Solution and solid-state fluorescence emission from cyanostyrene molecules with multiple nitrogen atoms.

A design strategy has been proposed to utilize structure-driven solution and solid-state fluorescence emission of polynitrogen atoms. The strategy uses benzimidazole as the electron donor and pyridine as the electron acceptor to construct D-A-type cyanopyridine ethylene molecules. Theoretical calculations reveal that compound 1 has energy-close isomers in dilute solutions, with planar conformation in S0 and S1 states, reducing molecular motion and thus enhancing radiation efficiency (quantum yield up to 42.7%). Conversely, the distorted cyanobenzene structure reduces the quenching effect of π-π stacking alignment, and hydrogen bonding between molecules limits molecular vibration and rotation, ultimately leading to strong emission in the solid state (quantum yield up to 27.4%). These dual-state luminescence systems have wide-ranging potential applications in information encryption and temperature sensors.

Hydrophilic Cocrystals with Water Switched Luminescence.

Utilizing water molecules to regulate the luminescence properties of solid materials is highly challenging. Herein, we develop a strategy to produce water-triggered luminescence-switching cocrystals by coassembling hydrophilic donors with electron-deficient acceptors, where 1,2,4,5-Tetracyanobenzene (TCNB) was used as the electron acceptor and pyridyl benzimidazole derivatives were used as the electron donors enabling multiple hydrogen-bonds. Two cocrystals, namely 2PYTC and 4PYTC were obtained and showed heat-activated emission, and such emission could be quenched or weakened by adding water molecules. The cocrystal structure exhibited the donor molecule that can form multiple hydro bonds with water and acceptor molecules due to the many nitrogen atoms of them. The analyses of the photophysical data, powder X-ray diffraction, and other data confirmed the reversible fluorescence "on-off" effects were caused by eliminating and adding water molecules in the crystal lattice. The density functional theory calculations indicate that the vibration of the O-H bond of water molecules in the cocrystal can absorb the excitation energy and suppress fluorescence. Furthermore, the obtained cocrystals also showed temperature, humidity, and H+ /NH4 + responsive emission behavior, which allows their applications as thermal and humidity sensors, and multiple information encryptions. This research paves the way for preparing intelligent hydrophilic organic cocrystal luminescent materials.

Engineering Tunable Ratiometric Dual Emission in Single Emitter-based Amorphous Systems.

Molecular emitters with multi-emissive properties are in high demand in numerous fields, while these properties basically depend on specific molecular conformation and packing. For amorphous systems, special molecular arrangement is unnecessary, but it remains challenging to achieve such luminescent behaviors. Herein, we present a general strategy that takes advantage of molecular rigidity and S1 -T1 energy gap balance for emitter design, which enables fluorescence-phosphorescence dual-emission properties in various solid forms, whether crystalline or amorphous. Subsequently, the amorphism of the emitters based polymethyl methacrylate films endowed an in situ regulation of the dual-emissive characteristics. With the ratiometric regulation of phosphorescence by external stimuli and stable fluorescence as internal reference, highly controllable luminescent color tuning (yellow to blue including white emission) was achieved. There properties together with a persistent luminous behavior is of benefit for an irreplaceable set of optical information combination, featuring an ultrahigh-security anti-counterfeiting ability. Our research introduces a concept of eliminating the crystal-form and molecular-conformational dependence of complex luminescent properties through emitter molecular design. This has profound implications for the development of functional materials.

Highly Efficient Room-Temperature Light-Induced Synthesis of Polymer Dots: A Programming Control Paradigm of Polymer Nanostructurization from Single-Component Precursor.

