Reflectance Spectra Research Articles

Blaze-angle led dark-blue iridescence and superhydrophobicity features of non-morpho Euploea midamus butterfly wing scale

We report on backlit iridescent blue structural coloration as well as superhydrophobicity in a non-morpho butterfly of Euploea midamus (blue-spotted crow) belonging to the Lepidoptera order. Select forewing and hindwing parts were characterized by employing optical microscopy, field emission electron microscopy, UV–vis-NIR spectrophotometry, and an advanced contact angle meter. As substantiated from variable incident angle reflectance spectra and chromaticity plots, the apparent visual effect is most pronounced in the forewing case and at an incident angle of 30–40°, with reflectance peak maxima positioned at ~ 412 nm and 478 nm. Additionally, the forewing scale of this butterfly acts as an anti-reflection filter (< 460 nm) for p-polarized light, showing greater polarization anisotropy in the lower wavelength region. Numerical simulationand microstructure-based analytical calculations with blaze angle grating effects have been considered to elucidate the observed dark-blue iridescence at large. Moreover, both the forewing and hindwing of the butterfly exhibit the ‘lotus effect’, with a contact angle as high as of ~ 150°, low contact angle hysteresis (16° and 13°) as well as low roll-off angles (10° and 7°) to favor self-cleaning action. Theoretical calculations attributing to dual roughnesses would encompass micro-textured and nanoscale asperities within the wing scale interface. The scope of the bifunctional features including optical and dewetting responses in natural systems would provide valuable insights and clues for biomimetics, particularly in nanophotonic and nanocoating applications.

Rapid estimates of leaf litter chemistry using reflectance spectroscopy

Measuring the chemical traits of leaf litter is important for understanding plants’ roles in nutrient cycles, including through nutrient resorption and litter decomposition, but conventional leaf trait measurements are often destructive and labor-intensive. Here, we develop and evaluate the performance of partial least-squares regression (PLSR) models that use reflectance spectra of intact or ground leaves to estimate leaf litter traits, including carbon and nitrogen concentration, carbon fractions, and leaf mass per area (LMA). Our analyses included more than 300 samples of senesced foliage from 11 species of temperate trees, including needleleaf and broadleaf species. Across all samples, we could predict each trait with moderate-to-high accuracy from both intact-leaf litter spectra (validation R2 = 0.543-0.941; %RMSE = 7.49-18.5) and ground-leaf litter spectra (validation R2 = 0.491-0.946; %RMSE = 7.00-19.5). Notably, intact-leaf spectra yielded better predictions of LMA. Our results support the feasibility of building models to estimate multiple chemical traits from leaf litter of a range of species. In particular, the success of intact-leaf spectral models allows non-destructive trait estimation in a matter of seconds, which could enable researchers to measure the same leaves over time in studies of nutrient resorption.

DFT insights into i-MAB phase, Mo4Y2Al3B6: a potential thermal barrier coating and solar heat reducing material

We have investigated the physical properties of the i-MAB: Mo4Y2Al3B6 phase via the density functional theory (DFT) approach. The optical properties, thermal properties, and Vickers hardness of the compound Mo4Y2Al3B6 have been studied theoretically for the first time. The correctness of the fine-tuned structural parameters is confirmed by their close match with experimental results. The compound’s metallic nature is established by an analysis of its electronic band structure, which is demonstrated by the overlap of the valence and conduction bands at the Fermi level. The mechanical and dynamic stability of the compound is supported by the single crystal elastic constants and computed phonon dispersion curve. The brittleness and machinability index has been studied to predict its usefulness in any form/shape. The compound’s ability to be exfoliated into 2D nanosheets has been proven by the f-index value. The obtained Vickers hardness value indicate the materials’ softness and ease of machining, aligning with the experimental findings. The thermodynamic properties are evaluated through phonon dispersion curves, including Debye temperature, free energy, enthalpy, entropy, and specific heat capacity. The potential of Mo4Y2Al3B6 as a thermal barrier coating (TBC) material is demonstrated by its low minimum thermal conductivity (K min), low volume expansion coefficient and high melting temperature (T m ). Key optical parameters, including dielectric functions, refractive index, photoconductivity, reflectivity, absorption coefficient, and loss function, have been computed and analyzed. The reflectivity spectrum suggests that the titled compound acts as a promising coating material for mitigating solar heating.

