Charge-transfer Absorption Band Research Articles

Intervalence charge transfer in aluminum oxide and aluminosilicate minerals at elevated temperatures

Abstract Single-crystal optical spectra of corundum (Al2O3) and the Al2SiO5 polymorphs andalusite, kyanite, and sillimanite, containing both Fe2+-Fe3+ and Fe2+-Ti4+ intervalence charge transfer (IVCT) absorption bands were measured at temperatures up to 1000 °C. Upon heating, thermally equilibrated IVCT bands significantly decreased in intensity and recovered fully on cooling. These trends contrast with the behavior of crystal field bands at temperature for Fe, Cr, and V in corundum, kyanite, and spinel. The effects of cation diffusion and aggregation, as well as the redistribution of band intensity at temperature, are also discussed. The loss of absorption intensity in the visible and near-infrared regions of the spectrum of these phases may point to a more general behavior of IVCT in minerals at temperatures within the Earth with implications for radiative conductivity within the Earth.

Synthesis, Structure, and Properties of Nontrivial Iridium(III) Complexes Based on Anthracene-Decorated Benzimidazole Ligand.

Reactions of iridium trichloride hydrate with bulky 2-(9-anthracenyl)-1-phenyl-benzimidazole (anbi) in the presence of N-donor ligands afforded a number of unique noncyclometalated complexes, while attempts to prepare a common μ-chloro-bridged bis-cyclometalated dimer systematically gave a monocyclometalated complex cis-[Ir(C,N-anbi)(N-anbi)Cl2] instead. The obtained complexes were characterized by 1H NMR, high-resolution mass spectrometry, single-crystal and powder X-ray diffraction, UV-vis spectroscopy, and cyclic voltammetry. The noncyclometalated complexes fac-[Ir(N-anbi)(N^N)Cl3)], where N^N are 4,4'-disubstituted 2,2'-bipyridines, are octahedral and contain the anthracene and 2,2'-bipyridine units in a close cofacial arrangement. These complexes were found to be exceptionally inert to the chloride ligand exchange even in the presence of silver triflate, forming a rare trinuclear Ir-μ-Cl3-Ag-μ-Cl3-Ir structure instead. In the monocyclometalated complex, the Ir(III) ion is pentacoordinated in a rare square-pyramidal geometry, where the bulky anthracene fragment is involved in the steric shielding of the metal center. This is in line with the results of gas-phase density functional theory calculations, demonstrating that the experimentally observed structure is energetically most preferable. The monocyclometalated complex is deeply colored due to intense charge-transfer absorption bands in the range 450-650 nm with ε = 2000-5000 M-1 cm-1, superior to the noncyclometalated complexes. The synthesis, structures, and properties of the new complexes are discussed in the context of the related mono-, bis-, and noncyclometalated iridium(III) compounds.

Exploring solvatochromism: a comprehensive analysis of research data of the solvent -solute interactions of 4-nitro-2-cyano-azo benzene-meta toluidine

This study investigates the solvatochromic behavior of a new D1 disperse dye, focusing on the 4-nitro-2-cyano-azo-Benzene-metaToluidine type. Using UV-visible spectroscopy, we analyze the dye’s performance in single solvents and binary mixtures. Our analysis includes the evaluation of solvent polarity parameters and dye structure parameters, with emphasis on the longest wavelength intramolecular charge transfer absorption band. We identify nonlinear and linear patterns in the electronic transition energies plots with respect to solvent composition. Statistical analysis considers correlation coefficients, root mean squared error, mean absolute percentage error, and other parameters, providing insights into data accuracy and precision. This experimental and statistical study explores the absorption spectrum, wavelength characteristics, absorption energy, and polarity of a novel azo dye across various solvent and solute environments. These findings contribute to a comprehensive understanding of the dye’s photophysical and photochemical properties, potentially enabling applications in optical sensors and advanced materials.Graphical abstract

Charge Transfer and Intersystem Crossing in Compact Naphthalenediimide-Phenothiazine Triads: Synthesis and Study of the Photophysical Property with Transient Optical and Electron Paramagnetic Resonance Spectroscopic Methods.

