UV-vis Absorption Properties Research Articles

Synthesis, Structure, and Light Absorption of Octanoyl Amino Acids

Amino acid lanthanide complexes are a promising class of environmentally friendly and non-toxic optical organic materials that find extensive applications in biomedicine, molecular probes, and optical devices. In this study, three amino acid lanthanide complexes, octanoyl glycine gadolinium (Gd(oct-ala)3×H2O), octanoyl serine gadolinium (Gd(oct-ser)3×H2O), and octanoyl phenylalanine gadolinium (Gd(oct-phe)3×H2O), were synthesized by reacting octanoyl amino acid ligands with gadolinium chloride. The coordination structure of the gadolinium complexes was determined by elemental analysis and infrared spectroscopy. XRD and polarized light microscopy confirmed the amorphous structure of the complexes. DSC and TG-DTA were used to investigate the thermodynamic stability of the gadolinium complexes, and their solubility and UV-visible light absorption properties were also evaluated. Our results demonstrate that all three gadolinium complexes exhibit excellent UV-visible light absorption performance, with the Gd(oct-phe)3×H2O containing a phenyl ring showing the highest light absorption efficiency.

Oxime esters: Potential alternatives to phosphine oxides, for overcoming oxygen inhibition in material jetting applications

Material jetting technology is emerging as a prominent technique within the additive manufacturing domain for printing multi-material objects. Despite its various advantages, including high printing resolution, oxygen inhibition remains the main issue for UV-curable materials. Oxime esters are interesting photoinitiators for this application due to their ability to undergo a photocleavage reaction followed by decarboxylation, limiting the diffusion of oxygen. A series of four commercially available oxime esters were studied as Type I photoinitiators, with the photoinitiating ability and photochemical properties of two of them never having been investigated before. Initially, their UV–visible absorption properties were studied, revealing significant absorption up to 420nm. Photopolymerization kinetic studies indicate that the oxime esters can outperformed benchmark photoinitiators such as phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO) by reaching around 80% of double bond conversion in 12µm layer under air (for O-16) against 60% for BAPO under the same conditions. Finally, the oxime esters were tested in 3D-inkjet printing applications, displaying highly promising results with tack-free surfaces.

Preparation, structure and optical properties of TCNB-based charge-transfer cocrystals

Organic charge transfer cocrystals exhibit interesting properties due to their multi-components synergistic and collective effect. Herein, using 1,2,4,5-tetracyanobenzene (TCNB) as electron acceptor, carbazole (CARB), dibenzothiophene (DBZP) and dibenzofuran (DBZF) as electron donors, three charge transfer cocrystals of CARB-TCNB, DBZP-TCNB and DBZF-TCNB were synthesized by solvent evaporation method and solvent-assisted grinding method. These cocrystals were constructed based on the π–π stacking interactions and CH…N hydrogen bonds and confirmed by the SXRD analysis. The stacking modes are consistent with the model that predicted by molecular electrostatic potential analysis (ESP). The IGM and AIM analyses suggested that the π-π stacking and CH…N hydrogen bonds are weak in nature. The purity and homogeneity of cocrystals and grinding products were verified by PXRD analysis. In addition, the IR, UV–vis absorption and luminescent properties were investigated, and the cocrystals and grinding products exhibited different behaviors from that of their precures. In short, this work not only reports the CT complexes synthesized by liquid- and solid- strategies, but also provides an in-depth understanding of the spectral changes caused by the CT interactions.

Lewis acid-catalyzed chemo- and stereoselective addition of pyrroles to skipped diynones: en route to novel pyrrole-based ketocyanine dyes and alkyne-tethered enones

The first chemo- and stereoselective syntheses of hitherto unknown pyrrole-based β,β′-disubstituted ketocyanine dyes and alkyne-tethered enones through Lewis acid-catalyzed addition of pyrroles to skipped diynones (penta-1,4-diyn-3-ones) are described. The protocols feature a good substrate tolerance, mild reaction conditions, and high yields of target products. A wide synthetic utility of synthesized alkyne-tethered enones as novel building blocks is demonstrated by the synthesis of diverse pyrrole-containing compounds. The UV–vis absorption properties for selected representatives of novel adducts are studied to preliminary access their potential as photoinitiators/sensitizers in visible light induced polymerization.

