Determination of the Structural Parameters of Heteronuclear (Phthalocyaninato)bis(crownphthalocyaninato)lanthanide(III) Triple-Deckers in Solution by Simultaneous Analysis of NMR and Single-Crystal X‑ray Data

Application of a general and convenient approach to the synthesis of heteronuclear crown-substituted triple-decker phthalocyaninates afforded two series of complexes containing one dia- and one paramagnetic Ln­(III) ion (for Y and almost the whole lanthanide family), [(15C5)₄Pc]­M*­[(15C5)₄Pc]­M­(Pc) (or [M*,M] for brevity sake), where (15C5) is 15-crown-5; (Pc^2–) is phthalocyaninato dianion; and M ≠ M* = Y, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb. This approach consists of using LaPc₂ as an efficient Pc^2– source. The solid-state structures of two complexes ([Tm*,Y] and [Yb*,Y]) were studied by single-crystal X-ray diffraction analysis, providing therefore a structural model for the assignment and analysis of ¹H NMR spectra of the complexes, which is strongly affected by the presence of paramagnetic lanthanide ions. Model validation was performed on complexes containing two different paramagnetic ions[Dy*,Gd] and [Gd*,Dy] as well as [Tb*,Tm] and [Tm*,Tb]synthesized by the above-mentioned method

A Molecular Chameleon: Reversible pH- and Cation-Induced Control of the Optical Properties of Phthalocyanine-Based Complexes in the Visible and Near-Infrared Spectral Ranges

A series of novel nonperipherally substituted tetra-15-crown-5-dibutoxyoxanthrenocyanines (H₂, Mg, Zn), acting as chameleons with the unique properties of switchable absorption and emission in the near-infrared (NIR) spectral range have been synthesized and characterized by X-ray diffraction. The attachment of 15-crown-5-α-dibutoxyoxanthreno moieties to phthalocyanine is responsible for the high solubility of the resulting molecules and the red shift of the Q band to the NIR region and offers a unique possibility for postsynthetic modification of the optical properties of the molecules. Both aggregation of phthalocyanine and its participation in an acid–base equilibrium strongly alter their optical properties. For example, the absorption of complexes can be reversibly tuned from 686 up to 1028 nm because of the cation-induced formation of supramolecular dimers or subsequent protonation of <i>meso</i>-N atoms orf macrocycle, in contrast to peripherally substituted tetra-15-crown-5-phthalocyanines without oxanthrene moieties. The reversibility of these processes can be controlled by the addition of [2.2.2]­cryptand or amines. All investigated compounds exhibit fluorescence with moderate quantum yield, which can also be switched between the ON and OFF states by the action of similar agents

Determination of the Structural Parameters of Heteronuclear (Phthalocyaninato)bis(crownphthalocyaninato)lanthanide(III) Triple-Deckers in Solution by Simultaneous Analysis of NMR and Single-Crystal X‑ray Data

Application of a general and convenient approach to the synthesis of heteronuclear crown-substituted triple-decker phthalocyaninates afforded two series of complexes containing one dia- and one paramagnetic Ln­(III) ion (for Y and almost the whole lanthanide family), [(15C5)₄Pc]­M*­[(15C5)₄Pc]­M­(Pc) (or [M*,M] for brevity sake), where (15C5) is 15-crown-5; (Pc^2–) is phthalocyaninato dianion; and M ≠ M* = Y, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb. This approach consists of using LaPc₂ as an efficient Pc^2– source. The solid-state structures of two complexes ([Tm*,Y] and [Yb*,Y]) were studied by single-crystal X-ray diffraction analysis, providing therefore a structural model for the assignment and analysis of ¹H NMR spectra of the complexes, which is strongly affected by the presence of paramagnetic lanthanide ions. Model validation was performed on complexes containing two different paramagnetic ions[Dy*,Gd] and [Gd*,Dy] as well as [Tb*,Tm] and [Tm*,Tb]synthesized by the above-mentioned method