In order to obtain a long-lived charge separation (CS) state in compact electron donor-acceptor molecular systems, we prepared a series of naphthalenediimide (NDI)-phenothiazine (PTZ) triads, with phenylene as the linker between the donor and acceptor. Conformation restriction is imposed to control the mutual orientation of the NDI and PTZ units by attaching methyl groups on the phenylene linker to tune the electronic coupling between the donor and the acceptor. Moreover, the PTZ moiety was oxidized to sulfoxide to tune the ordering of the CS state and the 3LE state (LE: locally excited state). UV-vis absorption spectra indicate electronic coupling between NDI with the phenylene linker as well as the PTZ units, manifested by the appearance of a charge-transfer (CT) absorption band, whereas this coupling is devoid in the triads with conformation restriction imposed. Fluorescence is strongly quenched in the triads compared to the reference compound, indicating electron transfer upon photoexcitation. Femtosecond transient absorption spectra indicate that the CS takes 0.8 ps, and then the 3LE state is formed by charge recombination in 83 ps. Nanosecond transient absorption (ns-TA) spectra show that the 3NDI state was observed in nonpolar solvents such as cyclohexane (triplet state lifetime: 95.7 μs), whereas the CS state was observed in more polar solvents. The CS state lifetimes are up to 1.2 μs (in toluene). Time-resolved electron paramagnetic resonance spectra of the triads in toluene consist of two types of signals: CS states (narrower signals, ∼10 mT) and 3LE states (broader signals, ∼50 to 200 mT). In the spectra of the triads containing PTZ, the CS state signals dominate, whereas for the triads containing oxidized PTZ, the 3NDI signals (zero-field splitting D ≈ 2000 MHz) prevail, both observations being in agreement with the ns-TA spectral studies. The electron spin polarization phase pattern of the 3NDI states of the triads indicates that the intersystem crossing (ISC) mechanism is spin-orbit charge-transfer ISC. Considering the 3CS state as ion pairs, the electron-exchange energy (J) is determined to be -39 to -59 MHz, and the electron spin dipolar interaction is 83-92 MHz.

Impact of Diimine Ligand on Singlet-to-Triplet Charge Transfer Electroabsorption in Iron and Ruthenium Complexes.

The electroabsorption and absorption spectra of eight homoleptic complexes of the general form [M(LL)3]2+ where M = Ru, Fe, and LL = 1,10-phenanthroline (phen), 2,2'-bipyridine (bpy), and 4,4',-(R)2-bpy where R = -OCH3, -CF3, were quantified at 77 K in a butyronitrile glass. Intense metal-to-ligand charge transfer (MLCT) absorption bands were evident in the visible region. Electroabsorption spectra measured with applied electric fields >0.2 MV/cm were analyzed by the two-state Liptay model. Significant light-induced dipole moment changes of = 4-13 D were found consistent with a metal-to-ligand charge transfer (MLCT) excited state comprised an electron localized on a single diimine ligand, [MIII(LL-)(LL)2]*2+, in the initially formed Franck-Condon excited state. A low energy feature evident in the electroabsorption spectra was assigned to a direct singlet-to-triplet MLCT excited state. The identity of the diimine ligand had an unexpected and large impact on these transitions. Analysis relative to the higher energy absorption provides a comparison of spin-allowed and disallowed transitions for first- and second-row transition metal complexes. With the notable exception of [Fe(CF3bpy)3]2+, the change in dipole moment for the 3MLCT excited states was less than or equal to that of the 1MLCT excited states. The charge transfer distances for the iron complexes were generally larger than those for the Ru complexes, a behavior attributed to a smaller degree of iron-diimine coupling in the ground state. A striking result was the sensitivity of the extinction coefficient and spectral profile of the low energy electroabsorption assigned to the identity of the diimine ligand; data that suggests electronic coupling with ligand localized triplet states and high spin metal centered states must be considered when modeling the Franck-Condon excited state.

A Halogen Bonding [2]Rotaxane Shuttle for Chloride-Selective Optical Sensing.