Assembly of Copper Alkynyl Clusters into Dimensionally Diverse Coordinated Polymers Mediated by Pyridine Ligands.

Surface ligands play crucial roles in modifying the properties of metal nanoclusters and stabilizing atomically precise structures, and also serve as vital linkers for constructing cluster-based coordination polymers. In this study, we present the results of the solvothermal synthesis of eight novel copper alkynyl clusters incorporating pyridine ligands using a one-pot method. The resulting compounds underwent characterization through elemental analysis, Fourier transform infrared (FT-IR) spectroscopy, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction (SCXRD). Our observations revealed that distinct pyridine ligands with varying lengths and coordination sites exert significant influence on the structure and dimensionality of the clusters. The structural diversity of these clusters led to the formation of one-dimensional (1D), two-dimensional (2D), or dimer arrangements linked by seven pyridine bridging ligands. Remarkably, these complexes exhibited unique UV-vis absorption and photoluminescence properties, which were influenced by the specific bridging ligand and structural framework. Furthermore, density functional theory (DFT) calculations demonstrated the capability of the conjugated system in the pyridine ligand to impact the band gap of clusters. This study not only unveils the inherent structural diversity in coordination polymers based on copper alkynyl clusters but also offers valuable insights into harnessing ligand engineering for structural and property modulation.

Enhancement of Visible Light Antibacterial Activities of Cellulose Fibers from Lotus Petiole Decorated ZnO Nanoparticles.

Cellulose/ZnO (CZ) nanocomposites are promising antimicrobial materials known for their antibiotic-free nature, biocompatibility, and environmental friendliness. In this study, cellulose fibers extracted from lotus petioles were utilized as a substrate and decorated with various shapes of ZnO nanoparticles (NPs), including small bean, hexagonal ingot-like, long cylindrical, and hexagonal cylinder-shaped NPs. Increasing zinc salt molar concentration resulted in highly crystalline ZnO NPs forming and enhanced interactions between ZnO NPs and -OH groups of cellulose. The thermal stability and UV-visible absorption properties of the CZ samples were influenced by ZnO concentration. Notably, at a ZnO molar ratio of 0.1, the CZ 0.1 sample demonstrated the lowest weight loss, while the optical band gap gradually decreased from 3.0 to 2.45eV from the CZ 0.01 to CZ 1.0 samples. The CZ nanocomposites exhibited remarkable antibacterial activity against both Staphylococcus aureus (S. aureus, Gram-positive) and Escherichia coli (E. coli, Gram-negative) bacteria under visible light conditions, with a minimum inhibitory concentration (MIC) of 0.005mg/mL for both bacterial strains. The bactericidal effects increased with higher concentrations of ZnO NPs, even achieving 100% inhibition. Incorporating ZnO NPs onto cellulose fibers derived from lotus plants presents a promising avenue for developing environmentally friendly materials with broad applications in antibacterial and environmental fields.

Spectroscopic and theoretical study of novel copper(II) complexes based on phenothiazine ligands: UV–Visible absorption and photoinduced electron transfer

This study presents three novel copper (II) complexes based on phenothiazine ligands that were synthesized and revealed their structures by spectral and analytical measurements. The synthesized complexes offered potential opportunities to explore their UV–visible absorption properties and photoinduced electron transfer with triethylamine. We performed density functional theory (DFT) calculations for Cu(II) (HL1)2 compounds and studied their frontier molecular orbitals in different environments. The calculations were done by using PBE1PBE functional and 6-31G(d)/Lanl2dz basis sets. We applied the LANL2DZ basis set for Cu. The treatment of all the other atoms was done by a 6-31G(d) basis set. For the calculation of the electronic structure, the basis set 6–31 + G(d)/Lanl2dz and SMD solvation model with MeCN and DMF were employed. We computed the frequencies to confirm the stability of the structures. Theoretical calculations can help explain the experimental findings, provide insights into the electronic transitions responsible for UV–visible absorption, and elucidate the photoinduced electron transfer processes involved.

