10 research outputs found
Роль семьи в процессе первичной социализации в отечественной и зарубежной литературе
A series of 5,15 push–pull <i>meso</i>-diarylzinc(II) porphyrinates, carrying one or two −COOH
or −COOCH<sub>3</sub> acceptor groups and a −OCH<sub>3</sub> or a −N(CH<sub>3</sub>)<sub>2</sub> donor group, show
in <i>N</i>,<i>N</i>-dimethylformamide and CHCl<sub>3</sub> solutions a negative and solvent-dependent second-order nonlinear-optical
(NLO) response measured by the electric-field-induced second-harmonic
generation (EFISH) technique, different from the structurally related
zinc(II) porphyrinate carrying a −N(CH<sub>3</sub>)<sub>2</sub> donor group and a −NO<sub>2</sub> acceptor group, where a
still solvent-dependent but positive EFISH second-order response was
previously reported. Moreover, when a −N(CH<sub>3</sub>)<sub>2</sub> donor group and a −COOH acceptor group are part of
a sterically hindered 2,12 push–pull β-pyrrolic-substituted
tetraarylzinc(II) porphyrinate, the EFISH response is positive and
solvent-independent. In order to rationalize these rather intriguing
series of observations, EFISH measurements have been integrated by
electronic absorption and IR spectroscopic investigations and by density
functional theory (DFT) and coupled-perturbed DFT theoretical and <sup>1</sup>H pulsed-gradient spin-echo NMR investigations, which prompt
that the significant concentration effects and the strong influence
of the solvent nature on the NLO response are originated by a complex
whole of different aggregation processes induced by the −COOH
group
Les calmars géants
8 páginas, 6 figurasPeer reviewe
Nonlinear-Optical Properties of α‑Diiminedithiolatonickel(II) Complexes Enhanced by Electron-Withdrawing Carboxyl Groups
We report the synthesis, characterization,
nonlinear-optical (NLO) properties, and density functional theory
(DFT) calculations for three nickel diiminedithiolate complexes [Ni(4,4′-R<sub>2</sub>carboxy-bpy)(L)] [R = methyl, L = 1,2-benzenedithiolate (bdt), <b>1</b>; R = ethyl, L = 5,6-dihydro-1,4-dithine-2,3-dithiolate (dddt), <b>2</b>; R = ethyl, L = 1-(<i>N</i>-methylindol-5-yl)ethene-1,2-dithiolate
(mi-5edt), <b>3</b>]. The crystal structure of <b>1</b> shows a square-planar coordination for the nickel ion and bond distances
consistent with a diiminedithiolate description for the complex. For
all complexes, the cyclic voltammetry measurements show two reversible
reduction processes (−1.353/–1.380 V and −0798/–0.830
V, respectively) and an anodic wave (+0.372/+0.601 V). The UV–vis
spectra present a band around 600–700 nm (ε = 4880–6000
dm<sup>3</sup> mol<sup>–1</sup> cm<sup>–1</sup>) mainly
attributed to a charge-transfer highest occupied molecular orbital
(HOMO)–lowest unoccupied molecular orbital (LUMO) transition,
which shows a large negative solvatochromic shift, characteristic
of push–pull complexes, and is responsible for the NLO properties
of these molecules. The charge-transfer character of this electronic
transition is confirmed by DFT calculations, with the HOMO mainly
centered on the dithiolate moiety and the LUMO on the bpy ligand,
with important contribution given by the carboxyl groups (≈13%).
Small contributions from the nickel(II) ion are present in both of
the frontier orbitals. The carboxyl groups enhance the optical properties
of this class of complexes, confirmed by comparison with the corresponding
unsubstituted compounds. The second-order NLO properties have been
measured by an electric-field-induced second-harmonic-generation technique
using a 10<sup>–3</sup> M solution in <i>N</i>,<i>N</i>-dimethylformamide and working with a 1.907 μm incident
wavelength, giving for μβ<sub>1.907</sub> (μβ<sub>0</sub>) values of −1095 (−581), −2760 (−954),
and −1650 (−618) × 10<sup>–48</sup> esu
for <b>1</b>–<b>3</b>, respectively. These values
are among the highest in the class of square-planar push–pull
complexes, similar to those found for dithionedithiolate compounds.