The first example of a [2]rotaxane shuttle capable of selective optical sensing of chloride anions over other halides is reported. The rotaxane was synthesised via a chloride ion template-directed cyclisation of an isophthalamide macrocycle around a multi-station axle containing peripheral naphthalene diimide (NDI) stations and a halogen bonding (XB) bis(iodotriazole) based station. Proton NMR studies indicate the macrocycle resides preferentially at the NDI stations in the free rotaxane, where it is stabilised by aromatic donor-acceptor charge transfer interactions between the axle NDI and macrocycle hydroquinone moieties. Addition of chloride ions in an aqueous-acetone solvent mixture induces macrocycle translocation to the XB anion binding station to facilitate the formation of convergent XB⋅⋅⋅Cl- and hydrogen bonding HB⋅⋅⋅Cl- interactions, which is accompanied by a reduction of the charge-transfer absorption band. Importantly, little to no optical response was induced by addition of bromide or iodide to the rotaxane, indicative of the size discriminative steric inaccessibility of the interlocked cavity to the larger halides, demonstrating the potential of using the mechanical bond effect as a potent strategy and tool in chloride-selective chemo-sensing applications in aqueous containing solvent environments.

Exploring the chemical physics in tetraphenylporphyrin-N-methylfulleropyrrolidine supramolecular complex by spectroscopic investigations and quantum chemical calculations

The interaction between N-methylfulleropyrrolidine (A) and 5,10,15,20-tetraphenylporphyrin, i.e., D, is studied in solution. Absorption spectrophotometric study reveals formation of charge transfer (CT) absorption band for the DA complex from which CT transition energy (hνCT) is estimated to be 1.673 eV. Quenching of fluorescence of D in presence of A is utilized for determination of the binding constant of the DA complex as 13780 dm3⋅mol−1. DFT calculations generate both geometry optimized and electronic structures of the DA complex and the estimated HOMO-LUMO energy gap, i.e., 1.683 eV, correlates excellently well with the experimentally obtained value of hνCT. Proton NMR studies provide substantial support in favour of strong binding between D and A and provide a clear picture regarding orientation of bound guest (here A) with host (here D). The DA system reported in present work would certainly provide very good perspective for the construction of fulleropyrrolidine based photochromic devices in near future.

Bridge-induced taming of the visible electronic circular dichroism signatures of helicoBODIPYs

Helically-flexible bis(BODIPY)s based on chiral ethane-1,2-diamine or −1,2-diol bridges (named helicoBODIPYs) are an interesting family of accessible and tunable small multichromophoric organic dyes enabling visible electronic circular dichroism (ECD) and, even visible circularly polarized luminescence (CPL). However, their CPL brightness (BCPL) is still limited (up to ca. 10 M−1cm−1), due to low fluorescence efficiency owing to a non-optimal participation of intramolecular charge transfer (CT) emission. Herein, we analyze in depth the origin and factors controlling this CT, demonstrating the key participation of a BODIPY-to-BODIPY symmetry-breaking induced CT (SBCT), beyond the expected CT within each single BODIPY chromophore due to their push-pull character. It is also demonstrated that increasing the overcrowding at the flexible helicoBODIPY ethane bridges leads to BODIPY-BODIPY faced dispositions, promoting the SBCT and enabling the detection of both CT absorption and CT emission bands under specific conditions. Interestingly, this SBCT enhances the visible ECD (absolute gabs values), supporting the key role of the involved forbidden CT transitions in the chiroptical activity of these dyes, as well as the possibility of modulating their valuable visible chiroptical signatures (e.g., visible CPL brightness) by easily playing with steric factors at the dye bridge.

Red phenanthrenequinone dyes with high thermal and photo-stability for LCD color filters

Color filters (CF) are essential integral parts of the liquid crystal display (LCD) and image sensor. Compared to traditional pigment colorants, organic dyes offer a promising alternative to realize CF with improved optical properties and higher resolution. However, organic dyes usually suffer from inferior thermal and photo-stability, limiting their applications in CF. Herein, four robust donor-acceptor organic dyes based on phenanthrenequinone chromophore were designed and synthesized by introducing aromatic amine derivatives as the electron donors. The strong donor-acceptor interactions in these dyes contribute to intense broad charge-transfer absorption bands from 375 nm to 600 nm with high molar extinction coefficients, thus realizing red color. Also, these dyes exhibit high thermal and photo-stability, good compatibility with the polymer binder and low aggregation tendencies, resulting in high thermal and photo-stability for the fabricated CF films. Remarkably, among these phenanthrenequinone dyes, DTPAP with multi-donor substitution and extended π-conjugation exhibited the best performance in terms of molar extinction coefficient, thermal and photo-stability, contributing to the highest thermal and photo-stability for the CF film with color difference values (ΔEab) below 0.75 under simulated industrial manufacturing processes. This work confirms that phenanthrenequinone is a robust chromophore and is conducive to developing thermal and photo-stable CF dyes, and paves a way to improve the optical properties and stability of donor-acceptor dyes for CF.