Advancing Evidence-Based Data Interpretation in UV-Vis and Fluorescence Analysis for Nanomaterials: An Analytical Chemistry Perspective.

UV-vis spectrophotometry and spectrofluorometry are indispensable tools in education, research, and industrial process controls with widespread applications in nanoscience encompassing diverse nanomaterials and fields. Nevertheless, the prevailing spectroscopic interpretations and analyses often exhibit ambiguity and errors, particularly evident in the nanoscience literature. This analytical chemistry Perspective focuses on fostering evidence-based data interpretation in experimental studies of materials' UV-vis absorption, scattering, and fluorescence properties. We begin by outlining common issues observed in UV-vis and fluorescence analysis. Subsequently, we provide a summary of recent advances in commercial UV-vis spectrophotometric and spectrofluorometric instruments, emphasizing their potential to enhance scientific rigor in UV-vis and fluorescence analysis. Furthermore, we propose potential avenues for future developments in spectroscopic instrumentation and measurement strategies, aiming to further augment the utility of optical spectroscopy in nano research for samples where optical complexity surpasses existing tools. Through a targeted focus on the critical issues related to UV-vis and fluorescence properties of nanomaterials, this Perspective can serve as a valuable resource for researchers, educators, and practitioners.

Cobalt-Catalyzed Enantioselective Hydrogenation of Diaryl Ketones with Ferrocene-Based Secondary Phosphine Oxide Ligands.

A new class of cobalt catalytic system for asymmetric hydrogenation of ketones was herein reported, involving the development of novel ferrocene-based secondary phosphine oxide ligands. An unusual P-O bidentate coordination pattern with cobalt was confirmed by an X-ray diffraction study. The bichelating tetrahedral cobalt(II) complexes afforded high reactivities (up to 99% yield) and good to excellent enantioselectivities (up to 92% ee) in the AH of various ortho-substituted diaryl ketones. In addition, the diferrocenyl cobalt complex was characterized with intriguing UV-vis absorption and electrochemical properties.

Novel Fluorescent Tetrahedral Zinc (II) Complexes Derived from 4-Phenyl-1-octyl-1H-imidazole Fused with Aryl-9H-Carbazole and Triarylamine Donor Units: Synthesis, Crystal Structures, and Photophysical Properties.

We present here the design, synthesis, and photophysical properties of two novel fluorescent zinc (II) complexes, ZnCl2(ImL1)2 and ZnCl2(ImL2)2, containing 4-(1-octyl-1H-imidazol-4-yl)-N,N-diphenyl-[1,1-biphenyl]-4-yl)-4-amine ImL1 and 9-(4-(1-octyl-1H-imidazol-4-yl)-[1,1-biphenyl]-4-yl)-9H-carbazole ImL2 ligands. The newly synthesized free ligands and their zinc (II) complexes were characterized using several spectroscopic techniques; their structures were identified by single-crystal X-ray diffraction; and their photophysical properties have been studied in the context of their chemical structure. The ZnCl2(ImL1)2 and ZnCl2(ImL2)2 complexes showed good thermal stability at 341 °C and 365 °C, respectively. Photophysical properties, including UV-Vis absorption spectra in ethanol solution and photoluminescence (PL) in both solid state and ethanol solution, were determined. UV-Vis adsorption data indicated that both free ligands had similar UV-Vis absorption properties, while their Zn (II) complexes had distinctive absorption characteristics. The fluorescence spectra show that both ligands and their corresponding Zn (II) complexes emit violet to cyan luminescence in the solid state at room temperature, while in ethanol solution at the same temperature, they exhibit efficient photoluminescence properties in the UV-A emission spectral region. Because of these photophysical properties, the synthesized ligands and their cognate Zn (II) complexes can be used as scaffolds for the potential development of optoelectronic materials.

Nonlinear Optical Properties and Phototunable Absorption of a Substituted Dihydroazulene-Vinylheptafulvene Pair of Photochromes.