Determination of the Structural Parameters of Heteronuclear (Phthalocyaninato)bis(crownphthalocyaninato)lanthanide(III) Triple-Deckers in Solution by Simultaneous Analysis of NMR and Single-Crystal X‑ray Data

Application of a general and convenient approach to the synthesis of heteronuclear crown-substituted triple-decker phthalocyaninates afforded two series of complexes containing one dia- and one paramagnetic Ln­(III) ion (for Y and almost the whole lanthanide family), [(15C5)₄Pc]­M*­[(15C5)₄Pc]­M­(Pc) (or [M*,M] for brevity sake), where (15C5) is 15-crown-5; (Pc^2–) is phthalocyaninato dianion; and M ≠ M* = Y, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb. This approach consists of using LaPc₂ as an efficient Pc^2– source. The solid-state structures of two complexes ([Tm*,Y] and [Yb*,Y]) were studied by single-crystal X-ray diffraction analysis, providing therefore a structural model for the assignment and analysis of ¹H NMR spectra of the complexes, which is strongly affected by the presence of paramagnetic lanthanide ions. Model validation was performed on complexes containing two different paramagnetic ions[Dy*,Gd] and [Gd*,Dy] as well as [Tb*,Tm] and [Tm*,Tb]synthesized by the above-mentioned method

A Molecular Chameleon: Reversible pH- and Cation-Induced Control of the Optical Properties of Phthalocyanine-Based Complexes in the Visible and Near-Infrared Spectral Ranges

A series of novel nonperipherally substituted tetra-15-crown-5-dibutoxyoxanthrenocyanines (H₂, Mg, Zn), acting as chameleons with the unique properties of switchable absorption and emission in the near-infrared (NIR) spectral range have been synthesized and characterized by X-ray diffraction. The attachment of 15-crown-5-α-dibutoxyoxanthreno moieties to phthalocyanine is responsible for the high solubility of the resulting molecules and the red shift of the Q band to the NIR region and offers a unique possibility for postsynthetic modification of the optical properties of the molecules. Both aggregation of phthalocyanine and its participation in an acid–base equilibrium strongly alter their optical properties. For example, the absorption of complexes can be reversibly tuned from 686 up to 1028 nm because of the cation-induced formation of supramolecular dimers or subsequent protonation of <i>meso</i>-N atoms orf macrocycle, in contrast to peripherally substituted tetra-15-crown-5-phthalocyanines without oxanthrene moieties. The reversibility of these processes can be controlled by the addition of [2.2.2]­cryptand or amines. All investigated compounds exhibit fluorescence with moderate quantum yield, which can also be switched between the ON and OFF states by the action of similar agents

A Molecular Chameleon: Reversible pH- and Cation-Induced Control of the Optical Properties of Phthalocyanine-Based Complexes in the Visible and Near-Infrared Spectral Ranges

A series of novel nonperipherally substituted tetra-15-crown-5-dibutoxyoxanthrenocyanines (H₂, Mg, Zn), acting as chameleons with the unique properties of switchable absorption and emission in the near-infrared (NIR) spectral range have been synthesized and characterized by X-ray diffraction. The attachment of 15-crown-5-α-dibutoxyoxanthreno moieties to phthalocyanine is responsible for the high solubility of the resulting molecules and the red shift of the Q band to the NIR region and offers a unique possibility for postsynthetic modification of the optical properties of the molecules. Both aggregation of phthalocyanine and its participation in an acid–base equilibrium strongly alter their optical properties. For example, the absorption of complexes can be reversibly tuned from 686 up to 1028 nm because of the cation-induced formation of supramolecular dimers or subsequent protonation of <i>meso</i>-N atoms orf macrocycle, in contrast to peripherally substituted tetra-15-crown-5-phthalocyanines without oxanthrene moieties. The reversibility of these processes can be controlled by the addition of [2.2.2]­cryptand or amines. All investigated compounds exhibit fluorescence with moderate quantum yield, which can also be switched between the ON and OFF states by the action of similar agents

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