Unusual Photophysical Properties Research Articles

Unusual Photophysical Properties of Porphyrin-Based Supramolecular Polymers Unveiled: The Role of Metal Ligands and Side Group Amide Connectivity

Unusual Photophysical Properties of Porphyrin-Based Supramolecular Polymers Unveiled: The Role of Metal Ligands and Side Group Amide Connectivity

Reductive Activation of Aryl Chlorides by Tuning the Radical Cation Properties of N-Phenylphenothiazines as Organophotoredox Catalysts.

Aryl chlorides as substrates for arylations present a particular challenge for photoredox catalytic activation due to their strong C(sp2 )-Cl bond and their strong reduction potential. Electron-rich N-phenylphenothiazines, as organophotoredox catalysts, are capable of cleaving aryl chlorides simply by photoinduced electron transfer without the need for an additional electrochemical activation setup or any other advanced photocatalysis technique. Due to the extremely strong reduction potential in the excited state of the N-phenylphenothiazines the substrate scope is high and includes aryl chlorides both with electron-withdrawing and electron-donating substituents. We evidence this reactivity for photocatalytic borylations and phosphonylations. Advanced time-resolved transient absorption spectroscopy in combination with electrochemistry was the key to elucidating and comparing the unusual photophysical properties not only of the N-phenylphenothiazines, but also of their cation radicals as the central intermediates in the photocatalytic cycle. The revealed photophysics allowed the excited-state and radical-cation properties to be fine-tuned by the molecular design of the N-phenylphenothiazines; this improved the photocatalytic activity.

Substituent-Dependent Azide Addition to Isocyanides Generates Strongly Luminescent Iridium Complexes.

Ligand-centered functionalization reactions offer diverse strategies to prepare luminescent organometallic compounds. These compounds can have unique structures that are not accessible via traditional coordination chemistry and can possess enhanced or unusual photophysical properties. Here we show that bis-cyclometalated iridium bis-isocyanide complexes (1) react with azide (N3-) to form novel luminescent structures. The fate of the reaction with azide is determined primarily by the substituent on the aryl isocyanide. Those with electron-withdrawing substituents (CF3 or NO2) react with 1 equiv of azide followed by N2 extrusion, forming aryl cyanamido products (2). With electron-donating groups on the aryl isocyanide the reactivity is more diverse, and three outcomes are possible. In two cases, the isocyanide and azide undergo a [3 + 2] cycloaddition to form a C-bound tetrazolato structure (3). In three other cases, 2 equiv of azide are involved in the formation of a previously unobserved structure, where a tetrazolato and aryl cyanamido couple and rearrange to form a chelating ligand comprised of an N-bound tetrazolato and an acyclic diaminocarbene (4). Finally, a bimetallic aryl cyanamido complex (5) is isolated in one case. All compounds are luminescent, some with exceptional photoluminescence quantum yields as high as 0.81 in solution for sky-blue emission, and 0.87 for yellow emission and 0.65 for orange-red emission in polymer films.

Steric Hindrance Governs the Photoinduced Structural Planarization of Cycloparaphenylene Materials.

Cycloparaphenylenes ([n]CPPs) and their derivatives are known for the unique size-dependent photophysical properties, which are largely attributed to the structural planarization-associated exciton localization, attracting substantial research attention. In this work, we show that the steric hindrance between neighboring structural units plays a key role in governing the photoinduced global/local structural planarization and electron-hole distribution features of [n]CPP materials, due to the tunable strength of H···H repulsion between neighboring units via structural modification or C-H distance variation as revealed by density functional theory (DFT) and time-dependent DFT calculations. According to our results, steric hindrance controls the manner and also the extent of excited-state structural planarization, where a weak (strong) steric hindrance favors (hinders) structural planarization upon relaxation in the first excited singlet (S1) state as compared to the ground (S0)-state structure. Depending on the molecular structures, steric hindrance leads to fully delocalized, partially separated, or more localized electron-hole distributions. For example, via H···H repulsion release by manually shortening the C-H distance or by chemical substitution of C-H with N atoms, the modified [10]CPP structures show fully planarized configurations (each dihedral angle can be less than 2°) and entirely delocalized electron-hole distribution upon photorelaxation. This work provides insights into the structural origin of the unusual photophysical properties of [n]CPPs and shows the promise of steric hindrance tuning in accessing diverse excited-state features in [n]CPP materials.