Quantum calculations were used to study UV-vis absorption properties and nonlinear optical characteristics of a variety of substituted dihydroazulene (DHA)/vinylheptafulvene (VHF) photoswitches. The absorption properties are substantially based on the position and nature of the substituent. In general, electron-donating groups cause red shifts compared to the parent compound. Any electron-withdrawing group, on the other hand, would generate a blue shift. Furthermore, the steric effect at some positions is accountable for the loss of planarity and, as a response, a decrease in electronic conjugation within the molecule, which in most cases result in blue shifts in maximum absorption. The purpose of this research is to investigate the influence of substitution at the seven-membered ring of the DHA/VHF system on the absorption spectra and nonlinear optical characteristics of dihydroazulene photoswitches. UV-vis spectra and hyperpolarizability are determined since a prospective photoswitch should have a minimum overlap of absorption spectra from both isomers. Furthermore, the differential in hyperpolarizability between DHA and VHF is critical for practical applications.

Architectures and Mechanisms of Perylene Diimide-Based Optical Chemosensors for pH Probing

The precise control and monitoring of pH values remain critical for many chemical, physiological and biological processes. Perylene diimide (PDI)-based molecules and materials exhibit excellent thermal, chemical and photochemical stability, unique UV-vis absorption and fluorescent emission properties, low cytotoxicity, as well as intrinsic electron-withdrawing (n-type semiconductor) nature and impressive molecular assembly capability. These features combined enable promising applications of PDIs in chemosensors via optical signal modulations (e.g., fluorescent or colorimetric). One of the typical applications lies in the probing of pH under various conditions, which in turn helps monitor the extracellular (environmental) and intracellular pH change and pH-relying molecular recognition of inorganic or organic ions, as well as biological species, and so on. In this review, we give a special overview of the recent progress in PDI-based optical chemosensors for pH probing in various aqueous and binary water–organic media. Specific emphasis will be given to the key design roles of sensing materials regarding the architectures and the corresponding sensing mechanisms for a sensitive and selective pH response. The molecular design of PDIs and structural optimization of their assemblies in order to be suitable for sensing various pH ranges as applied in diverse scenarios will be discussed in detail. Moreover, the future perspective will be discussed, focusing on the current key challenges of PDI-based chemosensors in pH monitoring and the potential approach of new research, which may help address the challenges.

Fluorinated Merophosphinine and Phosphinine Dyes: Synthesis and Evaluation of UV-Visible Light Absorption Properties

Merophosphinine and phosphinine dyes were reported as phosphorus atom equivalents of merocyanine and cyanine dyes in the 1960s. Although these dyes are excellent sensitizers for enhancing photographic performance, their development has been considerably retarded because of difficulties in the synthetic process. Previously, while investigating the reactivity of fluoroalkenes with various nucleophiles, we developed fluorinated merophosphinine and phosphinine scaffolds in a single reaction step; however, we did not investigate their ultraviolet-visible (UV-vis) light absorption properties further. Therefore, in this study, we synthesized fluorinated merophosphinines and phosphinine derivatives using triphenylphosphonium ylides with various R substituents [R = H, C6H5, 4-MeOC6H4, 4-PhC6H4, or C6F5] and octafluorocyclopentene to study their absorption characteristics. Thermogravimetric analyses (TGA) indicated that several synthesized derivatives were thermally stable at temperatures above 241 °C. Additionally, when studied in various solvents, the fluorinated merophosphinine and phosphinine dyes exhibited well-defined maximum absorption wavelengths (λabs) in the 364–375 and 420–474 nm ranges, respectively. Thus, fluorinated merophosphinine and phosphinine derivatives may serve as promising thermally stable functional dyes for future technical applications.

Synthesis, structures, and solid-state photoresponsive color change behavior of boronium complexes bearing a pyridine-imine, diimine, or pyridine-ketone bidentate ligand.

9-Borabicyclo[3.3.1]nonane-based boronium triflates bearing a N-substituted 2-pyridylmethanimine, N,N'-dialkylethane-1,2-diimine, or 2-arylcarbonylpyridine ligand were synthesized. Their tetracoordinate boron structures were determined using 11B NMR spectra and X-ray crystallography. The pyridine-imine complexes exhibited solid-state photoresponsive color changes upon UV irradiation, which indicated that boronium complexes without a bipyridine moiety also have photoresponsive capabilities. Combination of TD-DFT calculations and measurements of UV-vis absorption and fluorescence properties, diffuse reflectance spectra, and ESR spectra provided suggestions on the determining factor of the photoresponsive color change capabilities and structures of the photoproducts.