Construction of Zn0.5Cd0.5S/Bi4O5Br2 Heterojunction for Enhanced Photocatalytic Degradation of Tetracycline Hydrochloride

The development of efficient catalysts with visible light response for the removal of pollutants in an aqueous environment has been a hotspot in the field of photocatalysis research. A Zn0.5Cd0.5S (ZCS) nanoparticle/Bi4O5Br2 ultra-thin nanosheet heterojunction was constructed by ultrasound-assisted solvothermal method. The morphology, structure, and optoelectronic properties of the composite were characterized by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and UV–vis diffuse reflectance spectra. Under simulated visible light illumination, the photocatalytic performance was evaluated through degradation of tetracycline hydrochloride. Results show that the degradation effect by the optimum ZCS/Bi4O5Br2 catalyst is superior to pure materials with the kinetic constant that is 1.7 and 9.6 times higher than those of Bi4O5Br2 and ZCS, and also has better stability and reusability. Trapping experiments and electron paramagnetic resonance tests find that free radicals in the photocatalytic system are superoxide radicals and holes. This work provides a referable idea for the development of more efficient and recyclable photocatalysts.

Synthesis of multiple layers of alternating ZnO and TiO2 using atomic layer deposition and their optical characterization

We report the optical characterization of bi-layer and quadri-layers of TiO2/ZnO transparent oxide films having a net thickness of 100 nm. The atomic layer deposition (ALD) was used to grow these multiple-layered films. We examined their optical properties to understand the impact of the number of layers. The grazing incidence X-ray diffraction (GIXRD) was used to assess the microstructure of the films, which showed that the ZnO layers were polycrystalline, while the TiO2 layers were (X-ray) amorphous. The optical transmission and reflection spectra of the investigated films were recorded in the range of 150–2500 nm at room temperature. The refractive index (n), extinction coefficient (k), real and imaginary parts of the dielectric constant, optical conductivity, and loss factor agree well with those of other amorphous oxides. It was established that the indirect allowed optical transitions are favorable and the optical gap (Eg) increases from 3.03 eV to 3.14 eV as the number of layers increases. The contribution of polarizability (ξ) and electrical susceptibility (χe) to the dielectric constant was also discussed. The relation between the relative density (D) and the porosity (Pro) with the crystalline quality, layer thickness, and the number of layers was also estimated. The results obtained from the study of TiO2/ZnO multilayer films indicate that multilayer thin films improve the quality of film crystallinity and optical properties with the increase of the layers numbers, and could guide the development of potential applications.

2D Cadmium(II) Coordination Polymer Based on 2,5-Furandicarboxylate and 1,4-Bis(1H-imidazol-1-yl)butane Linkers: Synthesis, Characterization and DFT Studies

AbstractAs a result of hydrothermal synthesis of 2,5-furandicarboxylate (fdc2−), Cd(II) ion and bis(imidazole) derivative 1,4-bis(1H-imidazole-1-yl)butane (bib) ligand, a novel two-dimensional Cd(II) coordination polymer {[Cd(µ-fdc)(H2O)(µ-bib)]·H2O}n (1) was synthesized. According to the results of single crystal X-ray diffraction analysis, the complex was crystallized in the monoclinic system and in the P21/n space group. In addition, the thermal, luminescence and optical properties of the complex were investigated. The complex emits a maximum at 509 nm and also shows semi-conductor properties according to the solid-state UV–Vis diffuse reflection spectra results. To determine chemical structure, vibrational properties and some chemical properties of complex, theoretical calculations were carried out. All theoretical computations were performed using the DFT method at the B3LYP/LanL2DZ level of theory. The obtained experimental results were in good agreement with theoretical results. To calculate HOMO–LUMO energy values, which provided insights into the material's electronic properties, DFT calculations were used. Detailed information about the local and global chemical activity, as well as the electrophilic and nucleophilic nature of the complex, were also obtained.