Unusual photophysical properties of a new tricyclic derivative of thiopurines in terms of potential applications

The thio analogues of purine bases have been found to possess notable biological and pharmacological capabilities and have an important role to play as anticancer and immunosuppressive drugs. In this work a new tricyclic analogue of guanosine containing sulfur was synthesized, in particular, DTEG (2′,3′,5′-tri-O-acetyl-6,9-dithioethanoguanosine). Although there is promise for thiopurine derivatives for biomedical applications, there are some liabilities in regard to their exposure to light. As a preliminary survey for such difficulties with DTEG, this work looks into spectral and photophysical processes of DTEG using time-resolved and steady-state optical excitation. In contrast to other thiopurines, which have long-lived triplets, DTEG is shown to have a short-lived triplet making it less dangerous for singlet-oxygen sensitization. Even in anaerobic solutions, its photoreactivity is negligible. These various unusual photochemical properties of DTEG are consistent with DTEG being very promising as an alternative drug to the currently used 6-thiopurines. DTEG also has some interesting photophysical behavior that is distinct from other thioketones. Although thioketones have an unusual fluorescence violating Kasha’s Rule and emitting from the second excited singlet state, DTEG does this also, but, in addition, it shows dual fluorescence by emitting from its first excited singlet as well. The assignments of the nature of these excited states are supported by DFT results. This theory and associated kinetic analysis show quantitatively that the dual fluorescence is, in part, tied to the relatively fast S2 to S1 internal conversion compared to other S2 decays and, in part, tied to the relatively slow nonradiative decay of S1 itself.

Cu-related defects and optical properties in copper–indium–selenide quantum dots by a green synthesis

Quantum dots of I–III–VI ternary compounds exhibit unusual photophysical properties and technological utility, which attract attention and have been intensely investigated. CuInSe2 quantum dots are an environmentally friendly composition, a direct transition, and an adjustable bandgap. Here, we discuss the influence of the Cu/In molar ratio of CuInSe2 quantum dots on Cu-related defects and photo-physical properties, and CuInSe2 quantum dots are synthesized by a green, safe, and low-temperature method in triethylene glycol. The proportion of the +1 and +2 oxidation states of Cu in the quantum dots will change with the Cu/In molar atomic ratio. The +1-oxidation state of Cu will prolong the carrier recombination lifetime and provide favorable conditions for the transfer and collection of carriers. By adjusting for different defect types, we can better apply CISe quantum dots in devices and other fields.

Unusual photophysical properties of fluorescent cytosine analogues utilized in real-time detecting i-motif DNA: A theoretical study

In this work, we report a theoretical study on the optical properties of a set of fluorescent cytosine analogues as indicators to examine the structural changes during the four-stranded intercalated motif (i-motif) formation. Herein, the neutral bases, protonated monomers and hemiprotonated base pairs corresponding to different stages of the forming process are considered. The calculated results reveal that the modified cytosine analogues show red-shifted absorption and bright fluorescence emission arisen from the increased π-conjugation characters. Especially, the 1,3-diaza-2-oxophenoxazine (tCO) possesses high fluorescence intensity, large Stokes shift and distinct wavelengths for all considered configurations (445 nm for neutral base, 546 nm for protonated monomer and 509 nm for hemiprotonated base pair), in which the tCO becomes potential candidate for application in detecting i-motif structure. Besides, the fluorescence quenching induced by the proton transfer is observed depending on base pairing, which is another efficient optical probe during the i-motif formation. Also examined are the effects of binding to deoxyribose, which can red-shift the fluorescence emissions and enhance fluorescence intensities for both monomers and base pair.

