Synthesis, spectroscopy and crystal structure of α-isosparteine complexes with ZnX2 (X=Br, CN, Cl)

Jasiewicz, Beata; Boczoń, Władysław; Mumot, Anna; Warżajtis, Beata; Rychłewska, Urszula

doi:10.1016/j.molstruc.2004.10.031

Cited by 20 publications

(12 citation statements)

References 29 publications

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“…The IR spectrum of 4 presents two weak absorption bands at $\tilde {\nu}$ = 2077 and 2061 cm –1 attributed to the ν(CN) stretching frequency of the cyanido ligand. These bands are strongly shifted to low frequencies compared with those of some non‐porphyrinic zinc–cyanido complexes such as [Zn(CN) 2 (C 15 H 26 N 2 )] (2233 cm –1 ),22 [Zn(CN) 2 (C 16 H 28 N 2 )] (2217 cm –1 ),23 and [Zn(CN) 4 ] 2– (2144 cm –1 ) 24. This suggests that the cyanido ligand in 4 presents a strong π‐acceptor character 24.…”

Section: Resultsmentioning

confidence: 96%

Insights on the UV/Vis, Fluorescence, and Cyclic Voltammetry Properties and the Molecular Structures of Zn^II Tetraphenylporphyrin Complexes with Pseudohalide Axial Azido, Cyanato‐N, Thiocyanato‐N, and Cyanido Ligands

et al. 2015

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The syntheses, spectroscopic and photophysical properties, and molecular structures of azido-(1), cyanato-N-(2), thio cyanato-N-(3), and cyanido-(4) (meso-tetraphenylporphyrinato)zinc(II) complexes are reported. These species were prepared by using cryptand-222 to solubilize the pseudohalide salts in organic solvents. The UV/Vis spectra of these zinc metalloporphyrins are solvent-dependent and exhibit large redshifted Soret bands compared with those of the [Zn(Porph)L] derivatives in which Porph is a meso-porphyrinato ligand and L is a monodentate neutral axial ligand. The room-temperature fluorescence spectra of the zinc complexes 1-4 indicate that the Q bands are not very affected by the nature of the axial ligands, and their positions are very close to those of previously reported (meso-porphyrinato)zinc complexes. The quantum yields of the S 1 Ǟ S o fluorescence of 1-4 range between 2.8 and 5.5 %, and their fluorescence lifetimes are the same (1.7 ns). Cyclic voltammetry investigations on 1-4 show that the characteristic potentials for the reduction and the two first oxidations of the porphyrin ring 2596are not very affected by the nature of the axial ligand. A third irreversible oxidation of the porphyrin ring is observed. Additional anodic irreversible waves are observed for the thiocyanato-N (3) and cyanido (4) species. The solid-state molecular structures of 1-4 are the first examples of zinc porphyrin complexes with anionic ligands. The average equatorial zinc-pyrrole N atom (Zn-N p ) distances for 1-4 range between 2.083(1) and 2.117(2) Å and are much longer than those of the related pentacoordinate zinc porphyrin complexes with monodentate neutral ligands. As a consequence, the displacement of the Zn 2+ cation from the mean 24-atom plan of the porphyrin core is significant (ca. 0.5 Å), and the porphyrin core is very distorted. The crystal structures of 1-4 are stabilized by weak intermolecular π interactions, CH···Cg (Cg are the centroids of some six-membered phenyl rings and five-membered pyrrole rings). The molecular structure of 1 is further stabilized by weak intermolecular C-H···N hydrogen bonds between one carbon atom of cryptand-222 and the terminal nitrogen atom of the azido ligand.

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Section: Resultsmentioning

confidence: 96%

Insights on the UV/Vis, Fluorescence, and Cyclic Voltammetry Properties and the Molecular Structures of Zn^II Tetraphenylporphyrin Complexes with Pseudohalide Axial Azido, Cyanato‐N, Thiocyanato‐N, and Cyanido Ligands

et al. 2015

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“…Crystals of 1 are tetragonal, space group P4 3 2 1 2 ( Table 1) and belong to the isostructural series with the (À)a-Sp, ZnCl 2 , ZnBr 2 Zn(CN) 2 [35] (CSD refcodes: AMIQOC, FEXDOC, FESBOV) and CoCl 2 [36]) (ISPCCO) complexes. A case of isostructurality is well pronounced in the series of (À)-a-isosparteine isomers, as it is often combined with the inherent tendency of this group of compounds to utilize C 2 molecular symmetry in a crystal by forming either tetragonal crystals with P4 3 2 1 2 symmetry [35,36]) or orthorhombic with C222 1 symmetry [37].…”

