23 research outputs found
Functionalizing tetraphenylpyrazine with perylene diimides (PDIs) as high-performance nonfullerene acceptors
Perylene diimide (PDI)-based small molecular acceptors with a three-dimensional structure are thought to be essential for efficient photocurrent generation and high power conversion efficiencies (PCEs). Herein, a couple of new perylene diimide acceptors (PPDI-O and PPDI-Se) have been designed and successfully synthesized using pyrazine as the core-flanking pyran and selenophene-fused PDIs, respectively. Compared to PPDI-O, PPDI-Se exhibits a blue-shifted absorption in the 400–600 nm range, a comparable LUMO level, and a more distorted molecular geometry. The PPDI-Se-based organic solar cell device with PDBT-T1 as the donor achieved the highest PCE of 7.47% and a high open-circuit voltage (Voc) of up to 1.05 V. The high photovoltaic performance of PPDI-Se-based devices can be attributed to its high LUMO energy level, complementary absorption spectra with donor materials, favorable morphology and balanced carrier transport. The results demonstrate the potential of this type of fullerene-free acceptor for high efficiency organic solar cells
Luminescent metal-organic frameworks (MOFs) as a chemopalette: Tuning the thermochromic behavior of dual-emissive phosphorescence by adjusting the supramolecular microenvironments
Two classical copper(I)-cluster-based luminophores, namely, Cu 4I4 and [Cu3Pz3]2 (Pz=pyrazolate), are immobilized in a supramolecular system through the formation of metal-organic framework (MOF) materials. This series of luminescent MOF materials, namely, [Cu4I4(NH3)Cu 3(L1)3]n, [Cu4I4(NH 2CH3)Cu3(L1)3]n, and [Cu4I4Cu3(L2)3]n (L1=3-(4-pyridyl)-5-(p-tolyl)pyrazolate; L2=3-(4-pyridyl)-5-(2,4-dimethylphenyl) pyrazolate), exhibit diverse thermochromism attributed to the relative functioning efficacy of the two coordination luminophores. Such an intriguing chemopalette effect is regulated by the different supramolecular microenvironments between the two-dimensional layers of these MOFs, and in particular, by the fine-tuned Cu-Cu distances in the excimeric [Cu 3Pz3]2 luminophore. The structure-property elucidation of the thermochromic behavior allows one to understand these optical materials with unusual dual-emissive properties. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
An unprecedented 2-D CuSCN coordination network containing both regular and irregular [Cu3(SCN)3] rings supported by a tridentate N-donor ligand
A neutral 2-D (CuSCN)∞ containing both regular and irregular [Cu3(SCN)3] six-membered rings supported by an asymmetrical tridentate ligand 3,5-bis(3-pyridyl)-1H-pyrazole (Hbppz) were prepared with the formula [Cu3(SCN)3(Hbppz)] ∞. The compound gives strong green luminescence with an emission maximum at 536 nm. © 2010 The Royal Society of Chemistry
Excimer and exciplex formation in a pair of bright phosphorescent isomers constructed from Cu3(pyrazolate)3 and Cu3I3 coordination luminophores
Reported herein are a pair of supramolecular pseudo-isomers, namely, (Cu 3I 3)(Cu 3L 3) 2· H 2O (1) and (Cu 3I 3)(Cu 3L 3) 2 (2) (L = 3-(4-pyridyl)-5-isobutyl-pyrazolate), both of which incorporate Cu 3Pz 3 (Pz = pyrazolate) and Cu 3I 3 clusters as luminophores. The two complexes show distinct yellow (570 nm) and orange (638 nm) emissions, which are ascribed to the formation of the excimer and exciplex involving the same or different copper(i)-cluster-based luminophores. © 2011 The Royal Society of Chemistry
A luminescent edge-interlocked prismatic heteroleptic metallocage assembled through a ligand replacement reaction
A luminescent edge-interlocked heteroleptic metallocage based on Cu3(pyrazolate)3 was prepared through a ligand replacement reaction from a homoleptic metallocage and a new ligand. Its structure was confirmed by XRD and MALDI-TOF mass spectrometry. Theoretical calculations revealed the new ligand was evidently responsible for the bathochromic shift of the optimal excitation. This work provides a heteroleptic strategy to regulate the interlocking fashion and photophysical mechanism of metallocages based on Cu3(pyrazolate)3
Mechanically Triggered Fluorescence/Phosphorescence Switching in the Excimers of Planar Trinuclear Copper(I) Pyrazolate Complexes
Luminescence
mechanochromism of the well-known Cu<sub>3</sub>Pz<sub>3</sub>-type
(Pz = pyrazolate) complexes is reported here, which is unusual for
this family. Two types of new Cu<sub>3</sub>Pz<sub>3</sub> complexes,
namely Cu<sub>3</sub>(EBPz)<sub>3</sub> (<b>1</b>; EBPz = ethyl-4′-benzoate-3,5-dimethylpyrazolate)
and Cu<sub>3</sub>(MBPz)<sub>3</sub> (polymorphs <b>2a</b>–<b>c</b>; MBPz = methyl-4′-benzoate-3,5-dimethylpyrazolate),
have been synthesized and characterized. Their crystal structures
exhibit a similar chairlike dimer stacking supported by short Cu···Cu
contacts, which would facilitate the formation of photoinduced excimers.