Polymorph acceptor-based triads with photoinduced TADF for UV sensing

In contrast to many donor–acceptor type organic luminophores exhibiting thermally activated delayed fluorescence (TADF), two deep blue TADF emitters designed in this work contain only typical electron accepting moieties with different electron accepting abilities. Derivatives of benzophenone and diphenylsulfone substituted with phenothiazine-5,5-dioxide donor moieties were synthesized and studied. In addition to the TADF, green to blue emission color switching and strong fluorescence intensity enhancement by more than 60 times was detected for THF solution of the derivative of phenothiazine-5,5-dioxide and benzophenone under increase of UV excitation dose. We proved by a variety of experimental and theoretical studies that the unusual photophysical properties of the derivative of benzophenone are mainly related to the formation of different conformers. The photostimulated intensity enhancement of the compound is due to the rise of the quantity of triplet states and their further crossing to singlet states. To our knowledge, this is the first observation of a combination of photoinduced color switching and triplet-dependent emission intensity enhancement. These properties are shown to be useful for UV sensing with very low detection limits (less than 10 μW/cm2 for the toluene solution). Under gradual increase of UV excitation dose, the DMF solution demonstrated a green → blue color swishing from (0.34; 0.44) to (0.17; 0.18) of CIE coordinates that can be detected by naked eye.

Azulene-Based π-Functional Materials: Design, Synthesis, and Applications.

ConspectusAzulene, an isomer of naphthalene, is a molecule of historical interest for its unusual photophysical properties, including a beautiful blue color derived from the narrow HOMO-LUMO energy gap and anti-Kasha fluorescence from S2 to S0. More recently, it has attracted increasing attention for its novel electronic structure, including an electron-rich five-membered ring and an electron-deficient seven-membered ring with a dipole moment of 1.08 D resulting from resonance delocalization, its different reactivities at odd and even positions, and its stimuli-responsive behavior. As a key building block, azulene has been used in various fields because of its unique physicochemical properties. Recent studies have demonstrated the great potential of azulene for constructing advanced organic materials. However, exploring azulene-based materials has long been hindered by challenges in molecular design and synthesis. Most of the reported azulene-based materials have the azulene unit incorporated through the five-membered ring or seven-membered ring. Creating azulene-based novel building blocks for optoelectronics and using 2,6-connected azulene units to construct conjugated polymers that can adequately utilize the "donor-acceptor" structure of azulene remained underexplored before our contributions. Besides, for most azulene-fused polycyclic aromatic hydrocarbons (PAHs) and heteroaromatics, the azulene substructures were created during later synthesis stages, and the use of azulene derivatives as starting materials to design and synthesize PAHs and heteroaromatics intelligently is still limited.In this Account, we summarize our efforts on the design, synthesis, and applications of azulene-based π-functional materials. Our studies start with the creation of novel π-conjugated structures based on azulene. The design strategy, synthesis, and optoelectronic performance of the first class of azulene-based aromatic diimides, 2,2'-biazulene-1,1',3,3'-tetracarboxylic diimide (BAzDI) and its π-extended and π-bridged derivatives, are presented. Notably, antiparallel stacking between adjacent azulene units derived from azulene's dipole was observed in single crystals of BAzDI and its derivatives. Besides, we developed an azulene-fused isoindigo analogue, azulenoisoindigo, which combines the merits of both isoindigo and azulene, including reversible redox behavior and reversible proton responsiveness. Then we discuss our contributions to the design and synthesis of 2,6-azulene-based conjugated polymers. By incorporation of 2,6-connected azulene units into the polymeric backbone, two conjugated polymers with high organic field-effect transistor (OFET) performance were developed. Two 2,6-azulene-based polymers with proton responsiveness and high electrical conductivity upon protonation were also provided. We also discuss our recent studies on azulene-based heteroaromatics. Two azulene-fused BN-heteroaromatics were designed and synthesized, and they exhibited a selective response to fluoride ion and unexpected deboronization upon the addition of trifluoroacetic acid. An unexpected synthesis of azulene-pyridine-fused heteroaromatics (Az-Py) by reductive cyclization of 1-nitroazulenes and the OFET performance of Az-Py-1 are included. Afterward, we discuss several examples of azulene-capped organic conjugated molecules. The molecules capped with the five-membered ring of azulene favor hole transport, whereas the ones capped with the seven-membered ring favor electron transport.

Double π-Extended Undecabenzo[7]helicene.