Polymer dots (PDs) have raised considerable research interest due to their advantages of designable nanostructures, high biocompatibility, versatile photoluminescent properties, and recyclability as nanophase. However, there remains a lack of in situ, real-time, and noncontact methods for synthesizing PDs. Here we report a rational strategy to synthesize PDs through a well-designed single-component precursor (an asymmetrical donor-acceptor-donor' molecular structure) by photoirradiation at ambient temperature. In contrast to thermal processes that normally lack atomic economy, our method is mild and successive, based on an aggregation-promoted sulfonimidization triggered by photoinduced delocalized intrinsic radical cations for polymerization, followed by photooxidation for termination with structural shaping to form PDs. This synthetic approach excludes any external additives, rendering a conversion rate of the precursor exceeding 99%. The prepared PDs, as a single entity, can realize the integration of nanocore luminescence and precursor-transferred luminescence, showing 41.5% of the total absolute luminescence quantum efficiency, which is higher than most reported PD cases. Based on these photoluminescent properties, together with the superior biocompatibility, a unique membrane microenvironmental biodetection could be exemplified. This strategy with programming control of the single precursor can serve as a significant step toward polymer nanomanufacturing with remote control, high-efficiency, precision, and real-time operability.

Bright Free-Radical Emission in Ionic Liquids.

It is challenging to achieve stable and efficient radical emissions under ambient conditions. Herein, we present a rational design strategy to protect photoinduced carbonyl free radical emission through electrostatic interaction and spin delocalization effects. The host-guest system is constructed from tricarbonyl-substituted benzene molecules and a series of imidazolium ionic liquids as the guest and host, respectively, whereby the carbonyl anion radical emission can be in situ generated under the light irradiation and further stabilized by electrostatic interaction. More importantly, the anion species and the alkyl chain length of imidazolium ionic liquids show a noticeable effect on luminescence efficiency, with the highest radical emission efficiency is as high as 53.3 % after optimizing the imidazole ionic liquid's structure, which is about four times higher than the polymer-protected radical system. Theoretical calculations confirm the synergistic effect of strong electrostatic interactions and that the spin delocalization effect significantly stabilizes the radical emission. Moreover, such a radical emission system also could be integrated with a fluorescent dye to induce multi-color or even white light emission with reversible temperature-responsive characteristics. The radical emission system can also be used to detect different amine compounds on the basis of the emission changes and photoactivation time.

Odd-Number Cyclo[n]Carbons Sustaining Alternating Aromaticity.

Cyclo[n]carbons (n = 5, 7, 9, ..., 29) composed from an odd number of carbon atoms are studied computationally at density functional theory (DFT) and ab initio complete active space self-consistent field (CASSCF) levels of theory to get insight into their electronic structure and aromaticity. DFT calculations predict a strongly delocalized carbene structure of the cyclo[n]carbons and an aromatic character for all of them. In contrast, calculations at the CASSCF level yield geometrically bent and electronically localized carbene structures leading to an alternating double aromaticity of the odd-number cyclo[n]carbons. CASSCF calculations yield a singlet electronic ground state for the studied cyclo[n]carbons except for C25, whereas at the DFT level the energy difference between the lowest singlet and triplet states depends on the employed functional. The BHandHLYP functional predicts a triplet ground state of the larger odd-number cyclo[n]carbons starting from n = 13. Current-density calculations at the BHandHLYP level using the CASSCF-optimized molecular structures show that there is a through-space delocalization in the cyclo[n]carbons. The current density avoids the carbene carbon atom, leading to an alternating double aromaticity of the odd-number cyclo[n]carbons satisfying the antiaromatic [4k+1] and aromatic [4k+3] rules. C11, C15, and C19 are aromatic and can be prioritized in future synthesis. We predict a bond-shift phenomenon for the triplet state of the cyclo[n]carbons leading to resonance structures that have different reactivity toward dimerization.

Vibration-Regulated Multi-State Long-Lived Emission from Star-Shaped Molecules.

