Long-wavelength Band Research Articles

Photoluminescence of Ni(II), Pd(II), and Pt(II) Complexes [M(Me2dpb)Cl] Obtained from C‒H Activation of 1,5-Di(2-pyridyl)-2,4-dimethylbenzene (Me2dpbH).

The three complexes [M(Me2dpb)Cl] (M = Ni, Pd, Pt) containing the tridentate N,C,N-cyclometalating 3,5-dimethyl-1,5-dipyridyl-phenide ligand (Me2dpb−) were synthesised using a base-assisted C‒H activation method. Oxidation potentials from cyclic voltammetry increased along the series Pt < Ni < Pd from 0.15 to 0.74 V. DFT calculations confirmed the essentially ligand-centred π*-type character of the lowest unoccupied molecular orbital (LUMO) for all three complexes in agreement with the invariant reduction processes. For the highest occupied molecular orbitals (HOMO), contributions from metal dyz, phenyl C4, C2, C1, and C6, and Cl pz orbitals were found. As expected, the dz2 (HOMO-1 for Ni) is stabilised for the Pd and Pt derivatives, while the antibonding dx2−y2 orbital is de-stabilised for Pt and Pd compared with Ni. The long-wavelength UV-vis absorption band energies increase along the series Ni < Pt < Pd. The lowest-energy TD-DFT-calculated state for the Ni complex has a pronounced dz2-type contribution to the overall metal-to-ligand charge transfer (MLCT) character. For Pt and Pd, the dz2 orbital is energetically not available and a strongly mixed Cl-to-π*/phenyl-to-π*/M(dyz)-to-π* (XLCT/ILCT/MLCT) character is found. The complex [Pd(Me2dpb)Cl] showed a structured emission band in a frozen glassy matrix at 77 K, peaking at 468 nm with a quantum yield of almost unity as observed for the previously reported Pt derivative. No emission was observed from the Ni complex at 77 or 298 K. The TD-DFT-calculated states using the TPSSh functional were in excellent agreement with the observed absorption energies and also clearly assessed the nature of the so-called “dark”, i.e., d‒d*, excited configurations to lie low for the Ni complex (≥3.18 eV), promoting rapid radiationless relaxation. For the Pd(II) and Pt(II) derivatives, the “dark” states are markedly higher in energy with ≥4.41 eV (Pd) and ≥4.86 eV (Pt), which is in perfect agreement with the similar photophysical behaviour of the two complexes at low temperatures.

Solvatochromism of a D205 indoline dye at the interface of a small TiO2-anatase nanoparticle in acetonitrile: a combined molecular dynamics simulation and DFT calculation study

ABSTRACT A combined molecular dynamics (MD) simulation and density functional theory (DFT) calculations were used to investigate the effect of the acetonitrile (ACN) solution on the absorption and the charge transfer in a D205 indoline dye at the interface of a TiO2 nanoparticle. DFT calculations were carried out to estimate the equilibrium geometry of a small Ti30O62H4-anatase nanoparticle and to derive interaction parameters for bidentate binding of a D205 dye to TiO2. A series of the D205 dye configurations anchored to Ti30O62H4 were generated from the MD simulations and used as input for the time-dependent DFT (TD-DFT) calculations. We found that the immersion of the D205-Ti30O62H4 composite system into the polar ACN environment results in conformational changes of the dye moiety, which are accompanied by the solvatochromic redshift of its long-wavelength absorption band up to 1900 cm-1. Our results show that the HOMO and LUMO energy level alignment of the dye and the nanoparticle suggests a favourable driving force for charge transfer from the dye to TiO2. The MD/TD-DFT-estimated solvatochromic shift for the D205 dye at the TiO2/ACN interface is in good agreement with the experiment, showing that such computational approach enables reliable predictions of optical properties of other dye-TiO2 composites in solution.