PtII(C^N)(N-donor ligand)Cl-type complexes with the four-coordinate organoboron unit and their optoelectronic properties

In this research, we have developed a series of PtII(C^N)(N-donor ligand)Cl-type phosphorescent complexes with the four-coordinate organoboron unit in the C^N ligand. Through shifting the coordinating position of the Pt(II) center from phenyl ring to pyridyl ring of the 2-phenylpyridine-type (ppy-type) four-coordinate organoboron unit, the variation of >50 nm in charge-transfer (CT) absorption band and >40 nm in phosphorescent wavelength can be observed in the synthesized PtII(C^N)(N-donor ligand)Cl-type complexes, indicating effective tuning of their photophysical properties incurred by the four-coordinate organoboron unit. In addition, based on the cyclic voltammetry result, obvious variation of electron density on the Pt(II) center of these PtII(C^N)(N-donor ligand)Cl-type phosphorescent complexes can also be observed. Critically, these PtII(C^N)(N-donor ligand)Cl-type complexes with the ppy-type four-coordinate organoboron unit can exhibit aggregation enhanced phosphorescent emission (AEPE) behavior. It seems that the hydrogen bonding among the N-donor ligands and water molecules can affect their AEPE response greatly, representing a new way to tune the AEPE behavior in the PtII(C^N)(N-donor ligand)Cl-type complexes. In the solution-processed organic light-emitting diodes (OLEDs), peak electroluminescent (EL) efficiencies of 15.3%, 10.3 cd A−1 and 9.8 lm W−1 have been achieved with EL at ca. 648 nm. These impressive results have provided key information for tuning optoelectronic properties of the PtII(C^N)(N-donor ligand)Cl-type complexes by the four-coordinate organoboron unit and N-donor ligand.

Long-range Through-space Charge Transfer in a pH-responsive Mixed Cyclophane of Pyridine and Teropyrene.

A large, strained (SE=44.2 kcal/mol) and conformationally flexible mixed cyclophane of pyridine and teropyrene was synthesized using two intramolecular Wurtz coupling reactions and an unprecedented Scholl reaction between the unreactive 2 positions of the pyrene systems in a triply bridged pyrenophane. Protonation of the pyridine unit results in a greatly enhanced preference for nesting in the cavity of the highly bent teropyrene system (θcalc =162.6°) and emergence of a charge transfer absorption band (λmax =592 nm) due to a long range (5.0-5.5 Å), through-space intramolecular transition between the teropyrene and pyridinium units, which does not exist in the neutral cyclophane.

The Role of the si-Face Tyrosine of a Homodimeric Ferredoxin-NADP+ Oxidoreductase from Bacillus subtilis during Complex Formation and Redox Equivalent Transfer with NADP+/H and Ferredoxin.

In the crystal structure of ferredoxin-NADP+ oxidoreductase from Bacillus subtilis (BsFNR), Tyr50 stacks on the si-face of the isoalloxazine ring portion of the FAD prosthetic group. This configuration is highly conserved among the homodimeric ferredoxin-NAD(P)+ oxidoreductases (FNR) from Gram-positive bacteria and photosynthetic bacteria. In this report, pre-steady state reactions of Tyr50 variants with NADP+/NADPH and ferredoxin from B. subtilis (BsFd) were examined with stopped-flow spectrophotometry to assess the effects of the mutation on the formation of FNR-substrate complexes and following redox equivalent transfer. Mixing oxidized BsFNRs with NADPH resulted in a rapid complex formation followed by a rate-limiting hydride transfer. The substitution substantially modulated the intensity of the charge transfer absorption band and decreased the observed hydride transfer rates compared to the wild type. Reduction of the Y50W mutant by NADPH proceeded in a monophasic manner, while the Y50G and Y50S mutants did in biphasic phases. The reduced Tyr50 mutants hardly promoted the reduction of NADP+. Mixing oxidized BsFNRs with reduced BsFd resulted in the reduction of the FNRs. The observed FNR reduction rates of the three variants were comparable, but in the Y50G and Y50S mutants, the amount of the reduced FNR at the rapid phase was decreased, and a slow FNR reduction phase was observed. The obtained results suggest that the replacements of Tyr50 with Gly and Ser permitted the conformational change in the reduced form, which induced an asymmetric kinetic behavior between the protomers of the homodimeric BsFNR.