The dual emission from the organic fluorophore and excimeric copper
cluster phosphor is found to undergo mechanically induced intensity
switching between their high-energy (HE) and low-energy (LE) bands.
Specifically, the relative intensities of crystalline samples are
HE > LE, while the ground solid samples show LE > HE, resulting
in the overall emission color interchanging between bluish violet
and red. This switching can be reversed by application of solvent
to the ground samples, presumably due to recrystallization, and also
by heating. TD-DFT calculations reveal that the emissive singlet ligand
localized state (S<sub>1</sub>) and triplet cluster centered state
(T<sub>8</sub>) lie close in energy (separated by a gap of 0.1788
eV), suggesting the feasibility of dual emission and the possibility
of reverse intersystem crossing, consistent with the long fluorescent
lifetimes (10<sup>2</sup> ns scale) of the HE bands
Mechanically Triggered Fluorescence/Phosphorescence Switching in the Excimers of Planar Trinuclear Copper(I) Pyrazolate Complexes
Luminescence
mechanochromism of the well-known Cu<sub>3</sub>Pz<sub>3</sub>-type
(Pz = pyrazolate) complexes is reported here, which is unusual for
this family. Two types of new Cu<sub>3</sub>Pz<sub>3</sub> complexes,
namely Cu<sub>3</sub>(EBPz)<sub>3</sub> (<b>1</b>; EBPz = ethyl-4′-benzoate-3,5-dimethylpyrazolate)
and Cu<sub>3</sub>(MBPz)<sub>3</sub> (polymorphs <b>2a</b>–<b>c</b>; MBPz = methyl-4′-benzoate-3,5-dimethylpyrazolate),
have been synthesized and characterized. Their crystal structures
exhibit a similar chairlike dimer stacking supported by short Cu···Cu
contacts, which would facilitate the formation of photoinduced excimers.
The dual emission from the organic fluorophore and excimeric copper
cluster phosphor is found to undergo mechanically induced intensity
switching between their high-energy (HE) and low-energy (LE) bands.
Specifically, the relative intensities of crystalline samples are
HE > LE, while the ground solid samples show LE > HE, resulting
in the overall emission color interchanging between bluish violet
and red. This switching can be reversed by application of solvent
to the ground samples, presumably due to recrystallization, and also
by heating. TD-DFT calculations reveal that the emissive singlet ligand
localized state (S<sub>1</sub>) and triplet cluster centered state
(T<sub>8</sub>) lie close in energy (separated by a gap of 0.1788
eV), suggesting the feasibility of dual emission and the possibility
of reverse intersystem crossing, consistent with the long fluorescent
lifetimes (10<sup>2</sup> ns scale) of the HE bands
A real-world study of socioeconomic factors with survival in adults aged 18–64 years with renal cell carcinoma
Формирование адаптивной системы контроллинга в банке
У статті досліджено можливість формування адаптивної системи контролінгу в банку, визначено мету та основні етапи її здійснення, наведено характеристику принципів.This article explores the possibility of forming adaptive system controlling a bank specified purpose and main stages of its implementation, the characteristics of principles
Metallophilicity-Driven Dynamic Aggregation of a Phosphorescent Gold(I)–Silver(I) Cluster Prepared by Solution-Based and Mechanochemical Approaches
We
observed an unusual reversible aggregation process showing stimuli-responsive
structural dynamics and optical changes attributed to the formation
of a sandwich-like Au<sub>3</sub>–Ag–Au<sub>3</sub> cluster,
which can be synthesized through both solution and mechanochemical
methods. Unlike many other heteronuclear gold–silver clusters,
the affinity of two cyclic Au<sub>3</sub> complexes and a Ag<sup>I</sup> ion is solely bound by ligand unsupported Au–Ag bonding.
The assembly/disassembly behavior, further forming nanoaggregates,
is controllable by adjusting the concentration of the solution. In
the solid state, the insertion of Ag<sup>I</sup> ion can be implemented
through a mechanochemical approach, accompanied by visual color changes
and reversible luminochromism. Furthermore, an uncommon solid–liquid
extraction is demonstrated, showing the uniqueness of this labile
Au–Ag metallophilicity and hinting at the possibility of manipulating
a bonding process through a heterogeneous route