Conjugated-linker dependence of the photophysical properties and electronic structure of chlorin dyads

The synthesis, photophysical properties and electronic structure of seven new chlorin dyads and associated benchmark monomers are described. Each dyad contains two identical chlorins linked at the macrocycle [Formula: see text]-pyrrole 13-position. The extent of electronic communication between chlorin constituents depends on the nature of the conjugated linker. The communication is assessed by modification of prominent ground-state absorption and redox properties, rate constants and yields of excited-state decay processes, and molecular-orbital characteristics. Relative to the benchmark monomers, the chlorin dyads in toluene exhibit a substantial bathochromic shift of the long-wavelength absorption band (30 nm average), two-fold increased radiative rate constant [average (10 ns)[Formula: see text] vs. (22 ns)[Formula: see text]], reduced singlet excited-state lifetimes (average 5.0 ns vs. 8.2 ns), and increased fluorescence quantum yields (average 0.56 vs. 0.42). The excited-state lifetime and fluorescence yield for the chlorin dyad with a benzothiadiazole linker are reduced substantially in benzonitrile vs. toluene due largely to [Formula: see text]25-fold accelerated internal conversion. The results aid design strategies for molecular architectures that may find utility in solar-energy conversion and photomedicine.

The first representative of a new class of charge transfer complexes in o-quinone series for organic semiconductors

The first representative of a new class of charge transfer complexes for organic semiconductors was synthesized. The reaction of p-nitroaniline (PNA) with [1,10]-phenanthroline-5,6-dione (PD) results in the formation of a stable molecular charge transfer (CT) complex PNA3-PD2 in a ratio of 3:2. The structure of the molecular CT complex PNA3-PD2 was established by X-ray diffraction studies. Using the density functional theory method, it is shown that several types of intermolecular interactions are realized in the complex: between the PNA amino group and the nitro group of another PNA molecule, carbonyl groups, and PD nitrogen atoms. Complex PNA3-PD2 is stable only in solid form. The diffuse reflectance UV–vis spectrum of PNA3-PD2 crystal powder is characterized by the intense weakly structured long-wavelength absorption band up to 650 nm. Quantum chemical calculations of the electronic structure have shown that the complex PNA3-PD2 is a straight-band semiconductor with a band gap of 2.11 eV.

Nature of Fast Relaxation Processes and Spectroscopy of a Membrane-Active Peptide Modified with Fluorescent Amino Acid Exhibiting Excited State Intramolecular Proton Transfer and Efficient Stimulated Emission.

A fluorescently labeled peptide that exhibited fast excited state intramolecular proton transfer (ESIPT) was synthesized, and the nature of its electronic properties was comprehensively investigated, including linear photophysical and photochemical characterization, specific relaxation processes in the excited state, and its stimulated emission ability. The steady-state absorption, fluorescence, and excitation anisotropy spectra, along with fluorescence lifetimes and emission quantum yields, were obtained in liquid media and analyzed based on density functional theory quantum-chemical calculations. The nature of ESIPT processes of the peptide’s chromophore moiety was explored using a femtosecond transient absorption pump-probe technique, revealing relatively fast ESIPT velocity (∼10 ps) in protic MeOH at room temperature. Efficient superluminescence properties of the peptide were realized upon femtosecond excitation in the main long-wavelength absorption band with a corresponding threshold of the pump pulse energy of ∼1.5 μJ. Quantum-chemical analysis of the electronic structure of the peptide was performed using the density functional theory/time-dependent density functional theory level of theory, affording good agreement with experimental data.

Highly Fluorescent Dianionic Polymethines with a 1,3,2-Dioxaborine Core

The difluoroboron β-diketonate ring is ever more used for creating bright polymethine-type fluorophores for the visible and NIR range. Here, we report the synthesis and spectral properties of a series of dianionic cyanine dyes of the rare A1-π-A-π-A1 type, with the central dioxaborine ring (A) embedded into the polymethine chain and various electron-acceptor terminal groups A1. Depending on the nature of the end group, the maxima of their intensive (with molar extinctions up to 380 000 M-1 cm-1) and narrow long-wavelength absorption band lie in the range of 530-770 nm. Their absorption and fluorescence bands are nearly mirror-like and characterized by weak solvatochromism; the marked hypsochromic shifts are observed only when going from polar aprotic solvents to methanol. The designed dianionic dyes have fluorescence quantum yields up to 92 % in the visible range, and even for the NIR dyes, the values of 18-37 % are observed in DMF.

