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1.
Artigo em Inglês | MEDLINE | ID: mdl-32783293

RESUMO

Dual emission materials have found much interest in the past years for materials and life science applications; however, a systematic overview on the underlying processes is missing by now. This is done herein, classifying dual emission (DE) phenomena, relying either on one emitter with two emitting states (DE1), two independent emitters (DE2), or two correlated emitters (DE3). Relevant DE mechanisms for materials science are then briefly described, giving the electronic and/or geometrical conditions under which they occur; for further reading, reference to reviews and textbooks is given, which offer detailed insight into the complex mechanistic aspects of the various DE processes, provide overviews on materials' families, or their applications. Avoiding ambiguities and misinterpretations, this systematic, insightful tutorial review might inspire future targeted design of DE materials.

2.
Chemistry ; 2020 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-32696530

RESUMO

Several theoretical studies have proposed strategies to generate helical molecular orbitals (Hel-MOs) in [n]cumulenes. While chiral even-[n] cumulenes feature Hel-MOs, odd-[n] cumulenes may also present them if the terminal groups lie on different planes. However, the proposed systems have been either experimentally unfeasible or resulted in opposite pseudo-degenerated Hel-MOs. We hereby demonstrate the introduction of a remarkable energy difference between helical orbitals of opposite twist by fixing the torsion angle between the terminal groups in butadiyne fragments. In order to experimentally lock the conformation of the terminal groups, we designed and synthesized cyclic architectures by combining acetylenes with chiral spirobifluorenes. The high stability of these systems with distinct helical orbitals allowed their isolation and full characterization. In our view these results constitute a milestone in the development of real systems presenting helical molecular orbitals.

3.
Chemphyschem ; 21(16): 1797-1804, 2020 08 18.
Artigo em Inglês | MEDLINE | ID: mdl-32602989

RESUMO

A combined spectroscopic and TD-DFT case study was performed, to identify a robust method to calculate the complex near UV/Vis absorption spectra of various amino- vs. nitro-substituted 2,4-diphenylquinolines, which vary strongly under neutral and successively acidic conditions. For this, different DFT functionals were tested for geometry optimization and the TD part to calculate the neutral and different protonated species in a fast screening approach, i. e. using single point calculations in an implicit solvent. Offset-corrected M06HF, hitherto only applied to polymers, was identified as a suitable method to reproduce the absorption spectra in a reasonable fashion for all different substitution pattern and all different protonated species at different pH values; moreover, the method properly predicts the energetic ordering of low-lying n-π* and ππ* transitions, which is decisive for the non-/emissive nature of the different compounds. In all, this might provide a valuable tool for computer-aided design of related classes of compounds.

4.
Chemphyschem ; 21(7): 616-624, 2020 04 02.
Artigo em Inglês | MEDLINE | ID: mdl-31997580

RESUMO

Two polymorphs with distinctly different fluorescence emission (green and yellow; G, Y) emanating from excitonic and excimeric contributions were prepared from solution as well as by using physical vapour transport. Based on crystal structure investigations, the vibrationally-resolved excitonic emission is found to originate from a ß-Sheet arrangement (G), whereas a sandwich herringbone structure is responsible for the excimer emission (Y). The intermolecular interactions and energies were quantified to have a complete picture of the decisive factors that controls the self-assembly. Halogen-bond directed self-assembly was explored to fine-tune the intermolecular interactions through co-crystallization as well as a commercially viable liquid assisted grinding method. A smooth fluorescence shift from G to Y was achieved by co-assembly due to substantial differences in the π orbital overlap in the molecular packing. Our investigation provides a comprehensive understanding of the origin of excitonic and excimeric contributions of emission behaviour in conjunction with the molecular packing and π-π orbital overlap, and might provide a directive towards the engineering of fluorescent functional molecular materials.

5.
J Am Chem Soc ; 142(6): 2835-2843, 2020 02 12.
Artigo em Inglês | MEDLINE | ID: mdl-31957436

RESUMO

Absorption spectra of cyanine⊕·Br⊖ salts show a remarkable solvent dependence in non/polar solvents, exhibiting narrow, sharp band shapes in dichloromethane but broad features in toluene; this change was attributed to ion pair association, stabilizing an asymmetric dipolar structure, similar to the situation in the crystal (Bouit, P.-A., et al. J. Am. Chem. Soc. 2010, 132, 4328). Our density functional theory (DFT)-based quantum mechanics/molecular mechanics (QM/MM) calculations of the crystals evidence the crucial role of specific asymmetric anion positioning on the lowering of the symmetry. Molecular dynamics (MD) simulations prove the ion pair association in nonpolar solvents. Time-dependent DFT vibronic calculations in toluene show that ion pairing indeed stabilizes an asymmetric dipolar structure in the electronic ground state. This largely broadens the absorption spectrum in very reasonable agreement with experiment, while the principal pattern of vibrational modes is retained. The current findings allow us to establish a unified picture of the symmetry breaking of polymethine dyes in fluid solution.