In-Line Chemical Composition Monitoring for the Injection Molding Process of Biodegradable Polymer Blends Using Simultaneous Measurement of Near-Infrared Diffuse Reflectance and Transmission Spectra.

In the processing of polymer blends and composites, in-line near-infrared (NIR) spectroscopy enables monitoring of the composition and its composite uniformity and contributes to rapid process development and quality control. However, in the injection molding process, the study of the composition of polymer materials has been delayed due to high-pressure conditions. Our research group developed NIR probes for transmission and diffuse reflectance measurements that can withstand high-pressure and temperature conditions up to 130 MPa and 200 °C. In this research, transmission and diffuse reflectance spectra were measured inline during the injection molding process of polymer blends of poly(lactic acid) and polybutylene succinate adipate. The intensity of each polymer band in the second-derivative spectra exhibited a monotonic increase or decrease in response to changes in the blend ratio. Using transmission and diffuse reflectance spectra as explanatory variables of the partial least squares regression model simultaneously, the model showed high estimation accuracy for the entire region of the blend ratio. Finally, this model was applied to monitor the polymer changeover operation, and the change in the blend ratio in the molded product was successfully estimated in line.

Investigation of structural, electrical, magnetic, and optical properties of Cu (111) and the impact of Ag adatoms adsorption: A density functional theory study

Our study conducts a comprehensive investigation on the structural, electrical, magnetic and optical properties of pure Cu with a (111) crystallographic orientation, as well as the impact of the adsorption of Ag adatoms on a Cu (111) surface. To perform this analysis, we utilized the full potential linearized augmented plane-wave (FP-LAPW) approach in conjunction with Generalized Gradient Approximations (GGA + U) and the Wien2k simulation software. Specifically, we calculated electrical and optical properties including the band structure, density of states (DOS) for the Cu (111) surface with and without the presence of adsorbed Ag atoms. Based on the observed results, the overlapping of the electronic bands for simple Cu (111) is comparatively less than that of adsorbed Ag/Cu (111) slab, indicating higher conductivity. Moreover, the evolutions are also observed which are mainly due to d orbitals of Cu and Ag for Cu (111) and Cu/Ag (111) respectively. The calculated magnetic optimization and weak diamagnetic magnetic moments shows weak diamagnetism in these materials. The optical properties like Dielectric Function(ε), Refractive index(n), Extinction co-efficient(k), Reflectivity(R), Energy Loss (L), Absorption (α) and Optical conduction (σ) are calculated. Our research examines the importance of band structure calculation in relation to optical properties. We discuss how plasmon-energy plays a crucial role in producing peaks in the energy loss function, with a crystallographic axis of 13.7 eV and 13.6 eV for both Cu (111) and Ag/Cu (111) slab. In addition, we calculated the static dielectric function, absorption coefficient, and refraction values for these materials. Reflectivity spectra for both Cu (111) and Ag/Cu (111) exhibits Infra-red region, indicating good coating materials to reduce heating, for the application of electrical appliances and for optical application like anti-reflecting coating, optical fibers and solar cells.

Nanoparticles of ZrO2:xSr2+ produced by the sonochemical method: Structural, morphological, and photoluminescent characterization for optoelectronic applications

The pursuit of efficient materials for technological applications is essential. Among these materials, zirconia emerges as a promising candidate with potential for several applications, from applications related to mechanical resistance to optoelectronic applications. By introducing dopants into this compound, it becomes feasible to modulate its inherent properties. In this study, ZrO2 doped with strontium was synthesized for the first time via the sonochemical method at different percentages in mol (1, 2, 4, and 8 mol%). Analysis via X-ray diffraction (XRD) and Raman spectroscopy unveiled the formation of both monoclinic and tetragonal phases, with the latter being stabilized through the incorporation of the dopant element. In addition to observing irregular morphology through scanning electron microscopy (SEM-FEG), a reduction in particle size was also evidenced following the introduction of Sr2+ ions, a phenomenon corroborated via Rietveld refinement. The reflectance spectra of the doped samples exhibited an optical absorption tail characterized by the Urbach energy (EU), indicating an increase in structural disorder in the samples. The photoluminescence (PL) results indicated that the introduction of Sr2+ ions into the ZrO2 matrix induced modifications in the characteristics of the spectrum profile. The phase transformation observed in XRD was reflected in the changes observed in the photoluminescent behavior of the samples, which emitted light between the blue and green regions.