Synthesis, structural characterization and DNA binding properties of phthalazinylhydrazone-furan and triazolophthalazine-ferrocene compounds

A phthalazinylhydrazone (2) and two triazolophthalazines (3 and 4) derived from hydralazine were prepared and their structures were characterized by FTIR, 1H/13C NMR and elemental analysis. Compound 3 was prepared by cyclisation of compound 2 in the presence of FeCl2 as catalyst while compound 4 formed in the reaction without a catalyst. The crystal structures of the compounds 2 and 4 were determined by single crystal X-ray diffractions. The crystal structures of the compounds are mainly stabilised by π-π stacking interactions. The phthalazinylhydrazone (2) and triazolophthalazines compounds (3 and 4) showed distinctive UV-Vis absorption properties in solution. The structurally characterized compounds were studied for their double-stranded fish sperm DNA (Fsds-DNA) binding affinities. The UV-Vis spectral data showed that all three compounds exhibited comparable binding properties to Fsds-DNA with intrinsic binding (Kb) constants 4.50 × 104-4.85 × 105 M−1 range. The UV-Vis absorption data along with the ethidium bromide displacement and viscosity studies suggest that all three compounds interact with Fsds-DNA via intercalation.

A new heteroleptic cuprous polymer constructed by a cyanopyridine ligand exhibiting a supramolecular framework structure and luminescence.

Luminescent cuprous complexes are of great importance among coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The title heteroleptic cuprous polymer solvate, catena-poly[[[(9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane)-κ2P,P'](μ-pyridine-3-carbonitrile-κ2N1:N3)copper(I)] hexafluorophosphate dichloromethane trisolvate], {[Cu(C6H4N2)(C39H32OP2)]PF6·3CH2Cl2}n, conventionally abbreviated as {[Cu(3-PyCN)(Xantphos)]PF6·3CH2Cl2}n, where Xantphos and 3-PyCN represent (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane) and pyridine-3-carbonitrile, respectively, has been described. In this polymer solvate, the asymmetric unit consists of three dichloromethane solvent molecules, a hexafluorophosphate anion and a polymeric heteroleptic cuprous complex cation, in which the cuprous centre is in a CuP2N2 tetrahedral coordination and is coordinated by two P atoms from the Xantphos ligand and two N atoms from two 3-PyCN ligands (the pyridyl and cyano N atoms). It is through the connection of the μ2-bridging 3-PyCN ligand that these cuprous centres are linked into a one-dimensional helical chain structure. The chains are further assembled through C-H...π interactions to form a supramolecular metal-organic framework containing solvent-accessible channels. The UV-Vis absorption and photoluminescence properties of this heteroleptic cuprous polymer have been studied on as-synthesized samples. Its luminescence emission should mainly originate from the metal-to-ligand charge transfer excited state.

Borylation in the Second Coordination Sphere of FeII Cyanido Complexes and Its Impact on Their Electronic Structures and Excited-State Dynamics

Second coordination sphere interactions of cyanido complexes with hydrogen-bonding solvents and Lewis acids are known to influence their electronic structures, whereby the non-labile attachment of B(C6F5)3 resulted in several particularly interesting new compounds lately. Here, we investigate the effects of borylation on the properties of two FeII cyanido complexes in a systematic manner by comparing five different compounds and using a range of experimental techniques. Electrochemical measurements indicate that borylation entails a stabilization of the FeII-based t2g-like orbitals by up to 1.65 eV, and this finding was confirmed by Mössbauer spectroscopy. This change in the electronic structure has a profound impact on the UV–vis absorption properties of the borylated complexes compared to the non-borylated ones, shifting their metal-to-ligand charge transfer (MLCT) absorption bands over a wide range. Ultrafast UV–vis transient absorption spectroscopy provides insight into how borylation affects the excited-state dynamics. The lowest metal-centered (MC) excited states become shorter-lived in the borylated complexes compared to their cyanido analogues by a factor of ∼10, possibly due to changes in outer-sphere reorganization energies associated with their decay to the electronic ground state as a result of B(C6F5)3 attachment at the cyanido N lone pair.