How to utilize molecular vibration to tune triplet-involved emissions in multiple states is highly challenging. Here, star-shaped triphenylamine derivatives have been employed as model systems to understand how molecular vibration affects thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) emissions in multiple states. Nonplanar, star-shaped conformations allow molecules to generate appropriate vibrations in the solution state, facilitating vibronic coupling between their T1 and T2 states to generate effective TADF. More importantly, a relatively dispersed state can allow the molecules to efficiently vibrate in the solid state, and a crystalline environment further promotes a more efficient TADF. Lastly, by suppressing molecular vibration to inhibit the TADF, ultra-long RTP was observed upon doping these molecules into polymers. These molecules can be used in information encryption and storage as well as bioimaging.

Electronic Materials: An Antiaromatic Propeller Made from the Four-Fold Fusion of Tetraoxa[8]circulene and Perylene Diimides.

The synthesis of an antiaromatic tetraoxa[8]circulene annulated with four perylene diimides (PDI), giving a dynamic non-planar π-conjugated system, is described. The molecule contains 32 aromatic rings surrounding one formally antiaromatic planarized cyclooctatetraene (COT). The intense absorption (ϵ=3.35×105  M-1 cm-1 in CH2 Cl2 ) and emission bands are assigned to internal charge-transfer transitions in the combined PDI-circulene π-system. The spectroscopic data is supported by density functional theory calculations, and nuclear independent chemical shift calculation indicate that the antiaromatic COT has increased aromaticity in the reduced state. Electrochemical studies show that the compound can reversibly reach the tetra- and octa-anionic states by reduction of the four PDI units, and the deca-anionic state by reduction of the central COT ring. The material functions effectively in bulk hetero junction solar cells as a non-fullerene acceptor, reaching a power conversion efficiency of 6.4 %.

Photoexcitation-Based Supramolecular Access to Full-Scale Phase-Diagram Structures through in situ Phase-Volume Ratio Phototuning.

Controlling phase separation and transition plays a core role in establishing and maintaining the function of diverse self-assembled systems. However, it remains challenging to achieve wide-range continuous phase transition for dynamically producing a variety of assembled structures. Here, we developed a far-from-equilibrium system, upon the integration of photoexcitation-induced aggregation molecules and block copolymers, to establish an in situ phase-volume ratio photocontrol strategy. Thus, full-scale phase-diagram structures, from lamellar structure to gyroidal, cylindrical, and finally to a spherical one, can be accessed under different irradiation periods. Moreover, the phase transition was accompanied by considerable aggregation-induced phosphorescence and hydrophilicity/hydrophobicity change for building a functional surface. This strategy allows for a conceptual advance of accessing a wide range of distinct self-assembled structures and functions in real time.

Shape Preserving Single Crystal to Amorphous to Single Crystal Polymorphic Transformation Is Possible.

Many crystalline materials form polymorphs and undergo solid-solid transitions between different forms as a function of temperature or pressure. However, there is still a poor understanding of the mechanism of transformation. Conclusions about the transformation process are typically drawn by comparing the crystal structures before and after the conversion, but gaining detailed mechanistic knowledge is strongly impeded by the generally fast rate of these transitions. When the crystal morphology does not change, it is assumed that crystallinity is maintained throughout the process. Here we report transformation between polymorphs of ZnCl2(1,3-diethylimidazole-2-thione)2 which are sufficiently slow to allow unambiguous assignment of single crystal to single crystal transformation with shape preservation proceeding through an amorphous intermediate phase. This result fundamentally challenges the commonly accepted views of polymorphic phase transition mechanisms.

Dianthracenylazatrioxa[8]circulene: Synthesis, Characterization and Application in OLEDs.