Luminescent four-coordinate N-heterocyclic carbene (NHC) copper(I) complexes bearing the pyridyl-imidazolylidene ligand

The synthesis, characterization and photophysical properties of a series of the four-coordinate N-heterocyclic carbene (NHC) copper(I) complexes are reported. These NHC-Cu(I) complexes contain two bidentate ligands, the R-substituted pyridyl-imidazolylidene-type ligand and diphosphine ligand bis[(2-diphenylphosphino)phenyl] ether (POP). The photophysical properties of these complexes can be adjusted depending on the nature of substituents at 4-position of the phenyl ring in the NHC ligand. The metal-to-ligand charge transfer (MLCT) absorption band can be observed for all complexes at 348–362 nm, and the emission wavelengths can be fine-tuned to cover the spectral range of 543–555 nm with the higher photoluminescence efficiency of up to 66.2% in the solid state. Density functional theory (DFT) and time dependent density functional theory (TDDFT) calculations were employed to support potophysical properties of the NHC-Cu(I) complexes.

The effect of dark states on the intersystem crossing and thermally activated delayed fluorescence of naphthalimide-phenothiazine dyads.

A series of 1,8-naphthalimide (NI)-phenothiazine (PTZ) electron donor-acceptor dyads were prepared to study the thermally activated delayed fluorescence (TADF) properties of the dyads, from a point of view of detection of the various transient species. The photophysical properties of the dyads were tuned by changing the electron-donating and the electron-withdrawing capability of the PTZ and NI moieties, respectively, by oxidation of the PTZ unit, or by using different aryl substituents attached to the NI unit. This tuning effect was manifested in the UV-vis absorption and fluorescence emission spectra, e.g., in the change of the charge transfer absorption bands. TADF was observed for the dyads containing the native PTZ unit, and the prompt and delayed fluorescence lifetimes changed with different aryl substituents on the imide part. In polar solvents, no TADF was observed. For the dyads with the PTZ unit oxidized, no TADF was observed as well. Femtosecond transient absorption spectra showed that the charge separation takes ca. 0.6 ps, and admixtures of locally excited (3LE) state and charge separated (1CS/3CS) states formed (in n-hexane). The subsequent charge recombination from the 1CS state takes ca. 7.92 ns. Upon oxidation of the PTZ unit, the beginning of charge separation is at 178 fs and formation of 3LE state takes 4.53 ns. Nanosecond transient absorption (ns-TA) spectra showed that both 3CS and 3LE states were observed for the dyads showing TADF, whereas only 3LE or 3CS states were observed for the systems lacking TADF. This is a rare but unambiguous experimental evidence that the spin-vibronic coupling of 3CS/3LE states is crucial for TADF. Without the mediating effect of the 3LE state, no TADF is resulted, even if the long-lived 3CS state is populated (lifetime τCS ≈ 140 ns). This experimental result confirms the 3CS → 1CS reverse intersystem crossing (rISC) is slow, without coupling with an approximate 3LE state. These studies are useful for an in-depth understanding of the photophysical mechanisms of the TADF emitters, as well as for molecular structure design of new electron donor-acceptor TADF emitters.

Observation of Long-Lived Charge-Separated States in Anthraquinone-Phenothiazine Electron Donor-Acceptor Dyads: Transient Optical and Electron Paramagnetic Resonance Spectroscopic Studies.

