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]

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

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

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

Understanding Self-Assembly of Porphyrin-Based SURMOFs: How Layered Minerals Can Be Useful

Porphyrin-based metal–organic frameworks on surfaces are a new class of planar materials with promising features for applications in chemical sensing, catalysis, and organic optoelectronics at nanoscale. Herein, we studied systematically a series of the SURMOFs assembled from variously <i>meso</i>-carboxyphenyl/pyridyl-substituted porphyrins and zinc acetate on template monolayers of graphene oxide via layer-by-layer deposition. This microscopically flat template can initiate the growth of macroscopically uniform SURMOF films exhibiting well-resolved X-ray diffraction. By applying the D’yakonov method, which has been previously used for the extraction of self-convolution of electron density in clay minerals, to the analysis of the experimental diffraction patterns of the SURMOFs, we determined the relation between the structure of porphyrin linkers and the geometry of packing motives in the films. We showed that the packing of the SURMOFs differs significantly from that of bulk powders of similar composition because of steric limitations imposed on the assembly in 2D space. The results of microscopic examination of the SURMOFs suggest that the type of metal-to-linker chemical bonding dictates the morphology of the films. Our method provides an enlightening picture of the interplay between supramolecular ordering and surface-directed assembly in porphyrin-based SURMOFs and is useful for rationalizing the fabrication of various classes of layered metal–organic frameworks on solids