Biphotochromic and ionochromic benzoxazolyl-substituted spirobipyrans

Novel photochromic spirobipyrans bearing benzoxazole group in the 3H-naphthopyran fragment have been synthesized. Spiro-conjugated benzopyran and naphthopyran fragments cause the observed dual photochromism of the molecules. In the presence of Cd2+, Mn2+, Co2+, Ni2+, Zn2+, Cu2+ metal ions thermal isomerization of the spirobipyrans is observed, followed by the formation of the intensely coloured complexes of the merocyanine form. The long-wavelength absorption band of the complexes is located at λ>600 nm.

Synthesis and X-ray crystal structure of unexpected novel thiazolidinone/1,3,4-thiadiazole heterocycle via S-alkylation and Smiles rearrangement dual approaches

A new unexpected hybrid based on the arylidene-thiazolidinone and 1,3,4-thiadiazole scaffolds via combined S-alkylation and Smiles rearrangement dual protocols. The one-pot reaction of arylidene-thiazolidinone with the hydrazonoyl chloride in a basic medium (Et3N) with benzene as solvent afforded the discovered compound at room temperature (25 °C). The molecular architecture of the designed hybrid were assigned based on the spectrophotometric tools. Based on Hirshfeld analysis, the molecules are connected by short O…H (19.6%), S…H (7.3%), H…C (20.1%), and C…C (0.7%) interactions. Density-functional theory (DFT) calculations indicated polar molecules (7.595 Debye). Its structure is stabilized by different σ-σ*, π→π*, n→σ*, and n→π* intramolecular charge transfer (IMCT) processes. The two longest wavelength bands observed in the UV–Vis spectra of diethyl(S,Z)-2-(2-(5-(4-hydroxybenzylidene)-4-oxo-4,5-dihydrothiazol-2-yl)-2-phenylhydrazinyl)-3-phenyl-2,3-dihydro-1,3,4-thiadiazole-2,5-dicarboxylate 3 were calculated at 364.0 (HOMO→LUMO+1) and 305.1 nm (HOMO-2→LUMO), which considerably agree with the experimental data.

Recent Advances in High Speed Photodetectors for eSWIR/MWIR/LWIR Applications

High speed photodetectors operating at a telecommunication band (from 1260 to 1625 nm) have been well studied with the development of an optical fiber communication system. Recent innovations of photonic systems have raised new requirements on the bandwidth of photodetectors with cutoff wavelengths from extended short wavelength infrared (eSWIR) to long wavelength infrared (LWIR). However, the frequency response performance of photodetectors in these longer wavelength bands is less studied, and the performances of the current high-speed photodetectors in these bands are still not comparable with those in the telecommunication band. In this paper, technical routes to achieve high response speed performance of photodetectors in the extended short wavelength infrared/mid wavelength infrared/long wavelength infrared (eSWIR/MWIR/LWIR) band are discussed, and the state-of-the-art performances are reviewed.

Электронное строение и спектрально-флуоресцентные свойства лазерных красителей тиопирило-4-трикарбоцианинов

It was found that the long-wavelength absorption band of the laser dye IR 1061 and its analogue with an unsubstituted polymethine chain is strongly broadened and decreases in intensity in polar solvents, while the fluorescence band remains narrow and practically does not change in a wide range of solvent polarities. Based on the quantum-chemical calculations of these dyes by the ab initio DFT/B3LYP/6-31G (d,p) and TDDFT methods, taking into account the polarity of the medium by the PCM method, it is shown that the reason for this difference is the weakening of solvation in the fluorescent state as compared to the ground state due to the greater equalization of the charge in the first than in the latter. An increase in the alternation of bond orders in the polymethine chain in the fluorescent state was found, which causes an increase of vibronic interactions in the radiative transition as compared to the absorptive one. Spectral effects caused by a change in the angle of rotation of phenyl groups in the thiopyrylium cycle upon excitation have been analyzed.