We prepared a series of phenothiazine (PTZ)-anthraquinone (AQ) electron donor-acceptor dyads to study the relationship between molecular structures and the possibility of charge transfer (CT) and intersystem crossing (ISC). As compared to the previously reported PTZ-AQ dyad with a direct connection of two units via a C-N single bond, the PTZ and AQ units are connected via a p-phenylene or p-biphenylene linker. Conformation restriction is imposed by attaching ortho-methyl groups on the phenylene linker. UV-vis absorption spectra indicate electronic coupling between the PTZ and AQ units in the dyads without conformation restriction. Different from the previously reported PTZ-AQ, thermally activated delayed fluorescence (TADF) is observed for the dyads containing one phenylene linker (PTZ-Ph-AQ and PTZ-PhMe-AQ). The prompt fluorescence lifetime in cyclohexane is exceptionally long (τPF = 62.0 ns, population ratio: 99.2%) and 245.0 ns (93.5%) for PTZ-Ph-AQ and PTZ-PhMe-AQ, respectively (normally τPF <20 ns); the delayed fluorescence lifetimes for these two dyads were determined as τDF = 2.4 μs (6.5%) and 7.6 μs (0.8%), respectively. For the dyad containing a biphenylene linker (PTZ-Ph2Me-AQ), no TADF was observed. Charge-separated (CS) states were observed for PTZ-Ph-AQ and PTZ-PhMe-AQ, and the lifetimes were determined as 7.0 and 1.3 μs, respectively, indicating the triplet spin multiplicity of the CS state. The 3CS state lifetimes are shortened to 100 ns and 440 ns for the two dyads, respectively, in the polar solvent acetonitrile. For dyads with a longer linker, i.e., PTZ-Ph2Me-AQ, the CS state lifetime is not sensitive to solvent polarity (τCS = 1.8 and 1.3 μs in cyclohexane and acetonitrile, respectively). In reference dyads, where the PTZ unit is oxidized to sulfoxide, no CT absorption band and TADF were observed, which is attributed to the increased CS state energy (>3 eV) becoming higher than that of the AQ triplet (3AQ*) state (ca. 2.7 eV). These experimental evidence show that the presence of 1CS, 3CS, and 3LE (LE: locally excited) states sharing similar energy is essential for the occurrence of TADF. Population of the long-lived 3CS state (with a lifetime of a few μs) does not produce by itself TADF, because the ISC process of 1CS→3CS is nonsufficient. Femtosecond transient absorption spectra show that charge separation (CS) occurs readily (<5 ps) for most dyads, even in nonpolar solvents. Nanosecond pulsed laser-excited time-resolved electron paramagnetic resonance (TREPR) spectra show that either a spin correlated radical pair (SCRP) is formed, with the electron exchange energy 2J = +2.14 mT, or radical pairs with stronger interaction, |2J| > 6.57 mT. These studies are useful for in-depth understanding of the CS and ISC in compact electron donor-acceptor dyads and for design of efficient TADF emitters.

Does Twisted Molecular Structure Always Induce Intersystem Crossing? A Case Study with Near-IR Absorbing 1,8-Diazabicyclo[5.4.0]undec-7-ene-fused Naphthaldiimide.

Heavy atom-free organic chromophores showing absorption in the near-IR region with intersystem crossing (ISC) ability are important for applications in various fields, e.g., photocatalysis and photodynamic therapy. Herein, we studied the photophysical property of a naphthalenediimide (NDI) derivative, in which the NDI chromophore is fused with pentacyclic 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), which shows a strong charge-transfer (CT) absorption band (S0 → 1CT transition) in the near-IR region of 600-740 nm. The effect of extended π-conjugation framework in NDI-DBU compared with the derivative of mono-amino substitution (NDI-NH-Br) was studied by steady-state and nanosecond transient absorption (ns-TA) spectra, electron paramagnetic resonance (EPR) spectroscopy, and theoretical computations. The fluorescence is almost completely quenched for NDI-DBU (ΦF = 1.0%) as compared with NDI-NH-Br (ΦF = 24% in toluene). However, the ISC of NDI-DBU is poor, and the singlet oxygen quantum yield was determined as ΦΔ = 9% versus ΦΔ = 57% for NDI-NH-Br, although the compound has significantly twisted molecular structure. The ns-TA spectral study showed a long-lived triplet excited state (τT = 132 μs) in NDI-DBU, with T1 energy of 1.20-1.44 eV, and the ISC is via the S2 → T3 path, which is verified by theoretical calculations. This study displayed that the twisting of molecular geometry does not always assure efficient ISC.