Moreover, spectroelectrochemical experiments demonstrate the possibility
of using these complexes as redox-switchable NLO chromophores
Nonlinear-Optical Properties of α‑Diiminedithiolatonickel(II) Complexes Enhanced by Electron-Withdrawing Carboxyl Groups
We report the synthesis, characterization,
nonlinear-optical (NLO) properties, and density functional theory
(DFT) calculations for three nickel diiminedithiolate complexes [Ni(4,4′-R<sub>2</sub>carboxy-bpy)(L)] [R = methyl, L = 1,2-benzenedithiolate (bdt), <b>1</b>; R = ethyl, L = 5,6-dihydro-1,4-dithine-2,3-dithiolate (dddt), <b>2</b>; R = ethyl, L = 1-(<i>N</i>-methylindol-5-yl)ethene-1,2-dithiolate
(mi-5edt), <b>3</b>]. The crystal structure of <b>1</b> shows a square-planar coordination for the nickel ion and bond distances
consistent with a diiminedithiolate description for the complex. For
all complexes, the cyclic voltammetry measurements show two reversible
reduction processes (−1.353/–1.380 V and −0798/–0.830
V, respectively) and an anodic wave (+0.372/+0.601 V). The UV–vis
spectra present a band around 600–700 nm (ε = 4880–6000
dm<sup>3</sup> mol<sup>–1</sup> cm<sup>–1</sup>) mainly
attributed to a charge-transfer highest occupied molecular orbital
(HOMO)–lowest unoccupied molecular orbital (LUMO) transition,
which shows a large negative solvatochromic shift, characteristic
of push–pull complexes, and is responsible for the NLO properties
of these molecules. The charge-transfer character of this electronic
transition is confirmed by DFT calculations, with the HOMO mainly
centered on the dithiolate moiety and the LUMO on the bpy ligand,
with important contribution given by the carboxyl groups (≈13%).
Small contributions from the nickel(II) ion are present in both of
the frontier orbitals. The carboxyl groups enhance the optical properties
of this class of complexes, confirmed by comparison with the corresponding
unsubstituted compounds. The second-order NLO properties have been
measured by an electric-field-induced second-harmonic-generation technique
using a 10<sup>–3</sup> M solution in <i>N</i>,<i>N</i>-dimethylformamide and working with a 1.907 μm incident
wavelength, giving for μβ<sub>1.907</sub> (μβ<sub>0</sub>) values of −1095 (−581), −2760 (−954),
and −1650 (−618) × 10<sup>–48</sup> esu
for <b>1</b>–<b>3</b>, respectively. These values
are among the highest in the class of square-planar push–pull
complexes, similar to those found for dithionedithiolate compounds.
Moreover, spectroelectrochemical experiments demonstrate the possibility
of using these complexes as redox-switchable NLO chromophores
Light-Induced Regiospecific Bromination of <i>meso</i>-Tetra(3,5-di-<i>tert</i>-butylphenyl)Porphyrin on 2,12 β‑Pyrrolic Positions
The
antipodal introduction of two bromine atoms on the 2,12 β-pyrrolic
position of 5,10,15,20-tetra(3,5-di-<i>tert</i>-butylphenyl)porphyrin
was successfully achieved by a light-induced reaction of the substrate
with excess NBS. Complexation with Ni<sup>II</sup> of the major regioisomer
led to good quality crystals, suitable for X-ray structure determination
with unprecedented probability levels. The regiospecific character
of the synthetic procedure and the exactness of the bromine atom position
assignment were thus confirmed, suggesting an unexpected electrophilic
aromatic substitution pathway rather than a free-radical halogenation
process. A QTAIM topological analysis on the DFT-optimized wave function
of the monosubstituted free-base porphyrin intermediate carrying a
bromine atom in C2 β-pyrrolic position confirmed the largest
negative charge for the C12 carbon atom in antipodal position, in
agreement with the proposed electrophilic aromatic substitution mechanism
New Internal-Charge-Transfer Second-Order Nonlinear Optical Chromophores Based on the Donor Ferrocenylpyrazole Moiety
A series
of new N-arylated ferrocenepyrazole structures, carrying
different donor or acceptor substituents in the para position of the
aryl ring, has been synthesized by the Chan–Lam cross-coupling
reaction. The nonplanar geometric molecular structure of some of these
chromophores together with their crystal packing was determined by