Triplet States of Cyanine Dye Dimers

The results of investigations of the properties of cyanine dye dimers in the triplet state are presented. The formation of dimers is demonstrated as two absorption bands of differing intensities, which are due to splitting of the S*-level of monomers as a result of their resonance interaction. The cyanine dye dimers are characterized by a relatively high quantum yield of the intersystem crossing. In the triplet-triplet absorption spectra two bands appear, where the long-wavelength band is assigned to a charge transfer state. The cyanine dye dimers in the triplet state are involved in the energy and electron transfer and can act as the photosensitizes of redox reactions.

Trion-Facilitated Dexter-Type Energy Transfer in a Cluster of Single Perovskite CsPbBr3 Nanocrystals* *Supported by the National Key R&D Program of China (Grant Nos. 2019YFA0308704 and 2017YFA0303700), the National Natural Science Foundation of China (Grant Nos. 61974058, 11574147 and 11621091), and the PAPD of Jiangsu Higher EducationZ Institutions.

Semiconductor colloidal nanocrystals (NCs) can interact with each other to profoundly influence the charge transfer, transport and extraction processes after they have been assembled into a high-density film for optoelectronic device applications. These interactions normally occur among several nearby single colloidal NCs, which should be effectively separated from their surroundings to remove the ensemble average effect for fine optical characterizations. By means of atomic force microscopy (AFM) nanoxerography, here we prepare individual clusters of perovskite CsPbBr3 NCs and perform single-particle measurements on their optical properties at the cryogenic temperature. While discrete photoluminescence bands can be resolved from the several single CsPbBr3 NCs that are contained within an individual cluster, the shorter- and longer-wavelength bands are dramatically different in that their intensities show sub- and superlinear dependences on the laser excitation powers, respectively. This can be explained by the generation of charged excitons (trions) at high laser excitation powers, and their subsequent Dexter-type energy transfer from smaller- to larger-sized CsPbBr3 NCs. Our findings not only suggest that these individual clusters prepared by AFM nanoxerography can serve as a potent platform to explore few-NC interactions but they also reveal the long-neglected role played by trions in channeling photo-excited energies among neighboring NCs.

An Adaptive Blended Algorithm Approach for Deriving Bathymetry from Multispectral Imagery

The log-ratio method (LRM) proposed by Stumpf et al. has been widely used to map bathymetry from multispectral imagery for oligotrophic waters, while the selection criteria of bands for the LRM have been subject to tradeoffs between maximum detectable depth and sensitivity. In this article, we first applied a method for global sensitivity analysis to a semianalytical forward model of optically shallow waters with the WorldView-2 band-set. The results show that the sensitive wavelength band in water-leaving reflectance for water depth varies from the longer wavelength band to the shorter wavelength band with increasing water depth. Then, we developed an adaptive blended algorithm approach (ABAA) to seamlessly map bathymetry from the shallower region to the deeper region. The LRM with different band combinations was selected for the sub-algorithms of the ABAA. The subalgorithms and depth range used for each subalgorithm of the ABAA were automatically determined by the proposed applicable depth range analysis that considers logarithmic regression for the LRM. The ABAA was applied to WorldView-2 and Landsat-8 imagery of the Xisha Qundao. When the in situ bathymetry data are available, compared with the LRM with the blue and green bands, the ABAA significantly improves the accuracy of the estimated depth, especially for waters shallower than 6 m (root-mean- square error (RMSE) = 0.31 to 0.94 m for WorldView-2 data, RMSE= 0.25 to 1.42 m for Landsat-8 data). When the in situ bathymetry data are absent, the ABAA performs better than the LRM with a single band ratio and an optimization-based method overall.