Na3K6(CO3)3(NO3)2X·6H2O (X = NO3, Cl, Br): Exploring High-Performance UV Birefringent Crystals Induced by Coplanar π-Conjugated CO3 and NO3 Groups.

Planar π-conjugated groups, like CO3, NO3, and BO3 triangles, are ideal functional units for designing birefringent materials due to their large optical anisotropy and wide band gap. The key point for designing birefringent crystals is to select appropriate functional building blocks (FBBs) and the proper arrangement mode. It is well known that the substitution strategy has proven to be a promising and accessible approach. In this work, alkali metals were chosen to regulate and control two different π-conjugated groups, CO3 and NO3, to build new compounds with large birefringence. Subsequently, three new compounds, Na3K6(CO3)3(NO3)2X·6H2O (X = NO3, Cl, Br), were successfully synthesized using the hydrothermal method. The aliovalent substitution between the [NO3]- anionic group and halogen anions [Cl]-/[Br]- has been achieved in these compounds. Na3K6(CO3)3(NO3)2X·6H2O feature the well-coplanar CO3 and NO3 groups in their crystal structure. This coplanar arrangement mode may effectively enhance the anisotropic polarizability of Na3K6(CO3)3(NO3)2X·6H2O. And their experimental birefringence can reach 0.094-0.131 at 546 nm. Diffuse reflectance spectra demonstrate that these compounds exhibit short ultraviolet (UV) absorption edges of ∼235 nm. Meanwhile, Na3K6(CO3)3(NO3)2X·6H2O also have an easily grown capacity under facile conditions. This work not only reports three new potential UV birefringent crystals but also provides a strategy to make the π-conjugated MO3 group coplanar.

Construction of flexible BiOBr/W18O49/polyacrylonitrile discrete heterojunction nanofibers as a dual-functional photocatalyst for simultaneous hydrogen evolution and organic pollutant degradation

Dual-functional photocatalysis has attracted increasing attention due to its ability to achieve efficient synergistic hydrogen (H2) evolution and pollutant removal. Energy band structure engineering and surface morphology modification of photocatalysts is a useful strategy to improve the activity of photocatalysis. This paper uses a combination of electrospinning technology and hydrothermal method to prepare flexible BiOBr/W18O49/PAN discrete heterojunction flexible nanofibers (NFs) with staggered energy bands and spatially separated redox surfaces. The BiOBr/W18O49 heterojunction can improve carrier separation and migration, as evidenced by the photoluminescence and photoelectrochemical experiments. The localized surface plasmon resonance (LSPR) effect of W18O49 can achieve injection of “hot electrons” and lead to expanding the light absorption range according to the UV–visible-near infrared diffuse reflection spectra results. The discrete structure of BiOBr/W18O49/PAN NFs can provide spatially separated active sites for simultaneous photocatalytic redox reaction. As expected, the BiOBr/W18O49/PAN discrete heterojunction NFs greatly enhance the photocatalytic activity in simultaneous dual-functional reaction for H2 evolution and RhB degradation. The highest simultaneous H2 evolution rate and RhB degradation rate of BiOBr/W18O49/PAN NFs are 31.7 times and 34.1 times of BiOBr/PAN, respectively. The design and construction of this flexible discrete heterojunction NFs structures can provide novel ideas and directions for simultaneous dual-functional photocatalysts.

