13 research outputs found
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 LnÂ(III) ion
(for Y and almost the whole lanthanide family), [(15C5)<sub>4</sub>Pc]ÂM*Â[(15C5)<sub>4</sub>Pc]ÂMÂ(Pc) (or [M*,M] for brevity sake), where
(15C5) is 15-crown-5; (Pc<sup>2–</sup>) is phthalocyaninato
dianion; and M ≠M* = Y, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb. This
approach consists of using LaPc<sub>2</sub> as an efficient Pc<sup>2–</sup> 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 <sup>1</sup>H 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 ionsî—¸[Dy*,Gd] and [Gd*,Dy] as well as [Tb*,Tm]
and [Tm*,Tb]î—¸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
(H<sub>2</sub>, 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]Âcryptand 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 LnÂ(III) ion
(for Y and almost the whole lanthanide family), [(15C5)<sub>4</sub>Pc]ÂM*Â[(15C5)<sub>4</sub>Pc]ÂMÂ(Pc) (or [M*,M] for brevity sake), where
(15C5) is 15-crown-5; (Pc<sup>2–</sup>) is phthalocyaninato
dianion; and M ≠M* = Y, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb. This
approach consists of using LaPc<sub>2</sub> as an efficient Pc<sup>2–</sup> 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 <sup>1</sup>H 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 ionsî—¸[Dy*,Gd] and [Gd*,Dy] as well as [Tb*,Tm]
and [Tm*,Tb]î—¸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 LnÂ(III) ion
(for Y and almost the whole lanthanide family), [(15C5)<sub>4</sub>Pc]ÂM*Â[(15C5)<sub>4</sub>Pc]ÂMÂ(Pc) (or [M*,M] for brevity sake), where
(15C5) is 15-crown-5; (Pc<sup>2–</sup>) is phthalocyaninato
dianion; and M ≠M* = Y, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb. This
approach consists of using LaPc<sub>2</sub> as an efficient Pc<sup>2–</sup> 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 <sup>1</sup>H 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 ionsî—¸[Dy*,Gd] and [Gd*,Dy] as well as [Tb*,Tm]
and [Tm*,Tb]î—¸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
(H<sub>2</sub>, 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]Âcryptand 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
(H<sub>2</sub>, 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]Âcryptand 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 <sup>1</sup>H and <sup>31</sup>P NMR and UV–vis spectroscopies and in
the solid state by X-ray diffraction on single crystal, of a series
of galliumÂ(III) and indiumÂ(III) <i>meso</i>-monoÂ(diethoxyphosphoryl)Âporphyrins
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 galliumÂ(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 <sup>1</sup>H and <sup>31</sup>P NMR and UV–vis spectroscopies and in
the solid state by X-ray diffraction on single crystal, of a series
of galliumÂ(III) and indiumÂ(III) <i>meso</i>-monoÂ(diethoxyphosphoryl)Âporphyrins
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 galliumÂ(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 <sup>1</sup>H and <sup>31</sup>P NMR and UV–vis spectroscopies and in
the solid state by X-ray diffraction on single crystal, of a series
of galliumÂ(III) and indiumÂ(III) <i>meso</i>-monoÂ(diethoxyphosphoryl)Âporphyrins
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 galliumÂ(III) cations of adjacent porphyrin molecules
[Ga–O = 1.9708(13) Å]
Unusual Formation of a Stable 2D Copper Porphyrin Network
CopperÂ(II) 5,15-bisÂ(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 copperÂ(II) porphyrins. The resulting 2D structure is a rare example
of an assembly based on copperÂ(II) porphyrins where the copperÂ(II)
central metal ion is six-coordinated because of a weak interaction
with two phosphoryl groups of adjacent porphyrins. The other polymorph
of copperÂ(II) 5,15-bisÂ(diethoxyphosphoryl)-10,20-diphenylporphyrin
contains individual (isolated) porphyrin molecules with four-coordinated
copperÂ(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-bisÂ(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 copperÂ(II) porphyrin containing two axially
coordinated dioxane molecules was also obtained and characterized
by X-ray diffraction crystallography. The association of copperÂ(II)
5,15-bisÂ(diethoxyphosphoryl)-10,20-diphenylporphyrin in solution was
also studied