A soluble, green-blue fluorescent, π-extended azatrioxa[8]circulene was synthesized by oxidative condensation of a 3,6-dihydroxycarbazole and 1,4-anthraquinone by using benzofuran scaffolding. This is the first circulene to incorporate anthracene within its carbon framework. Solvent-dependent fluorescence and bright green electroluminescence accompanied by excimer emission are the key optical properties of this material. The presence of sliding π-stacked columns in the single crystal of dianthracenylazatrioxa[8]circulene is found to cause a very high electron-hopping rate, thus making this material a promising n-type organic semiconductor with an electron mobility predicted to be around 2.26 cm2 V-1 s-1 . The best organic light-emitting diode (OLED) device based on the dianthracenylazatrioxa[8]circulene fluorescent emitter has a brightness of around 16 000 Cd m-2 and an external quantum efficiency of 3.3 %. Quantum dot-based OLEDs were fabricated by using dianthracenylazatrioxa[8]circulene as a host matrix material.

Photoinduced Radical Emission in a Coassembly System.

Developing radical emission at ambient conditions is a challenging task since radical species are unstable in air. In the present work, we overcome this challenge by coassembling a series of tricarbonyl-substituted benzene molecules with polyvinyl alcohol (PVA). The strong hydrogen bonds between the guest dopants and the PVA host matrix protect the free radicals of carbonyl compounds after light irradiation, leading to strong solid state free radical emission. Changing temperature and peripheral functional groups of the tricarbonyl-substituted benzenes can influence the intensity of the radical emission. Quantum-chemical calculations predict that such free radical fluorescence originates from anti-Kasha D2 →D0 vertical emission by the anion radicals. The photoinduced radical emission by the tricarbonyl-substituted benzenes was successfully utilized for information encryption application.

A Fully Conjugated Planar Heterocyclic [9]Circulene.

Fully aromatic [n]circulenes have only been known to encompass up to eight aromatic rings (n = 8), with no reports of endeavors in the synthesis of higher-order analogues (n > 8). Herein we present the first [9]circulene, formally a diazatrioxa[9]circulene, along with a tetrahydro-diazatetraoxa[10]circulene. The key transformation, for construction of the macrocyclic framework, is a simple high-yielding dimerizing condensation between 3,6-dihydroxycarbazole and glyoxal. Single crystal X-ray analysis reveals the [9]circulene to be perfectly planar and containing elongated benzene rings, which is induced by strain to accommodate planarity. Alternating bond lengths in the solid state indicate contribution from a [9]radialene resonance structure in the [9]circulene π-system. The central nonaromatic rings of both circulenes have paratropic ring currents, as evident by nucleus independent chemical shift (NICS) and anisotropy of the induced current density (ACID) calculations, which can be attributed to induced paratropicity from the surrounding aromatic rings.

Compressing a Non-Planar Aromatic Heterocyclic [7]Helicene to a Planar Hetero[8]Circulene.

This work describes a synthetic approach where a non-planar aromatic heterocyclic [7]helicene is compressed to yield a hetero[8]circulene containing an inner antiaromatic cyclooctatetraene (COT) core. This [8]circulene consists of four benzene rings and four heterocyclic rings, and it is the first heterocyclic [8]circulene containing three different heteroatoms. The synthetic pathway proceeds via a the flattened dehydro-hetero[7]helicene, which is partially a helicene and partially a circulene: it is non-planar and helically chiral as helicenes, and contains a COT motif like [8]circulenes. The antiaromaticity of the COT core is confirmed by nucleus independent chemical shift (NICS) calculations. The planarization from a helically π-conjugated [7]helicene to a fully planar heterocyclic [8]circulene significantly alters the spectroscopic properties of the molecules. Post-functionalization of the [7]helicenes and the [8]circulenes by oxygenation of the thiophene rings to the corresponding thiophene-sulfones allows an almost complete fluorescence emission coverage of the visible region of the optical spectrum (400-700 nm).

Aromaticity of Even-Number Cyclo[n]carbons (n = 6-100).