The subtle usage of NH4BF4: Facile and economical fabrication of Ti black surface for enhanced optical absorption performance

The Ti black surface has been widely used in aerospace and photocatalysis for many years. However, the preparation technique for the Ti black surface has several disadvantages, such as a complex process, high cost and safety concerns. In this study, a new chemical immersion method using the mixed aqueous solution of 0.715 mol/L NH4BF4 and 0.004 mol/L HF was proposed to prepare a uniform Ti black surface, which is very facile, economical and efficient. Due to the etching of HF, the light-trapping nanostructure was formed on Ti surface. Grazing incidence X-ray diffraction (GIXRD) and X-ray photoelectron spectroscopy (XPS) observations indicated that the black surface was covered by the film mainly composed of TiOx, Ti(OH)x, and TiH2. The diffuse reflectance spectra demonstrated that the black surface exhibited great optical absorption performance with the maximum reflectance of 7.6 % to the UV–visible light and 35.3 % to the near-infrared light. The as-fabricated TiOx film with narrower bandgap could be contributed to the doping of Ti3+ and F− ions. The presence of F− ions in the film prevented the Ti3+ ions in the bulk of TiOx from being oxidized. The combined contribution of light-trapping nanostructure and TiOx film enhanced the optical absorption performance of Ti surface.

Empirical BRDF model for goniochromatic materials and soft proofing with reflective inks.

The commonly used analytic bidirectional reflectance distribution functions (BRDFs) do not model goniochromatism, that is, angle-dependent material color. The material color is usually defined by a diffuse reflectance spectrum or RGB vector and a specular part based on a spectral complex index of refraction. Extension of the commonly used BRDFs based on wave theory can help model goniochromatism, but this comes at the cost of significant added model complexity. We measured the goniochromatism of structual color pigments used for additive color printing and found that we can fit the observed spectral angular dependence of the bidirectional reflectance using a simple modification of the standard microfacet BRDF model. All we need to describe the goniochromatism is an empirically-based spectral parameter, which we use in our model together with a specular reflectance spectrum instead of the spectral complex index of refraction. We demonstrate the ability of our model to fit the measured reflectance of red, green, and blue commercial structural color pigments. Our BRDF model enables straightforward implementation of a shader for interactive preview of 3D objects with printed spatially and angularly varying texture.

Silver Sulfide Anchored Anatase TiO2 Nanoparticles for Ultrafast Degradation of Selective Textile Dyes

AbstractThe surface modification of the TiO2 with selective narrow band gap of metal or metal sulfide is an attractive attention in recent years. Herein, tiny Ag2S nanoparticles are well anchored on the TiO2 surface by a cost‐effective chemical precipitation method for efficient photocatalytic activity. The decoration of Ag2S nanoparticles is clearly identified through electron microscopy studies. The UV‐Vis diffuse reflection spectra (DRS) revealed that TiO2/Ag2S composites absorbed broad spectrum in the visible region. The reduced band‐gap of 2.41 eV by anchored the Ag2S on TiO2 may boosted the photocatalytic activity. Particularly, incorporation of Ag2S nanoparticles increased charge separation efficiency, lowering recombination, and improving photocatalytic performance. Because of their unique structural and optical properties, TiO2/Ag2S composites have increased photocatalytic activity. The photocatalytic performance of the pristine Ag2S and Ag2S anchored TiO2 are Crystal violet (CV) and Methyl orange (MO) dye molecules under same experimental condition. As expected, the TiO2/Ag2S showed highest photocatalytic degradation efficiency than alone TiO2.

Facile encapsulation of a cobalt complex inside the micropores of ZIF-8 through the bottle around the ship method: A novel heterogeneous catalyst for epoxidation of alkenes