Section: Single Crystal X-ray Resultsmentioning

confidence: 99%

“…A case of isostructurality is well pronounced in the series of (À)-a-isosparteine isomers, as it is often combined with the inherent tendency of this group of compounds to utilize C 2 molecular symmetry in a crystal by forming either tetragonal crystals with P4 3 2 1 2 symmetry [35,36]) or orthorhombic with C222 1 symmetry [37]. However, so far it did not concerned the copper(II) complexes; the two known tetrahedral Cu(II) complexes with (À)-a-isosparteine, namely (À)a-SpCu(NO 3 ) 2 (ASUBOF [38]) and (À)a-SpCu(N 3 ) 2 (IFIBEE [39]) crystallize in space group P2 1 2 1 2 1 lacking the special position sites.…”

Section: Single Crystal X-ray Resultsmentioning

confidence: 99%

Variety of polymorphic forms contrasted with uniform crystal packing in sparteine ML2 complexes: Crystal structure, spectroscopic and magnetic properties of (−)-α-isosparteine and (−)-sparteine complexes with CuBr2

Jasiewicz

Warżajtis

Rychłewska

et al. 2009

Journal of Molecular Structure

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“…On the other hand, it has been reported that (-)-a-isosparteine remains structurally unchanged upon complexation 17 ( Fig. 2).…”

Section: 25mentioning

confidence: 87%

Electron ionization and fast atom bombardment mass spectral study for differentiation of ligand of zinc(II) (–)‐sparteine and (–)‐α‐isosparteine complexes

Jasiewicz

Wyrzykiewicz

2008

Rapid Comm Mass Spectrometry

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Electron ionization and fast atom bombardment mass spectral study for differentiation of ligand of zinc(II) (-)-sparteine and (-)-a-isosparteine complexesThe (-)-sparteine bis-quinolizidine alkaloid produced by lupine species has generated much interest due to its pharmacological properties, 1-3 and its application in asymmetric synthesis. 4,5 The basic bis-quinolizidine system of (-)-sparteine consists of four rings, two of which (A/B) form a double-chair system of trans-quinolizidine, which is relatively resistant (for thermodynamic reasons) to conformationalconfigurational changes. The second system of rings (C/D) is much more susceptible to inversion at the N16 nitrogen atom and it can occur in either the trans boat-chair or the cis double-chair conformation. According to Haasnoot, 6 sparteine adopts exclu-

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Synthesis, spectroscopy and crystal structure of α-isosparteine complexes with ZnX2 (X=Br, CN, Cl)

Cited by 20 publications

References 29 publications

Insights on the UV/Vis, Fluorescence, and Cyclic Voltammetry Properties and the Molecular Structures of Zn^II Tetraphenylporphyrin Complexes with Pseudohalide Axial Azido, Cyanato‐N, Thiocyanato‐N, and Cyanido Ligands

Insights on the UV/Vis, Fluorescence, and Cyclic Voltammetry Properties and the Molecular Structures of Zn^II Tetraphenylporphyrin Complexes with Pseudohalide Axial Azido, Cyanato‐N, Thiocyanato‐N, and Cyanido Ligands

Variety of polymorphic forms contrasted with uniform crystal packing in sparteine ML2 complexes: Crystal structure, spectroscopic and magnetic properties of (−)-α-isosparteine and (−)-sparteine complexes with CuBr2

Electron ionization and fast atom bombardment mass spectral study for differentiation of ligand of zinc(II) (–)‐sparteine and (–)‐α‐isosparteine complexes

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Synthesis, spectroscopy and crystal structure of α-isosparteine complexes with ZnX2 (X=Br, CN, Cl)

Cited by 20 publications

References 29 publications

Insights on the UV/Vis, Fluorescence, and Cyclic Voltammetry Properties and the Molecular Structures of ZnII Tetraphenylporphyrin Complexes with Pseudohalide Axial Azido, Cyanato‐N, Thiocyanato‐N, and Cyanido Ligands

Insights on the UV/Vis, Fluorescence, and Cyclic Voltammetry Properties and the Molecular Structures of ZnII Tetraphenylporphyrin Complexes with Pseudohalide Axial Azido, Cyanato‐N, Thiocyanato‐N, and Cyanido Ligands

Variety of polymorphic forms contrasted with uniform crystal packing in sparteine ML2 complexes: Crystal structure, spectroscopic and magnetic properties of (−)-α-isosparteine and (−)-sparteine complexes with CuBr2

Electron ionization and fast atom bombardment mass spectral study for differentiation of ligand of zinc(II) (–)‐sparteine and (–)‐α‐isosparteine complexes

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Insights on the UV/Vis, Fluorescence, and Cyclic Voltammetry Properties and the Molecular Structures of Zn^II Tetraphenylporphyrin Complexes with Pseudohalide Axial Azido, Cyanato‐N, Thiocyanato‐N, and Cyanido Ligands

Insights on the UV/Vis, Fluorescence, and Cyclic Voltammetry Properties and the Molecular Structures of Zn^II Tetraphenylporphyrin Complexes with Pseudohalide Axial Azido, Cyanato‐N, Thiocyanato‐N, and Cyanido Ligands