Copper( ii ) complexes with phosphorylated 1,10-phenanthrolines: from molecules to infinite supramolecular arrays

International audienceThe reaction of phosphorylated 1,10-phenanthrolines 3-Pphen, 3,8-Pphen and 4,7-Pphen (3-Pphen = 3-diethoxyphosphorylphenanthroline, 3,8-Pphen = 3,8-bis(diethoxyphosphoryl) phenanthroline, 4,7-Pphen = 4,7-bis(diethoxyphosphoryl) phenanthroline) and hydrated copper(II) nitrate in a 1 : 1 ratio leads to the formation of supramolecular architectures. In the 1D coordination polymer [Cu(3-Pphen)(NO3)(2)](n) (2) the copper atom is coordinated to only one phenanthroline ligand and the coordination sphere is completed by two oxygen atoms of nitrate anions and the oxygen atom of the phosphoryl group from the neighbouring phenanthroline ligand. Complex Cu(3,8-Pphen)(NO3)(2) (3) crystallizes from dichloromethane/ether in two polymorphic forms. Form 3-I is a dimeric complex in which two phenanthroline rings are parallel and offset-shifted due to the formation of two (P) O-Cu bonds. The crystals of the polymorph 3-II are composed of polymeric chains in which the coordination sphere of the metal centres and the arrangement of the mononuclear fragments are similar to those of complex 2. Complex [Cu(4,7-Pphen)(NO3)(2)](2) (4) crystallizes from toluene/acetonitrile and exhibits a dimeric structure which is similar to that of 3-I

On the synthesis of functionalized porphyrins and porphyrin conjugates via β-aminoporphyrins

International audienceThe synthesis of functionalized porphyrins and their conjugates from meso-tetraarylporphyrins through the acylation and the oxidation of beta-aminoporphyrins was investigated. 2,3-Dioxochlorins were prepared by the oxidation of a variety of beta-aminoporphyrins and subsequently used in a condensation reaction with functionalized aromatic aldehydes and ammonium acetate to form beta-functionalized porphyrins bearing a fused imidazole ring. Under optimized experimental conditions both reactions tolerate various functional groups and afford the products in an appropriate overall yield. The mildness and usefulness of this methodology are illustrated by several examples including the synthesis of porphyrins bearing receptor groups and water-solubilizing moieties

Gallium(III) and Indium(III) Complexes with meso-Monophosphorylated Porphyrins: Synthesis and Structure. A First Example of Dimers Formed by the Self-Assembly of meso-Porphyrinylphosphonic Acid Monoester

International audienceThe synthesis and structural characterization, both in solution by means of H-1 and P-31 NMR and UV-vis spectroscopies and in the solid state by X-ray diffraction on single crystal, of a series of gallium(III) and indium(III) meso-mono(diethoxyphosphoryl)porphyrins bearing different peripheral substituents as well as the corresponding monoesters and phosphonic acids are reported. This work describes the first example of the X-ray structure of a self-assembled dimer formed via strong binding between the oxygen atom of the phosphonate substituent and the gallium(III) cations of adjacent porphyrin molecules [Ga-O = 1.9708(13) angstrom]

Gallium(III) and Indium(III) Complexes with <i>meso</i>-Monophosphorylated Porphyrins: Synthesis and Structure. A First Example of Dimers Formed by the Self-Assembly of <i>meso</i>-Porphyrinylphosphonic Acid Monoester

The synthesis and structural characterization, both in solution by means of ¹H and ³¹P NMR and UV–vis spectroscopies and in the solid state by X-ray diffraction on single crystal, of a series of gallium­(III) and indium­(III) <i>meso</i>-mono­(diethoxyphosphoryl)­porphyrins bearing different peripheral substituents as well as the corresponding monoesters and phosphonic acids are reported. This work describes the first example of the X-ray structure of a self-assembled dimer formed via strong binding between the oxygen atom of the phosphonate substituent and the gallium­(III) cations of adjacent porphyrin molecules [Ga–O = 1.9708(13) Å]