The recently synthesized cyclo[18]carbon molecule has been characterized in a number of studies by calculating electronic, spectroscopic, and mechanical properties. However, cyclo[18]carbon is only one member of the class of cyclo[n]carbons-standalone carbon allotrope representatives. Many of the larger members of this class of molecules have not been thoroughly investigated. In this work, we calculate the magnetically induced current density of cyclo[n]carbons in order to elucidate how electron delocalization and aromatic properties change with the size of the molecular ring (n), where n is an even number between 6 and 100. We find that the Hückel rules for aromaticity (4k + 2) and antiaromaticity (4k) become degenerate for large Cn rings (n > 50), which can be understood as a transition from a delocalized electronic structure to a nonaromatic structure with localized current density fluxes in the triple bonds. Actually, the calculations suggest that cyclo[n]carbons with n > 50 are nonaromatic cyclic polyalkynes. The influence of the amount of nonlocal exchange and the asymptotic behavior of the exchange-correlation potential of the employed density functionals on the strength of the magnetically induced ring current and the aromatic character of the large cyclo[n]carbons is also discussed.

Charge inversion under plasma-nanodroplet reaction conditions excludes Fischer esterification for unsaturated fatty acids: a chemical approach for type II isobaric overlap.

Direct infusion ionization methods provide the highest throughput strategy for mass spectrometry (MS) analysis of low-volume samples. But the trade-off includes matrix effects, which can significantly reduce analytical performance. Herein, we present a novel chemical approach to tackle a special type of matrix effect, namely type II isobaric overlap. We focus on detailed investigation of a nanodroplet-based esterification chemistry for differentiating isotopologue [M + 2] signal due to unsaturated fatty acid (FA) from the monoisotopic signal from a saturated FA. The method developed involves the online fusion of nonthermal plasma with charged nanodroplets, enabling selective esterification of saturated FAs. We discovered that unsaturated FAs undergo spontaneous intramolecular reaction via a novel mechanism based on a carbocation intermediate to afford a protonated lactone moiety (resonance stabilized cyclic carbonium ion), whose mass is the same as the original protonated unsaturated FA. Therefore, the monoisotopic signal from any saturated FA can be selectively shifted away from the mass-to-charge position where the isobaric interference occurs to enable effective characterization by MS. The mechanism governing the spontaneous intramolecular reactions for unsaturated FAs was validated with DFT calculations, experimentation with standards, and isotope labeling. This novel insight achieved via the ultrafast plasma-nanodroplet reaction environment provides a potentially useful synthetic pathway to achieve catalyst-free lactone preparation. Analytically, we believe the performance of direct infusion MS can be greatly enhanced by combining our approach with prior sample enrichment steps for applications in biomedicine and food safety. Also, combination with portable mass spectrometers can improve the efficiency of field studies since front-end separation is not possible under such conditions.

Photo-controlled order-to-order host-guest self-assembly transfer for an afterglow effect with water resistance.

Due to the general incompleteness of photochemical reactions, the photostationary structure in traditional photo-controlled host-guest self-assembly transfer is usually disordered or irregular. This fact readily affects the photoregulation or improvement of related material properties. Herein, a photoexcitation-induced aggregation molecule, hydroxyl hexa(thioaryl)benzene (HB), was grafted into ß-cyclodextrin to form a host-guest system. Upon irradiation, the excited state conformational change of HB can drive an order-to-order phase transition of the system, enabling the transfer of the initial linear nanostructure to a photostationary worm-like nanostructure with orderliness and crystallinity capability. Along with the photoexcitation-controlled phase transition, an afterglow effect was obtained from the films prepared by doping the host-guest system into poly(vinyl alcohol). The afterglow effect had a superior water resistance, which successfully overcame the general sensitivity of doped materials with the afterglow effect to water vapor. These results are expected to provide new insights for pushing forward chemical self-assembly from the light perspective, towards materials with superior and stable properties under light treatment.

Edible Long-Afterglow Photoluminescent Materials for Bioimaging.