This work reports the first double π-extended undecabenzo[7]helicene 1, which is a large chiral nanographene, composed of 65 fused rings and 186 conjugated carbon atoms. The molecular identity of 1 has been confirmed by single crystal X-ray diffraction. A wine coloured solution of 1 in dichloromethane absorbs light from ultraviolet to the near infrared, featuring an extremely large molar absorption coefficient of 844 000 M-1 cm-1 at 573 nm. Optically pure 1 shows a record high electronic circular dichroism intensity in the visible spectral range (|Δϵ|=1375 M-1 cm-1 at 430 nm) known for any discrete polycyclic aromatic hydrocarbon. These unusual photophysical properties of 1 contrast sharply with those of a mono-undecabenzo[7]helicene derivative 2.

Double π‐Extended Undecabenzo[7]helicene

AbstractThis work reports the first double π‐extended undecabenzo[7]helicene 1, which is a large chiral nanographene, composed of 65 fused rings and 186 conjugated carbon atoms. The molecular identity of 1 has been confirmed by single crystal X‐ray diffraction. A wine coloured solution of 1 in dichloromethane absorbs light from ultraviolet to the near infrared, featuring an extremely large molar absorption coefficient of 844 000 M−1 cm−1 at 573 nm. Optically pure 1 shows a record high electronic circular dichroism intensity in the visible spectral range (|Δϵ|=1375 M−1 cm−1 at 430 nm) known for any discrete polycyclic aromatic hydrocarbon. These unusual photophysical properties of 1 contrast sharply with those of a mono‐undecabenzo[7]helicene derivative 2.

One‐Dimensional Molecular Metal Halide Materials: Structures, Properties, and Applications

Metal halides with low‐dimensional molecular structures are the rising stars in the horizon of functional materials research. Among them, 1D metal halide hybrids are very promising for future optoelectronic applications because of their unusual photophysical properties resulting from strong quantum confinement. In the past few years, besides lead‐based 1D metal halide hybrids, research has been extended to lead‐free organic and all‐inorganic metal halides. Due to near‐unity photoluminescence quantum yield and excellent structural stability, all‐inorganic 1D metal halides are suitable for environmentally friendly optoelectronic devices. Moreover, the distortion and connectivity mode of metal halide octahedra arouse the formation of self‐trapped excitons within 1D metal halides, thus endowing the materials with distinct optical properties. Recent investigations have revealed many exciting characteristics of this new class of materials, such as ferroelectricity, ferromagnetism, optical cooling, and so on. This perspective presents not only structure–property correlations and recent applications of 1D metal halides but also the existing challenges and future research directions.

Self-assembly of amphiphilic meso-aryl-substituted porphyrin derivatives in the presence of surfactants

Surfactant-assisted self-assembly of porphyrin molecules in aqueous solutions sometimes leads to the formation of hybrid supramolecular structures with unusual photophysical properties resulting from the dipole–dipole interactions between the neighboring aromatic systems. The macrocycle orientation and interchromophore distance in such assemblies are determined by the dye–surfactant interactions, and hence, strongly depend on the molecular structure of both surfactant and porphyrin molecules. In this paper we studied the influence of the number and position of the peripheral alkyl chains of amphiphilic meso-aryl-substituted porphyrins on their aggregation behavior and intermolecular interactions with different surfactants in aqueous solutions. The studies revealed a crucial role of the local acidity on the micellar surface in the protolytic equilibrium of the porphyrin derivatives, as well as the influence of the macrocycle hydrophilic–lipophilic balance on its solubilization site within a micellar system. These findings enable prediction of the photophysical properties of amphiphilic porphyrin derivatives in the presence of different solubilizing agents and membrane-mimetic systems, and hence, selection the most suitable drug delivery systems for the novel amphiphilic porphyrin-based photosensitizers.

Spectroscopic and Magneto-Optical Signatures of Cu1+ and Cu2+ Defects in Copper Indium Sulfide Quantum Dots.