X-ray diffraction, and the HOMO and LUMO energy levels were evaluated
by electrochemical and optical measurements and by density functional
theoretical (DFT) calculations. By the investigation of solvent effects
and time-dependent DFT (TD-DFT) calculations, the intense electronic
absorption band around 270–310 nm was confirmed to be an internal-charge-transfer
(ICT) band, showing a significant red shift by increasing the electron
withdrawing properties of the substituent on the para position of
the aryl ring. TD-DFT calculations and electric field induced second
harmonic generation (EFISH) measurements of the quadratic hyperpolarizability
have shown that also the second-order nonlinear optical (NLO) response
of these new ICT chromophores can be tuned by changing the nature
of the substituent. Both theoretical μβ and β and
experimental EFISH μβ<sub>1907</sub> and β<sub>1907</sub> values are significant, with a quite satisfactory correlation of
the general trend of theoretical μβ and EFISH μβ<sub>1907</sub> values. The highest value of EFISH μβ<sub>1907</sub> (410 × 10<sup>–48</sup> esu) was measured
for the chromophore carrying the strong electron withdrawing NO<sub>2</sub> group
Physicochemical Investigation of the Panchromatic Effect on β‑Substituted Zn<sup>II</sup> Porphyrinates for DSSCs: The Role of the π Bridge between a Dithienylethylene Unit and the Porphyrinic Ring
Three novel dyes based on Zn<sup>II</sup> porphyrinates combined, in β-pyrrolic position, with
the π unit dithienylethylene (DTE) have been synthesized and
investigated for application in DSSCs. The panchromatic effect due
to elongation of the π-delocalized system through a bridge between
the porphyrinic ring and the DTE unit such as the 4-ethynylstyryl
(<b>1</b>), ethynyl (<b>2</b>), and ethenyl (<b>3</b>) bonds have been investigated by computational, electrochemical,
and photoelectrochemical methods. For all three dyes the π conjugated
substituents in the β position produced the expected panchromatic
effect with broadened electronic absorption spectra over a wide range
of wavelengths and IPCE spectra featuring a broad plateau in the region
430–650 nm. In addition both DFT computational and electrochemical
data have shown a smaller HOMO–LUMO energy gap for dye <b>3,</b> when compared to dye <b>2</b> suggesting a slightly
more facile conjugation between the porphyrinic core and the DTE unit
through the ethenylic bond. Conversely the photoelectrochemical investigation
showed improved DSSC performances from <b>3</b> to <b>1</b>. These results have been rationalized by an in-depth DFT computational
study of dyes <b>2</b> and <b>3</b> interacting with a
cluster of 82 TiO<sub>2</sub> units. The small energetic overlap between
the LUMO and the TiO<sub>2</sub> conduction band characterizing the
more structurally distorted dye <b>3</b> would suggest low quantum
yield of electron injection, while dye <b>2</b> shows a greater
interaction between the LUMO of the dye and the semiconductor. Consequently
the increased linearity and planarity of the structure of dye <b>1</b> seems to be the origin of its best performance in DSSC.
Therefore it appears that the nature of the bridge between the DTE
unit and the porphyrinic ring is quite relevant for the efficiency
of these dyes for DSSC, due to distortion from the planarity and linearity
of the structure of the dye and the consequent changes on the dye
π conjugation
Influence of Porphyrinic Structure on Electron Transfer Processes at the Electrolyte/Dye/TiO<sub>2</sub> Interface in PSSCs: a Comparison between meso Push–Pull and β‑Pyrrolic Architectures
Time-resolved photophysical and photoelectrochemical
investigations
have been carried out to compare the electron transfer dynamics of
a 2-β-substituted tetraarylporphyrinic dye (ZnB) and a 5,15-meso-disubstituted
diarylporphyrinic one (ZnM) at the electrolyte/dye/TiO<sub>2</sub> interface in PSSCs. Although the meso push–pull structural
arrangement has shown, up to now, to have the best performing architecture
for solar cell applications, we have obtained superior energy conversion
efficiencies for ZnB (6.1%) rather than for ZnM (3.9%), by using the
I<sup>–</sup>/I<sub>3</sub><sup>–</sup>-based electrolyte.