Confining luminophores into modified hydrophilic matrices or polymers is a straightforward and widely used approach for afterglow bioimaging. However, the afterglow quantum yield and lifetime of the related material remain unsatisfactory, severely limiting the using effect especially for deep-tissue time-resolved imaging. This fact largely stems from the dilemma between material biocompatibility and the quenching effect of water environment. Herein an in situ metathesis promoted doping strategy is presented, namely, mixing ≈10-3 weight ratio of organic-emitter multicarboxylates with inorganic salt reactants, followed by metathesis reactions to prepare a series of hydrophilic but water-insoluble organic-inorganic doping afterglow materials. This strategy leads to the formation of edible long-afterglow photoluminescent materials with superior biocompatibility and excellent bioimaging effect. The phosphorescence quantum yield of the materials can reach dozens of percent (the highest case: 66.24%), together with the photoluminescent lifetime lasting for coupes of seconds. Specifically, a long-afterglow barium meal formed by coronene salt emitter and BaSO4 matrix is applied into animal experiments by gavage, and bright stomach afterglow imaging is observed by instruments or mobile phone after ceasing the photoexcitation with deep tissue penetration. This strategy allows a flexible dosage of the materials during bioimaging, facilitating the development of real-time probing and theranostic technology.

Photoinduced Carbonyl Radical Luminescence in Host-Guest Systems.

Developing a free radical emission system in different states, especially in water, is highly challenging and desired. Herein, a host-guest coassembly strategy was used to protect the in situ photoactivated radical emission of carbonyl compounds in solid and aqueous solutions by doping them into a series of small molecules with hydroxyl groups. The intermolecular interactions between host and guest and the electron-donating ability of the hydroxyl group can significantly promote the formation and stabilization of luminescence by carbonyl radicals. Accordingly, the stimuli-responsive property of the free radical system was investigated in detail, and the self-assembled aggregates showed photoactive and thermoresponsive behaviors. In addition, an advanced ammonia compound identification system can be built based on a radical emission system. Our design strategy sheds light on developing free radical systems that can emit in various states, which will greatly broaden the application range of free radicals.

Thermally activated delayed fluorescence in a deep red dinuclear iridium(iii) complex: a hidden mechanism for short luminescence lifetimes.

The high luminescence efficiency of cyclometallated iridium(iii) complexes, including those widely used in OLEDs, is typically attributed solely to the formally spin-forbidden phosphorescence process being facilitated by spin-orbit coupling with the Ir(iii) centre. In this work, we provide unequivocal evidence that an additional mechanism can also participate, namely a thermally activated delayed fluorescence (TADF) pathway. TADF is well-established in other materials, including in purely organic compounds, but has never been observed in iridium complexes. Our findings may transform the design of iridium(iii) complexes by including an additional, faster fluorescent radiative decay pathway. We discover it here in a new dinuclear complex, 1, of the form [Ir(N^C)2]2(µ-L), where N^C represents a conventional N^C-cyclometallating ligand, and L is a bis-N^O-chelating bridging ligand derived from 4,6-bis(2-hydroxyphenyl)-pyrimidine. Complex 1 forms selectively as the rac diastereoisomer upon reaction of [Ir(N^C)2(µ-Cl)]2 with H2L under mild conditions, with none of the alternative meso isomer being separated. Its structure is confirmed by X-ray diffraction. Complex 1 displays deep-red luminescence in solution or in polystyrene film at room temperature (λem = 643 nm). Variable-temperature emission spectroscopy uncovers the TADF pathway, involving the thermally activated re-population of S1 from T1. At room temperature, TADF reduces the photoluminescence lifetime in film by a factor of around 2, to 1 µs. The TADF pathway is associated with a small S1-T1 energy gap ΔEST of approximately 50 meV. Calculations that take into account the splitting of the T1 sublevels through spin-orbit coupling perfectly reproduce the experimentally observed temperature-dependence of the lifetime over the range 20-300K. A solution-processed OLED comprising 1 doped into the emitting layer at 5 wt% displays red electroluminescence, λEL = 625 nm, with an EQE of 5.5% and maximum luminance of 6300 cd m-2.