Sonochemical synthesis of interconnected SnS nanocrystals for supercapacitor and solar-physical conversion applications

Tin Sulfide (SnS) nanostructures based solar energy conversion and energy storage have attracted the research interest in the recent years. We have reported the ultrasonically synthesized interconnected SnS nanocrystals and their performance in supercapacitor, photovoltaic and photocatalytic applications. The SnS nanoparticles exhibited the orthorhombic crystalline nature with the crystalline sizes of 11 nm, 7.2 nm and 4.5 nm for various quantity of polyvinyl pyrrolidone (PVP), utilized as agglomeration preventing agent. The electron microscopic images were clearly evidenced the interconnected SnS nanoparticles with an average particle size of 7 nm. The nanoparticles exhibited the size dependent UV–vis absorption properties and the band gap values were found to be 1.18 eV, 1.26 eV and 1.34 eV for SnS nanoparticles. The SnS nanoparticles had shown the excellent supercapacitor behaviour with the specific capacitance value of 1421.05 F/g and superior recyclability. Ultrasonically produced SnS nanoparticles had shown 12% efficiency in DSSC Solar cell applications. Also, the SnS nanoparticles had shown the excellent performance in photocatalytic degradation of methylene blue under LED light illumination.

Zinc(II) and copper(II) complexes with benzothiadiazole Schiff-base ligands

The ligand (2-[4-(2,1,3-benzothiadiazole)imino]methyl-phenol) HL1 containing the electron poor benzothiadiazole (BTD) unit, conveniently prepared by condensation of 4-amino-2,1,3-benzothiadiazole and salicylaldehyde, has been structurally characterized by single crystal X-ray diffraction. Two energy minima have been determined, by DFT calculations, for HL1 and for its ortho-vanillin analogue HL2, corresponding either to the conformer observed in the solid state or to the chelating tridentate form. TD-DFT calculations have been performed on HL1 and HL2 in order to assign their experimental UV–visible absorption bands. Reaction of HL1 and HL2 with copper (II) hexafluoroacetylacetonate (hfac), zinc (II) hexafluoroacetylacetonate or zinc (II) acetate provided the neutral complexes [Cu(L1)(hfac)] (1), [Zn(L1)2] (2), [Cu(L2)2] (3) and [Zn(L2)2] (4) which were structurally characterized, with a focus on the coordination sphere of the metal centre and on the intermolecular interactions. The UV–visible absorption properties of the Zn(II) complexes 2 and 4 have been experimentally and theoretically investigated and compared to those of the ligands. Finally, the cryomagnetic study of 1 and 3 in the temperature range 2.0–295.0 K reveals a Curie-Weiss law behaviour with very weak intermolecular antiferromagnetic interactions in the low temperature region.

New porphyrin photosensitizers—Synthesis, singlet oxygen yield, photophysical properties and application in PDT

This research on porphyrin-based photosensitizer system has a very important theoretical and practical significance in the photodynamic therapy (PDT) treatment of cancer. Based on this, in this article, a series of porphyrin derivatives were first designed and synthesized, and a “push-pull” porphyrin photosensitizer with two symmetrical ethanethioate groups was finally constructed. Based on the characterization of their chemical structures (1H and13C NMR, MS, IR, and UV–Vis spectroscopy) and the use of the density functional theory (DFT) and time-dependent DFT (TDDFT) to address the nature of the excited states as well as the dark/phototoxicity, the results have indicated the relationship between the porphyrin structure and properties. The experimental and theoretical UV–Vis absorption properties of porphyrins were discussed. The four porphyrin compounds synthesized all demonstrated a high capacity to generate singlet oxygen under long-wavelength (590 nm) light and low dark toxicity. Compared with the conventional porphyrin photosensitizers, P4 with a CT band (from 580 to 750 nm) is beneficial to the penetration of the light, presenting the potential for applications in PDT.