Colloidal quantum dots (QDs) of I-III-VI ternary compounds such as copper indium sulfide (CIS) and copper indium selenide (CISe) have been under intense investigation due to both their unusual photophysical properties and considerable technological utility. These materials feature a toxic-element-free composition, a tunable bandgap that covers near-infrared and visible spectral energies, and a highly efficient photoluminescence (PL) whose spectrum is located in the reabsorption-free intragap region. These properties make them attractive for light-emission and light-harvesting applications including photovoltaics and luminescent solar concentrators. Despite a large body of literature on device-related studies of CISe(S) QDs, the understanding of their fundamental photophysical properties is surprisingly poor. Two particular subjects that are still heavily debated in the literature include the mechanism(s) for strong intragap emission and the reason(s) for a poorly defined (featureless) absorption edge, which often "tails" below the nominal bandgap. Here, we address these questions by conducting comprehensive spectroscopic studies of CIS QD samples with varied Cu-to-In ratios using resonant PL and PL excitation, femtosecond transient absorption, and magnetic circular dichroism measurements. These studies reveal a strong effect of stoichiometry on the concentration of Cu1+ vs Cu2+ defects (occurring as CuIn″ and CuCu• species, respectively), and their effects on QD optical properties. In particular, we demonstrate that the increase in the relative amount of Cu2+ vs Cu1+ centers suppresses intragap absorption associated with Cu1+ states and sharpens band-edge absorption. In addition, we show that both Cu1+ and Cu2+ centers are emissive but are characterized by distinct activation mechanisms and slightly different emission energies due to different crystal lattice environments. An important overall conclusion of this study is that the relative importance of the Cu2+ vs Cu1+ emission/absorption channels can be controlled by tuning the Cu-to-In ratio, suggesting that the control of sample stoichiometry represents a powerful tool for achieving functionalities (e.g., strong intragap emission) that are not accessible with ideal, defect-free materials.

The photophysical properties and imaging application of a new polarity-sensitive fluorescent probe.

A new excited-state intramolecular proton transfer (ESIPT) based and polarity-sensitive fluorescent probe M-HA was easily developed by conjugated connection of indole and 2'-hydroxyacetophenone through (E)-2-chloro-3-(hydroxymethylene)cyclohex-1-enecarbaldehyde. M-HA shows near-infrared fluorescence, high molar absorption coefficient and a large Stokes shift in various common solvents. In particular, M-HA exhibits red-shifted maximum emission wavelength, and extraordinarily high fluorescence intensity and quantum yield in high-polarity solvents. The theoretical calculation results indicate that the reduced electron-vibration coupling related to out-of-plane motions of benzene units in more polar solvents is mainly responsible for such unusual photophysical properties. For further application, M-HA was utilized to image live cells. The confocal fluorescence imaging results demonstrate that M-HA possesses excellent membrane permeability and can fluoresce brightly in the cytoplasm. Overall, M-HA, as a polarity-sensitive fluorescent probe, will serve as an excellent tool for quantitative determination of polarity in vitro and in-depth study of the polarity biology in physiopathology in future.

Abnormal Nucleophilic Substitution on Methoxytropone Derivatives: Steric Strategy to Synthesize 5-Substituted Azulenes.

Azulene is a non-alternant non-benzenoid aromatic system, and in turn, it possesses unusual photophysical properties. Azulene-based conjugated systems have received increasing interest in recent years as optoelectronic materials. Despite the routes available for the preparation of substituted azulene derivatives, there remain few methods that allow regioselective substitution on the seven-membered ring of azulenes due to the subtle reactivity difference among the various positions. This report explores the reactivity of substituted tropolones as the azulene precursors and also provides a new method to create 5-substituted azulenes. The reaction of cyanoacetate enolate with unsubstituted 2-methoxytropone affords azulene through the attack of the nucleophile on the C-2 center (normal pathway). We have observed that 3-substituted 2-methoxytropones undergo steric-guided nucleophilic addition at the C-7 center (abnormal pathway) to afford 5-substituted azulene derivatives. Based on this observation and DFT calculation, a new synthetic strategy is devised for the regioselective synthesis of 5-substituted multifunctional azulenes, which cannot be accessed by any other method.

Curious Case of 2-Selenouracil: Efficient Population of Triplet States and Yet Photostable.