6.
Phys Chem Chem Phys ; 21(40): 22429-22439, 2019 Oct 16.
Artigo em Inglês | MEDLINE | ID: mdl-31580353

RESUMO

In the framework of optoelectronic luminescent materials, non-radiative decay mechanisms are relevant to interpret efficiency losses. These radiationless processes are herein studied theoretically for a series of stilbenoid derivatives, including distyrylbenzene (DSB) and cyano-substituted distyrylbenzene (DCS) molecules in vacuo. Given the difficulties of excited-state reaction path determinations, a simplified computational strategy is defined based on the exploration of the potential energy surfaces (PES) along the elongation, twisting, and pyramidalization of the vinyl bonds. For such exploration, density functional theory (DFT), time-dependent (TD)DFT, and complete-active-space self-consistent field/complete-active-space second-order perturbation theory (CASSCF/CASPT2) are combined. The strategy is firstly benchmarked for ethene, styrene, and stilbene; next it is applied to DSB and representative DCS molecules. Two energy descriptors are derived from the approximated PES, the Franck-Condon energy and the energy gap at the elongated, twisted, and pyramidalized structures. These energy descriptors correlate fairly well with the non-radiative decay rates, which validates our computational strategy. Ultimately, this strategy may be applied to predict the luminescence behavior in related compounds.

7.
Adv Mater ; 31(6): e1805554, 2019 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-30549300

RESUMO

The addition of chemical additives is considered as a promising approach for obtaining high-quality perovskite films under mild conditions, which is essential for both the efficiency and the stability of organic-inorganic hybrid perovskite solar cells (PeSCs). Although such additive engineering yields high-quality films, the inherent insulating property of the chemical additives prevents the efficient transport and extraction of charge carriers, thereby limiting the applicability of this approach. Here, it is shown that organic conjugated molecules having rhodanine moieties (i.e., SA-1 and SA-2) can be used as semiconducting chemical additives that simultaneously yield large-sized perovskite grains and improve the charge extraction. Using this strategy, a high power conversion efficiency of 20.3% as well as significantly improved long-term stability under humid air conditions is achieved. It is believed that this approach can provide a new pathway to designing chemical additives for further improving the efficiency and stability of PeSCs.

8.
J Phys Chem Lett ; 9(14): 3870-3877, 2018 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-29939753

RESUMO

Water-soluble, highly fluorescent host-guest chromophore-cucurbit[8]uril supramolecular polymer bundles are investigated by polarized time-resolved photoluminescence spectroscopy, structural methods, and quantum chemistry to fully reveal structural organization and heterogeneity but, in particular, energy-transfer dynamics, being of crucial importance for the design of supramolecular artificial light-harvesting systems.

9.
Nanoscale ; 9(44): 17415-17421, 2017 Nov 16.
Artigo em Inglês | MEDLINE | ID: mdl-29104980

RESUMO

In this work, plasmonic nano-gaps consisting of a silver nanoparticle coupled to an extended silver film have been fully optimized for single molecule Surface-Enhanced Raman Scattering (SERS) spectroscopy. The SERS signal was found to be strongly dependent on the particle size and the molecule orientation with respect to the field inside the nano-gap. Using Finite Difference Time Domain (FDTD) simulations to complement the experimental measurements, the complex interplay between the excitation enhancement and the emission enhancement of the system as a function of particle size were highlighted. Additionally, in conjunction with Density Functional Theory (DFT), the well-defined field direction in the nano-gap enables to recover the orientation of individual molecules.

10.
Angew Chem Int Ed Engl ; 56(51): 16207-16211, 2017 12 18.
Artigo em Inglês | MEDLINE | ID: mdl-29110380

RESUMO

The highly sensitive optical detection of oxygen including dissolved oxygen (DO) is of great interest in various applications. We devised a novel room-temperature-phosphorescence (RTP)-based oxygen detection platform by constructing core-shell nanoparticles with water-soluble polymethyloxazoline shells and oxygen-permeable polystyrene cores crosslinked with metal-free purely organic phosphors. The resulting nanoparticles show a very high sensitivity for DO with a limit of detection (LOD) of 60 nm and can be readily used for oxygen quantification in aqueous environments as well as the gaseous phase.