Gallium(III) and Indium(III) Complexes with <i>meso</i>-Monophosphorylated Porphyrins: Synthesis and Structure. A First Example of Dimers Formed by the Self-Assembly of <i>meso</i>-Porphyrinylphosphonic Acid Monoester

The synthesis and structural characterization, both in solution by means of ¹H and ³¹P NMR and UV–vis spectroscopies and in the solid state by X-ray diffraction on single crystal, of a series of gallium­(III) and indium­(III) <i>meso</i>-mono­(diethoxyphosphoryl)­porphyrins bearing different peripheral substituents as well as the corresponding monoesters and phosphonic acids are reported. This work describes the first example of the X-ray structure of a self-assembled dimer formed via strong binding between the oxygen atom of the phosphonate substituent and the gallium­(III) cations of adjacent porphyrin molecules [Ga–O = 1.9708(13) Å]

Supramolecular Assembly of Organophosphonate Diesters Using Paddle-Wheel Complexes: First Examples in Porphyrin Series

The reactions of dicopper tetrapivalate complex Cu₂(μ-OOC-<i>t-</i>Bu)₄­(NCMe)₂ (<b>1</b>) with triphenylphosphine oxide and diethyl phosphite allow paddle-wheel (PW) copper­(II) complexes with phosphorus-containing axial ligands (<b>2</b>, <b>3</b>) to be obtained. When <i>meso</i>-bis­(diethoxyphosphoryl)­porphyrins <b>4M</b> were employed in this ligand exchange reaction, a series of one-dimensional (1D) homo- and heterometallic coordination polymers <b>5M</b> composed of PW subunits and organophosphonate diesters were prepared and characterized by means of single crystal X-ray analysis. Planar porphyrinate <b>4Pd</b> and nonplanar metalloporphyrinates <b>4Cu</b> and <b>4Ni</b> proved to be appropriate molecular structural blocks for assembly of coordination polymers. The structural parameters of the tetrapyrrolic macrocycles incorporated into the polymer chain are determined by the nature of the metal center of the porphyrin moiety. While the geometry of palladium­(II) and nickel­(II) porphyrinates <b>4Pd</b> and <b>4Ni</b> does not change significantly in the polymer chain, saddle-shaped Cu­(II) porphyrinate <b>4Cu</b> exhibits a nearly planar core configuration, being coordinated to the copper centers of PW fragments by two peripheral phosphoryl groups in the polymer chain. The geometry of the tetrapyrrolic core is a key parameter influencing the structural properties of the polymeric materials. For <b>5Pd</b> and for isostructural <b>5Cu</b>, all metal centers of the polymeric chain are aligned. The planar macrocycles of adjacent chains are parallel and are shifted one to another in such a way that the angle between the Pd···P and Pd···Pd directions is 40.4°, and the distance between the nearest palladium­(II) atoms of neighboring chains is 11.668 Å. There is no free volume in these crystals. In the crystals of <b>5Ni</b>, formed by nonplanar porphyrinates, only copper atoms of the PW pivalate moiety are located in one plane, and zigzag chains are formed so that two adjacent tetrapyrrolic macrocycles are located in alternating positions with respect to this plane, the nickel atoms being displaced from this plane by 1.548 Å. This arrangement naturally leads to the formation of regular pores. The resulting channels have an effective cross-section of about 10 × 12 Å and represent ca. 18% of the volume of the crystal. The exchange reaction between the free-base porphyrin <b>4H</b>_<b>2</b> and an excess of copper­(II) pivalate complex <b>1</b> is accompanied by the metalation of the porphyrin core affording the polymer <b>5Cu</b>. Moreover, self-assembly of metalloporphyrinate <b>4Zn</b> is observed under studied experimental conditions, which interferes with the formation of the target mixed coordination polymers

Gallium(III) and Indium(III) Complexes with <i>meso</i>-Monophosphorylated Porphyrins: Synthesis and Structure. A First Example of Dimers Formed by the Self-Assembly of <i>meso</i>-Porphyrinylphosphonic Acid Monoester