Platinum and palladium complexes of tridentate −C^N^N (phen-ide)-pyridine-thiazol ligands – A case study involving spectroelectrochemistry, photoluminescence spectroscopy and TD-DFT calculations

Four Pd(II) and Pt(II) complexes [M(C^N^N)Cl] (HC^N^N = 2-(6-phenylpyridin-2-yl)thiazoles) were synthesised, analysed and characterised using 1H NMR and MS in solution, as well as single crystal XRD in the solid. Cyclic voltammetry of the square planar complexes showed reversible or partially reversible reductions and irreversible oxidations. DFT calculations allowed assigning them to essentially metal-centred oxidations and ligand-centred reductions. Absorption spectra of the complexes show intense absorption bands into π-π* states in the UV to visible spectral range and long-wavelength bands which were assigned to transitions into mixed metal-to-ligand charge transfer (MLCT)/π-π* states, based on TD-DFT calculations. Comparison of Pt and Pd derivatives showed that the energy of the (MLCT)/π-π* bands are increased for Pd over Pt. This was also observed for the phosphorescence at 77 K and is attributed to the higher oxidation potential for Pd and supported by spectroelectrochemical measurements. The photoluminescence quantum yield (ΦL) drops drastically from Pt to Pd at room temperature, where only the two Pt(II) complexes are luminescent showing a broad unstructured phosphorescence from a 3MLCT state. At 77 K, the phosphorescence is blue-shifted and shows a clear vibrational progression, which is related to an enhanced ligand-centred character due to the lack of solvent stabilisation in the frozen matrix that otherwise increases the MLCT contribution. The Pd(II) complexes are not emissive at 298 K, but luminesce at 77 K. This is due to metal-centred dissociative d-d* states that facilitate radiationless deactivation, which cannot be thermally populated at low temperatures. Thus, similar ΦL are observed in frozen glassy matrices for both metals. TD-DFT calculations provided insight into the excited states and showed that the substitution pattern does not affect the emission, due to the lack of participation of the phenyl unit in the orbitals that are relevant for the description of the emissive state.

The structural basis of far-red light absorbance by allophycocyanins.

Phycobilisomes (PBS), the major light-harvesting antenna in cyanobacteria, are supramolecular complexes of colorless linkers and heterodimeric, pigment-binding phycobiliproteins. Phycocyanin and phycoerythrin commonly comprise peripheral rods, and a multi-cylindrical core is principally assembled from allophycocyanin (AP). Each AP subunit binds one phycocyanobilin (PCB) chromophore, a linear tetrapyrrole that predominantly absorbs in the orange-red region of the visible spectrum (600-700nm). AP facilitates excitation energy transfer from PBS peripheral rods or from directly absorbed red light to accessory chlorophylls in the photosystems. Paralogous forms of AP that bind PCB and are capable of absorbing far-red light (FRL; 700-800nm) have recently been identified in organisms performing two types of photoacclimation: FRL photoacclimation (FaRLiP) and low-light photoacclimation (LoLiP). The FRL-absorbing AP (FRL-AP)from the thermophilic LoLiP strain Synechococcus sp. A1463 was chosen as a platform for site-specific mutagenesis to probe the structural differences between APs that absorb in the visible region and FRL-APsand to identify residues essential for the FRL absorbance phenotype. Conversely, red light-absorbing allophycocyanin-B (AP-B; ~ 670nm) from the same organism was used as a platform for creating a FRL-AP. We demonstrate that the protein environment immediately surrounding pyrrole ring A of PCB on the alpha subunit is mostly responsible for the FRL absorbance of FRL-APs. We also show that interactions between PCBs bound to alpha and beta subunits of adjacent protomers in trimeric AP complexes are responsible for a large bathochromic shift of about ~ 20nm and notable sharpening of the long-wavelength absorbance band.

Panchromatic Organoboron Molecules with Tunable Absorption Spectra.

Panchromatic molecules, e. g. organic small molecules with wide absorption spectra, are very desirable for solar energy-related applications. Here, we report the development of a series of organoboron compounds composed of an organoboron core unit, two π-bridging units and two electron-withdrawing end-capping units. All seven molecules have the HOMO localized on the core unit and the LUMO delocalized on the whole conjugated backbone. They exhibit wide absorption spectra consisting of two strong absorption bands with the full width at half maximum of ca. 280 nm. These panchromatic compounds can be used as electron acceptors in organic solar cells. We elucidate the relationship between the chemical structures and opto-electronic properties of these organoboron panchromatic compounds. Increasing the electron-withdrawing capability of the core units results in a downshifted HOMO level as well as blueshifted long-wavelength absorption band with increased extinction coefficient. Extending the π-bridging units causes an increased HOMO level and blueshifted long-wavelength absorption band with increased extinction coefficients. Weakening the electron-withdrawing capability of the end-capping units leads to an upshifted LUMO level and blueshifted long-wavelength absorption peak with decreased extinction coefficient. This work provides insight into the absorption spectrum manipulation of panchromatic molecules and would pave the way for the development of solar energy-related applications.