11.
Adv Mater ; 29(36)2017 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-28745406

RESUMO

A new 2:1 donor (D):acceptor (A) mixed-stacked charge-transfer (CT) cocrystal comprising isometrically structured dicyanodistyrylbenzene-based D and A molecules is designed and synthesized. Uniform 2D-type morphology is manifested by the exquisite interplay of intermolecular interactions. In addition to its appealing structural features, unique optoelectronic properties are unveiled. Exceptionally high photoluminescence quantum yield (ΦF ≈ 60%) is realized by non-negligible oscillator strength of the S1 transition, and rigidified 2D-type structure. Moreover, this luminescent 2D-type CT crystal exhibits balanced ambipolar transport (µh and µe of ≈10-4 cm2 V-1 s-1 ). As a consequence of such unique optoelectronic characteristics, the first CT electroluminescence is demonstrated in a single active-layered organic light-emitting transistor (OLET) device. The external quantum efficiency of this OLET is as high as 1.5% to suggest a promising potential of luminescent mixed-stacked CT cocrystals in OLET applications.

12.
J Chem Phys ; 147(3): 034903, 2017 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-28734298

RESUMO

A time-dependent density functional theory study is performed to reveal the excited state absorption (ESA) features of distyrylbenzene (DSB), a prototype π-conjugated organic oligomer. Starting with a didactic insight to ESA based on simple molecular orbital and configuration considerations, the performance of various density functional theory functionals is tested to reveal the full vibronic ESA features of DSB at short and long probe delay times.

13.
J Phys Chem Lett ; 8(1): 91-101, 2017 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-27958747

RESUMO

Fluorination is frequently used to significantly change the properties of conjugated organic materials due to fluorine's exceptional properties; well-known is its impact on electronic structure, but it also impacts the geometry despite fluorine's small size. Less known, the changes in the electronic and geometrical properties may provoke drastic changes of the excited state properties like batho- and hypsochromic shifts of absorption and emission bands (inter alia leading to excited state switching), hypo- and hyperchromic effects, spectral broadening, and changes of the nonradiative deactivation pathways. The state of the art on these issues is summarized in the current Perspective to stimulate further discussions on this intriguing subject.

14.
Angew Chem Int Ed Engl ; 55(51): 15915-15919, 2016 12 19.
Artigo em Inglês | MEDLINE | ID: mdl-27860154

RESUMO

Supramolecular polymers (SPs) have received great attention because of their potential for various practical applications. As part of our search for SPs that are highly fluorescent in aqueous media, we designed a system based on a cucurbit[8]uril (CB[8]) host and a newly designed cyanostilbene guest. Fluorescence quantum yields of ≈0 % in the disassembled monomer state and 91 % in the CB[8]-induced SP state were obtained. The intriguing photophysical properties of the SP are elucidated through detailed experimental and computational analysis, paving the way towards a fascinating class of water-soluble fluorescent SPs.

15.
Chemistry ; 22(38): 13588-98, 2016 Sep 12.
Artigo em Inglês | MEDLINE | ID: mdl-27555050

RESUMO

A set of triads in which o- and m-carborane clusters are bonded to two stilbene units through Ccluster -CH2 bonds was synthesized, and their structures were confirmed by X-ray diffraction. A study on the influence of the o- and m- isomers on the absorption and photoluminescence properties of the stilbene units in solution revealed no charge-transfer contributions in the lowest excited state, as confirmed by (TD)DFT calculations. The presence of one or two B-I groups in m-carborane derivatives does not affect the emission properties of the stilbenes in solution, probably due to the rather large distance between the iodo substituents and the fluorophore. Nevertheless, a significant redshift of the photoluminescence (PL) emission maximum in the solid state (thin films and powder samples) compared to solution was observed; this can be traced back to PL sensitization, most probably due to more densely packed stilbene moieties. Remarkably, the PL absolute quantum yields of powder samples are significantly higher than those in solution, and this was attributed to the restricted environment and the aforementioned sensitization. Thus, the bonding of the carborane clusters to two stilbene units preserves their PL behavior in solution, but produces significant changes in the solid state. Furthermore, iodinated species can be considered to be promising precursors for theranostic agents in which both imaging and therapeutic functions could possibly be combined.