Excited-state MS-CASPT2 and ADC(2) quantum chemical calculations and nonadiabatic dynamics simulations show that 2-selenouracil is able to both efficiently populate and depopulate reactive triplet states in an ultrashort time scale. Thus, the heavier homologue of 2-thiouracil unites the ultrafast, high-yield intersystem crossing of 2-thiouracil with the short excited-state lifetime and photostability of the parent nucleobase uracil-two properties that have been traditionally thought to be diametrically opposed. Remarkably, while the S2 → S1 → T2 → T1 deactivation dynamics of 2-selenouracil is analogous to that of 2-thiouracil, the calculations show that the triplet lifetime of 2-selenouracil should decrease by up to 3 orders of magnitude in comparison to that 2-thiouracil, possibly down to the few-picosecond time scale. The main reasons for this decrease are the lack of a second T1 minimum, the enhanced spin-orbit coupling, and the reduction of the energy barrier to access the T1/ S0 crossing-in particular in aqueous solution-compared to 2-thiouracil. Such unusual photophysical properties, together with its significant red-shifted absorption spectrum, could make 2-selenouracil a useful specialized photosensitizer for photodynamical therapy.

BN Polystyrenes: Emerging Optical Materials and Versatile Intermediates.

BN polystyrenes are an emerging class of polyolefins functionalized with aromatic side chains in which at least one CC bond is replaced with a BN bond. This class of structures exhibits unusual photophysical properties relative to organic polymers. BN polystyrenes serve as intermediates in the preparation of functional polymers, including stereoregular polar polyolefins. The consequences of BN for CC bond substitution on reactivity and properties are highlighted.

Magnesium Porphine Supermolecules and Two-Dimensional Nanoaggregates Formed Using the Langmuir-Schaefer Technique.

Porphyrins are functional elements of important biomolecules, whose assemblies play a central role in fundamental processes such as electron transfer, oxygen transport, enzymatic catalysis, and light harvesting. Here we report an approach to formation of porphyrin supermolecules, a particular type of nanoparticles with unusually strong noncovalent intermolecular interactions. Key differences between the supermolecules and noncovalent nanostructures described earlier are as follows. (1) Supermolecules consist of molecules of the same type without side groups promoting the self-assembly and without any spacers; no surfactant or catalyst to assist the process is needed. (2) They exhibit unusual photophysical properties and remain stable even in organic solvents. Their formation occurs under specially selected conditions at the air-water interface at room temperature. Following this route, we have formed supermolecules of magnesium porphine, a functional element of chlorophyll. The properties of these supermolecules are markedly different from those of the constituent molecules. For example, in contrast to the pink color of the monomer solution, solutions of supermolecules are transparent for visible light and absorb in the ultraviolet and near-infrared regions. We also present atomic force microscopy visualization of the porphyrin two-dimensional nanoaggregates forming at the air-water interface that were predicted in our previous works. This approach offers a guideline for the discovery of new supermolecules, including complex biological ones, and the formation of supermolecular materials with novel properties.

Photophysical properties of cationic dyes captured in the mesoscale channels of micron-sized metal-organic framework crystals

The optical properties of dye molecules in confined spaces can differ from the solution phase due to confinement effects. Pre-organized mesoscale channels of metal-organic frameworks (MOFs) are very suited for hosting various dyes, and the robust frameworks often render the encapsulated dyes with certain preferential geometries, which are different from those found in solution. Furthermore, pre-organized open channels can efficiently guide the uniform and unique spatial distribution of dye molecules in a controlled manner, which are otherwise difficult to achieve. Thus, sufficiently large dye molecules can avoid the formation of complex aggregates when captured inside open channels. In contrast, small dye molecules can form well-defined dimers or aggregates. The resulting dye-encapsulated MOFs can display unusual photophysical properties of the captured dyes. An anionic framework of In-BTB with mesoscale 3D channels is utilized for the efficient encapsulation of various cationic dyes through cation-exchange processes. Six different cationic dyes are encapsulated in the anionic framework of In-BTB, and their crystal structures are completely solved. Novel photophysical properties of these spatially distributed dye molecules in dye@In-BTBs are investigated.