To gain deeper insights about these unexpected results, we have investigated
whether the intrinsic structural features of the two different porphyrinic
dyes can play a key role on electron transfer processes occurring
at the dye-sensitized TiO<sub>2</sub> interface. We have found that
charge injection yields into TiO<sub>2</sub> are quite similar for
both dyes and that the regeneration efficiencies by I<sup>–</sup>, are also comparable and in the range of 75–85%. Moreover,
besides injection quantum yields above 80%, identical dye loading,
for both ZnB and ZnM, has been evidenced by spectrophotometric measurements
on transparent thin TiO<sub>2</sub> layers after the same adsorption
period. Conversely, major differences have emerged by DC and AC (electrochemical
impedance spectroscopy) photoelectrochemical investigations, pointing
out a slower charge recombination rate when ZnB is adsorbed on TiO<sub>2</sub>. This may result from its more sterically hindered macrocyclic
core which, besides guaranteeing a decrease of π-staking aggregation
of the dye, promotes a superior shielding of the TiO<sub>2</sub> surface
against charge recombination involving oxidized species of the electrolyte
Coupling of Zinc Porphyrin Dyes and Copper Electrolytes: A Springboard for Novel Sustainable Dye-Sensitized Solar Cells
The combination of β-substituted
Zn<sup>2+</sup> porphyrin dyes and copper-based electrolytes represents
a sustainable route for economic and environmentally friendly dye-sensitized
solar cells. Remarkably, a new copper electrolyte, [Cu(2-mesityl-1,10-phenanthroline)<sub>2</sub>]<sup>+/2+</sup>, exceeds the performance reached by Co<sup>2+/3+</sup> and I<sup>–</sup>/I<sub>3</sub><sup>–</sup> reference electrolytes
A Multitechnique Physicochemical Investigation of Various Factors Controlling the Photoaction Spectra and of Some Aspects of the Electron Transfer for a Series of Push–Pull Zn(II) Porphyrins Acting as Dyes in DSSCs
A multitechnique physicochemical comparative investigation involving TDDFT theoretical calculations, steady-state and time-resolved electronic absorption spectra, and electrochemical and photoelectrochemical investigations was carried out on a family of push–pull porphyrinic sensitizers ([5-(4′-carboxy-phenylethynyl)-15-(4″-methoxy-phenylethynyl)-10,20-bis(3,5-di-<i>tert</i>-butylphenyl)porphyrinate]Zn(II) (<b>1</b>) and [5-(4′-carboxy-phenylethynyl)-15-(4″-<i>N</i>,<i>N</i>-dimethylamino-phenylethynyl)-10,20-bis(3,5-di-<i>tert</i>-butylphenyl)porphyrinate]Zn(II) (<b>2</b>) and the new fluorinated porphyrinic dye [5-(4′-carboxy-2′,3′,5′,6′-tetrafluorophenylethynyl)-15-(4″-<i>N</i>,<i>N</i>-dimethylamino-phenylethynyl)-10,20-bis(3,5-di-<i>tert</i>-butylphenyl)porphyrinate]Zn(II) (<b>3</b>)) with the aim of identifying the structurally related electronic properties at the basis of efficient interfacial charge separation. We found for all dyes a photoconversion nearly twice more effective for the B band than for the Q band, which could not be explained only by considerations based on the electron collection efficiency but also by a more energetically favorable electron injection from the S2 excited state. The lower photoconversion of the fluorinated dye <b>3</b>, when compared to dyes <b>1</b> and <b>2</b>, was explained not only by a more difficult absorption on the TiO<sub>2</sub> photoanode but also by a lower electron injection efficiency and a less successful hole transfer to the electrolyte, leading to increased charge recombination