The synthesis and structural characterization, both in solution by means of ¹H and ³¹P NMR and UV–vis spectroscopies and in the solid state by X-ray diffraction on single crystal, of a series of gallium­(III) and indium­(III) <i>meso</i>-mono­(diethoxyphosphoryl)­porphyrins bearing different peripheral substituents as well as the corresponding monoesters and phosphonic acids are reported. This work describes the first example of the X-ray structure of a self-assembled dimer formed via strong binding between the oxygen atom of the phosphonate substituent and the gallium­(III) cations of adjacent porphyrin molecules [Ga–O = 1.9708(13) Å]

Unusual Formation of a Stable 2D Copper Porphyrin Network

Copper­(II) 5,15-bis­(diethoxyphosphoryl)-10,20-diphenylporphyrin was obtained and characterized by means of cyclic voltammetry, electron paramagnetic resonance, Fourier transform infrared, and UV–visible spectroscopy. Three crystalline forms were grown and studied by means of X-ray diffraction methods (single crystal and powder). The highly electron-withdrawing effect of phosphoryl groups attached directly to the porphyrin macrocycle results in a self-assembling process, with formation of a stable 2D coordination network, which is unusual for copper­(II) porphyrins. The resulting 2D structure is a rare example of an assembly based on copper­(II) porphyrins where the copper­(II) central metal ion is six-coordinated because of a weak interaction with two phosphoryl groups of adjacent porphyrins. The other polymorph of copper­(II) 5,15-bis­(diethoxyphosphoryl)-10,20-diphenylporphyrin contains individual (isolated) porphyrin molecules with four-coordinated copper­(II) in a distorted porphyrin core. This polymorph can be obtained only by slow diffusion of a copper acetate/methanol solution into solutions of free base 5,15-bis­(diethoxyphosphoryl)-10,20-diphenylporphyrin in chloroform. It converts to the 2D structure after dissolution in chloroform followed by consecutive crystallizations, using slow diffusion of hexane. A six-coordinated copper­(II) porphyrin containing two axially coordinated dioxane molecules was also obtained and characterized by X-ray diffraction crystallography. The association of copper­(II) 5,15-bis­(diethoxyphosphoryl)-10,20-diphenylporphyrin in solution was also studied

Unusual Formation of a Stable 2D Copper Porphyrin Network

Copper­(II) 5,15-bis­(diethoxyphosphoryl)-10,20-diphenylporphyrin was obtained and characterized by means of cyclic voltammetry, electron paramagnetic resonance, Fourier transform infrared, and UV–visible spectroscopy. Three crystalline forms were grown and studied by means of X-ray diffraction methods (single crystal and powder). The highly electron-withdrawing effect of phosphoryl groups attached directly to the porphyrin macrocycle results in a self-assembling process, with formation of a stable 2D coordination network, which is unusual for copper­(II) porphyrins. The resulting 2D structure is a rare example of an assembly based on copper­(II) porphyrins where the copper­(II) central metal ion is six-coordinated because of a weak interaction with two phosphoryl groups of adjacent porphyrins. The other polymorph of copper­(II) 5,15-bis­(diethoxyphosphoryl)-10,20-diphenylporphyrin contains individual (isolated) porphyrin molecules with four-coordinated copper­(II) in a distorted porphyrin core. This polymorph can be obtained only by slow diffusion of a copper acetate/methanol solution into solutions of free base 5,15-bis­(diethoxyphosphoryl)-10,20-diphenylporphyrin in chloroform. It converts to the 2D structure after dissolution in chloroform followed by consecutive crystallizations, using slow diffusion of hexane. A six-coordinated copper­(II) porphyrin containing two axially coordinated dioxane molecules was also obtained and characterized by X-ray diffraction crystallography. The association of copper­(II) 5,15-bis­(diethoxyphosphoryl)-10,20-diphenylporphyrin in solution was also studied