ cages. The single crystal X-ray diffraction study of <b>1a</b> and <b>2a</b> confirms the expected octahedral shape with a ca. 2000 ų cavity and ca. 11 Å wide apertures. The crystallographically determined diameters of <b>1a</b> and <b>2a</b> are 3.7 and 3.6 nm, respectively. The hydrodynamic diameters obtained from the DOSY NMR in CDCl₃:CD₃OD (4:1), and diameters calculated from collision cross sections (CCS) acquired by ion-mobility mass spectrometry (IM-MS) were for all four cages similar. In solution, the cage structures have diameters between 3.3 to 3.6 nm, while in the gas phase the corresponding diameters varied between 3.4 to 3.6 nm. In addition to the structural information the relative stabilities of the Pt₆L₄ and Pd₆L₄ cages were studied in the gas phase by collision-induced dissociation (CID) experiments, and the photophysical properties of the ligands <b>L1</b> and <b>L2</b> and cages <b>1a</b>, <b>1b</b>, <b>2a</b>, and <b>2b</b> were studied by UV–vis and fluorescence spectroscopy

DOSY NMR, X‑ray Structural and Ion-Mobility Mass Spectrometric Studies on Electron-Deficient and Electron-Rich M₆L₄ Coordination Cages

A novel modular approach to electron-deficient and electron-rich M₆L₄ cages is presented. From the same starting compound, via a minor modulation of the synthesis route, two <i>C</i>₃-symmetric ligands <b>L1</b> and <b>L2</b> with different electronic properties are obtained in good yield. The trifluoro-triethynylbenzene-based ligand <b>L1</b> is more electron-deficient than the well-known 2,4,6-tri­(4-pyridyl)-1,3,5-triazine, while the trimethoxy-triethynylbenzene-based ligand <b>L2</b> is more electron-rich than the corresponding benzene analogue. Complexation of the ligands with cis-protected square-planar [(dppp)­Pt­(OTf)₂] or [(dppp)­Pd­(OTf)₂] corner-complexes yields two electron-deficient (<b>1a</b> and <b>1b</b>) and two electron-rich (<b>2a</b> and <b>2b</b>) M₆L₄ cages. The single crystal X-ray diffraction study of <b>1a</b> and <b>2a</b> confirms the expected octahedral shape with a ca. 2000 ų cavity and ca. 11 Å wide apertures. The crystallographically determined diameters of <b>1a</b> and <b>2a</b> are 3.7 and 3.6 nm, respectively. The hydrodynamic diameters obtained from the DOSY NMR in CDCl₃:CD₃OD (4:1), and diameters calculated from collision cross sections (CCS) acquired by ion-mobility mass spectrometry (IM-MS) were for all four cages similar. In solution, the cage structures have diameters between 3.3 to 3.6 nm, while in the gas phase the corresponding diameters varied between 3.4 to 3.6 nm. In addition to the structural information the relative stabilities of the Pt₆L₄ and Pd₆L₄ cages were studied in the gas phase by collision-induced dissociation (CID) experiments, and the photophysical properties of the ligands <b>L1</b> and <b>L2</b> and cages <b>1a</b>, <b>1b</b>, <b>2a</b>, and <b>2b</b> were studied by UV–vis and fluorescence spectroscopy

DOSY NMR, X‑ray Structural and Ion-Mobility Mass Spectrometric Studies on Electron-Deficient and Electron-Rich M₆L₄ Coordination Cages

A novel modular approach to electron-deficient and electron-rich M₆L₄ cages is presented. From the same starting compound, via a minor modulation of the synthesis route, two <i>C</i>₃-symmetric ligands <b>L1</b> and <b>L2</b> with different electronic properties are obtained in good yield. The trifluoro-triethynylbenzene-based ligand <b>L1</b> is more electron-deficient than the well-known 2,4,6-tri­(4-pyridyl)-1,3,5-triazine, while the trimethoxy-triethynylbenzene-based ligand <b>L2</b> is more electron-rich than the corresponding benzene analogue. Complexation of the ligands with cis-protected square-planar [(dppp)­Pt­(OTf)₂] or [(dppp)­Pd­(OTf)₂] corner-complexes yields two electron-deficient (<b>1a</b> and <b>1b</b>) and two electron-rich (<b>2a</b> and <b>2b</b>) M₆L₄ cages. The single crystal X-ray diffraction study of <b>1a</b> and <b>2a</b> confirms the expected octahedral shape with a ca. 2000 ų cavity and ca. 11 Å wide apertures. The crystallographically determined diameters of <b>1a</b> and <b>2a</b> are 3.7 and 3.6 nm, respectively. The hydrodynamic diameters obtained from the DOSY NMR in CDCl₃:CD₃OD (4:1), and diameters calculated from collision cross sections (CCS) acquired by ion-mobility mass spectrometry (IM-MS) were for all four cages similar. In solution, the cage structures have diameters between 3.3 to 3.6 nm, while in the gas phase the corresponding diameters varied between 3.4 to 3.6 nm. In addition to the structural information the relative stabilities of the Pt₆L₄ and Pd₆L₄ cages were studied in the gas phase by collision-induced dissociation (CID) experiments, and the photophysical properties of the ligands <b>L1</b> and <b>L2</b> and cages <b>1a</b>, <b>1b</b>, <b>2a</b>, and <b>2b</b> were studied by UV–vis and fluorescence spectroscopy