Spectral manifestation of protonation of photochromic naphthopyrans

The formation of proton complexes of the photoinduced colored open form of naphthopyrans in solutions was first discovered and investigated by spectral-kinetic method. The complexes exhibit a new absorption band in the visible region, which is bathochromically shifted relative to the absorption band of the photoinduced colored open form. With an increase in the concentration of perchloric or hydrochloric acid, this long-wavelength absorption band appears immediately after the addition of acids to solutions of photochromic compounds. The protonation efficiency depends on the strength of the acids.

Effect of cation alkyl chain length on photo-luminescence dynamics of ionic liquids containing dicyanoaurate(I) anion

Viscosity and photo-luminescence dynamics of N-alkyl-N-methylpyrrolidinium dicyanoaurate (I) ([Py1n][Au(CN)2]) (n = 4, 6, 8, and 12) and 1-alkyl-3-methylimidazolium dicyanoaurate (I) ([Cnmim][Au(CN)2]) (n = 4, 8, and 12) were studied. The viscosity increased with increasing alkyl chain length for both cations, and the temperature dependence of the viscosity showed a good fit with the Vogel–Fulcher–Tammann equation. Steady-state luminescence of both [Py1n][Au(CN)2] and [Cnmim][Au(CN)2] showed dual luminescent bands at around 370 nm and 460 nm. The band with the shorter wavelength most likely arose owing to fluorescence of the trimer of the anion, and the longer-wavelength band could be assigned to phosphorescence of the linear oligomers of the anion. The relative ratio of the intensity of the fluorescence to that of the phosphorescence of [Py1n][Au(CN)2] was significantly smaller than that of [Cnmim][Au(CN)2]. The luminescent dynamics measured by a streak camera revealed a short lifetime of fluorescence, and the phosphorescence peak shift with time. The phosphorescence peak shift was attributed to two contributions from the amplitudes and the time constants. Based on the dependence on the solvent viscosity and the anion concentration, the slower time constant was assigned to the dynamics of tetramer formation owing to a reaction between the trimer and the monomer. The faster dynamics were assigned to the solvation dynamics, which were accompanied by the structural change of the trimer after intersystem crossing.

Structurally-thrifty and visible-absorbing fluorophores.

Fluorophores with a minimal push-pull backbone are actively pursued due to their potentials in biological labelling. Herein a series of structurally-thrifty and visible-absorbing fluorophores (SDXs) were successfully constructed following the D'D-π-A design strategy, in which a secondary donor (D') was introduced in conjugation with the donor (D) to enhance its electron donating capability. For a very small scaffold, SDXs exhibit a surprisingly long-wavelength absorption band in the visible spectral range (λabs=420nm) and a strong green fluorescence emission (λem=530nm) with a fluorescence quantum yield up to 0.84. Notably, fluorescence of SDXs was quenched in hydrogen-bonding solvents, e.g. MeOH and H2O. This phenomenon renders SDXs feasibility for imaging of cellular non-hydrogen-bonding microenvironment, as demonstrated with BEAS-2B cells. These results proved that the D'D-π-A is a powerful design strategy to construct novel structurally-thrifty fluorophores.

Novel Photo- and Ionochromic Benzothiazole-Substituted Spirobipyrans

Novel photochromic spirobipyrans containing benzothiazole group in the 2H-chromene moiety have been synthesized. The spirobipyrans combine with Co2+, Ni2+, Zn2+, and Cu2+ ions to give intensely colored complexes of merocyanine form with long-wavelength absorption bands at λ > 600 nm.