16.
Adv Mater ; 28(41): 9169-9174, 2016 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-27572671

RESUMO

Naphthalenediimide-based random copolymers (PNDI-TVTx) with different π-conjugated dithienylvinylene (TVT) versus π-nonconjugated dithienylethane (TET) unit ratios (x = 100→0%) are investigated. The PNDI-TVTx-transistor electron/hole mobilities are affected differently, a result rationalized by molecular orbital topologies and energies, with hole mobility vanishing but electron mobility decreasing only by ≈2.5 times when going from x = 100% to 40%.

17.
Phys Chem Chem Phys ; 18(24): 16501-8, 2016 Jun 28.
Artigo em Inglês | MEDLINE | ID: mdl-27263988

RESUMO

The photophysics (spectral positions, band shapes, fluorescence quantum yields and lifetimes) of a series of fluorinated ladder type quaterphenyls L4P and L4P-Fn (n = 2, 4, 6) depend strongly on the degree and position of fluorine, despite the fact that substitution is not performed in the rings but only in methylene-bridges. This is driven by subtle differences in the molecular orbitals (MOs) participating in the electronic transitions, and in the vibronic pattern of the S0 and S1 electronic states as revealed by (TD)DFT calculations. Solid state spectra for n = 0, 2, 4 are similar to those of solution due to small intermolecular interactions as revealed by combined X-ray and (TD)DFT analysis.

18.
J Phys Condens Matter ; 28(13): 134002, 2016 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-26931487

RESUMO

Organic semiconductors (OSC) are attracting much interest for (opto)electronic applications, such as photovoltaics, LEDs, sensors or solid state lasers. In particular, crystals formed by small π-conjugated molecules have shown to be suitable for constructing OSC devices. However, the (opto)electronic properties are complex since they depend strongly on both the mutual orientation of molecules as well as the perfection of bulk crystal surfaces. Hence, there is an urgent need to control nano-topographic OSC features in real space. Here we show that friction force microscopy in water is a very suitable technique to image the free surface morphology of an OSC single crystal (TDDCS) with sub-nanometer resolution. We demonstrate the power of the method by direct correlation to the structural information extracted from combined single crystal (SC-) and specular (s-) XRD studies, which allows us to identify the pinning centers encountered in the stick-slip motion of the probing tip with the topmost methyl groups on the TDDCS surface.

19.
Chem Rev ; 116(9): 4937-82, 2016 05 11.
Artigo em Inglês | MEDLINE | ID: mdl-26959943

RESUMO

Natural anthocyanin pigments/dyes and phenolic copigments/co-dyes form noncovalent complexes, which stabilize and modulate (in particular blue, violet, and red) colors in flowers, berries, and food products derived from them (including wines, jams, purees, and syrups). This noncovalent association and their electronic and optical implications constitute the copigmentation phenomenon. Over the past decade, experimental and theoretical studies have enabled a molecular understanding of copigmentation. This review revisits this phenomenon to provide a comprehensive description of the nature of binding (the dispersion and electrostatic components of π-π stacking, the hydrophobic effect, and possible hydrogen-bonding between pigment and copigment) and of spectral modifications occurring in copigmentation complexes, in which charge transfer plays an important role. Particular attention is paid to applications of copigmentation in food chemistry.


Assuntos
Antocianinas/química , Corantes/química , Fenóis/química , Pigmentos Biológicos/química , Cor , Ligação de Hidrogênio
20.
Chem Sci ; 7(3): 2359-2363, 2016 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-29997779

RESUMO

Metal-free organic phosphors can be an attractive smart optical sensing materials since, in such compounds, intersystem crossing (ISC) and the phosphorescence process are placed in subtle competition with fluorescence, internal conversion (IC), and non-radiative decay pathways. Here, we report a unique environment-dependent multi-luminescence switching behavior of metal-free organic phosphorescent materials. Through combined photophysical measurements and computational electronic structure analysis, we systematically investigated how physicochemical properties of organic solvents affect the photophysical pathways of the metal-free organic phosphors. By rationally adapting the finding into phosphor-doped electrospun polymer fibers, we developed a new luminometric sensory platform and achieved selective detection of eight different common organic solvents. The presented finding provides new possibilities for metal-free organic phosphors to be a novel class of smart optical sensory materials.

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