Constructing 1-Ethoxyphenanthro[9,10-e]acephenanthrylene for the Synthesis of a Polyaromatic Hydrocarbon Containing a Formal Azulene Unit.

peri-Acenoacenes are attractive synthetic targets, but their non-benzenoid isomeric counterparts were unnoticed. 1-Ethoxyphenanthro[9,10-e]acephenanthrylene 8 was synthesized and converted to azulene-embedded 9, which is a tribenzo-fused non-alternant isomeric motif of peri-anthracenoanthracene. Aromaticity and single-crystal analyses suggested a formal azulene core for 9, which showed a smaller highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gap with a charge-transfer absorption band and brighter fluorescence than 8 (quantum yield (Φ): 9 = 41.8%, 8 = 8.9%). The reduction potentials of 8 and 9 were nearly identical, and the observations were further supported by density functional theory (DFT) calculations.

Manipulating Host‐Guest Charge Transfer of a Water‐Soluble Double‐Cavity Cyclophane for NIR‐II Photothermal Therapy

AbstractWater‐soluble small organic photothermal agents (PTAs) over NIR‐II biowindow (1000–1350 nm) are highly desirable, but the rarity greatly limits their applications. Based on a water‐soluble double‐cavity cyclophane GBox‐44+, we report a class of host–guest charge transfer (CT) complexes as structurally uniform PTAs for NIR‐II photothermal therapy. As a result of its high electron‐deficiency, GBox‐44+ can bind different electron‐rich planar guests with a 1 : 2 host/guest stoichiometry to readily tune the CT absorption band that extends to the NIR‐II region. When using a diaminofluorene guest substituted with an oligoethylene glycol chain, the host–guest system realized both good biocompatibility and enhanced photothermal conversion at 1064 nm, and was then exploited as a high‐efficiency NIR‐II PTA for cancer cell and bacterial ablation. This work broadens the potential applications of host–guest cyclophane systems and provides a new access to bio‐friendly NIR‐II photoabsorbers with well‐defined structures.

Manipulating Host-Guest Charge Transfer of a Water-Soluble Double-Cavity Cyclophane for NIR-II Photothermal Therapy.

Water-soluble small organic photothermal agents (PTAs) over NIR-II biowindow (1000-1350 nm) are highly desirable, but the rarity greatly limits their applications. Based on a water-soluble double-cavity cyclophane GBox-44+ , we report a class of host-guest charge transfer (CT) complexes as structurally uniform PTAs for NIR-II photothermal therapy. As a result of its high electron-deficiency, GBox-44+ can bind different electron-rich planar guests with a 1 : 2 host/guest stoichiometry to readily tune the CT absorption band that extends to the NIR-II region. When using a diaminofluorene guest substituted with an oligoethylene glycol chain, the host-guest system realized both good biocompatibility and enhanced photothermal conversion at 1064 nm, and was then exploited as a high-efficiency NIR-II PTA for cancer cell and bacterial ablation. This work broadens the potential applications of host-guest cyclophane systems and provides a new access to bio-friendly NIR-II photoabsorbers with well-defined structures.

Theoretical Design of New Healthy Organic Dyes for Solar Cell Applications with Favorite Medicinal Effect

In this work, a computational investigation was used to design and study new materials based on carminic acid isomers as organic dyes for DSSCs. Density functional theory (DFT) was applied to report the ground state and the excited state characteristic was reported by utilizing time-dependent DFT (TDDFT) methods. Some electronic, optical, photolytic and electron transfer properties are evaluated to achieve our study. The results indicate that modifying the chemical structure of a dye by doping improves light harvesting efficiency while reducing the driving force for electron injection and the potential of dye renewal while boosting dye aggregation on the electrode surface. The new structures dyes displays strong charge transfer absorption bands in the visible, excellent electronic, sufficient driving force and photoelectric conversion efficiency in comparison with carminic acid. Also, All suggested dyes have sufficient properties to achieve high PCE of the DSSCs. These results are adequate for a potential effective electron injection process. Accordingly, the theoretical methods are significant to provide experimental methods for designing new, highly efficient materials for optoelectronic applications. It was found that these dyes do not have any medical effect on human health.