A novel and stable heterogeneous catalyst for alkene epoxidation reaction, named as CoDMG@ZIF-8, has been synthesized by facile encapsulation of Co(III) complex i.e. [Co(DMGH)(DMGH2)Cl2] (abbreviated as CoDMG, DMGH2 denotes for dimethylglyoxime and DMGH denotes for dimethylglyoxime mono anion) inside the ZIF-8 micropores via a solvothermal process. Based on the results of fourier transform-infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) technique and field emission scanning electron microscopy (FE-SEM), it was observed that the catalyst has maintained the structure, crystallinity and morphology of the parent ZIF-8 as well. Furthermore, CHN, DRS (diffuse reflectance spectra), energy dispersive X-ray (EDX), induced coupled plasma (ICP-OES), thermal gravimetric (TGA) and nitrogen adsorption-desorption (BET method) analyses have confirmed the encapsulation of the CoDMG complex. The epoxidation reaction was performed using tert‑butyl hydroperoxide (TBHP) in CH3CN solvent in the presence of catalyst. By optimizing the reaction parameters, a total conversion of 96 % with 82 % selectivity towards the epoxide product, was achieved. It was found that both CoDMG complex and ZIF-8 exhibited lower efficiency individually, while the encapsulation of this complex inside the ZIF-8 micropores has resulted to superior activity. Finally, the epoxidation of various alkenes such as cyclohexene, 2-norbornene, α-pinene, styrene and 1-hexene under the optimized reaction condition, have been studied and the catalytic mechanism was also proposed.

Ba5Gd3(BO3)6F: A new alkaline earth-rare earth fluoroborate with magnetocaloric effect

A new alkaline-earth and Gd3+ borate, Ba5Gd3(BO3)6F, has been successfully grown through a high-temperature solution method employing a BaF2-NaF-B2O3 flux. This compound crystallizes in the monoclinic space group P21/c with lattice parameters of a = 13.679(4) Å, b = 8.694(3) Å, c = 7.664(2) Å, β = 99.116(7)°, V = 899.9(5) Å3, and Z = 1. Its three-dimensional structure consists of the [Ba/GdO] polyhedra and [FBa4Gd2] octahedra layers. Magnetic analysis reveals that Ba5Gd3(BO3)6F exhibits a magnetocaloric effect with a maximum −ΔSm of 29.86 J kg–1 K–1 at 3 K and 9 T. Additionally, the thermal stability, along with infrared (IR) and ultraviolet–visible–near-infrared (UV–Vis–NIR) diffuse reflectance spectra, were thoroughly examined. First-principles calculations further explored the electronic band structure and densities of states.

Comparison of optical absorption and diffuse reflectance spectra techniques for determining the optical energy band gap of dried and calcined Ni0.5Mn0.5Fe2O4 nanoferrite

Ultrafine particles of Ni0.5Mn0.5Fe2O4 were synthesized by coprecipitation technique to study the effect of both physical forms (ferrofluid and powder) and thermal treatment (drying at 100 °C and calcination at 600 °C for two hours) on the structural properties of Ni0.5Mn0.5Fe2O4 nanoferrite. In addition, the work presents a comparison between using optical absorption and optical diffuse reflectance spectra in studying the optical direct energy band gap. x-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to study the phase, size, and morphology of dried and calcined Ni0.5Mn0.5Fe2O4 nanoparticles, respectively. Fourier transform infrared (FTIR) spectra revealed the characteristic peaks of the synthesized ferrite and provided further information on the functional groups. The optical absorption spectra were used to evaluate the optical direct energy band gap of dried and calcined Ni0.5Mn0.5Fe2O4 nanoferrite as a ferrofluid, whereas, the optical diffuse reflectance spectra were used to evaluate the optical direct energy band gap of dried and calcined Ni0.5Mn0.5Fe2O4 nanoferrite in powder form.

Strong coupling between colloidal quantum dots and dielectric cavity investigated by both photoluminescence spectrum and reflection spectrum at room temperature

In this study, the angle-resolved photoluminescence spectra and reflection spectra from colloidal quantum dots on SiO2/Si material were investigated at room temperature. The strong coupling between quantum dots and F-P cavity was verified by both the photoluminescence spectral splitting and reflection dispersion. A Rabi splitting was obtained from both angle-resolved photoluminescence spectra and reflection spectra. The Hopfield coefficient of exciton and photon for polariton branches were calculated and analyzed. The relationship between Rabi frequency and excitation power for colloidal quantum dots was also studied. A method was proposed and used to characterize the cavity mode and the reflection dispersion by using open-aperture and close-aperture reflection spectra.

Selective gas detection using phase change material infused photonic crystal

A photonic crystal-based optical gas detector is proposed, incorporating phase change material (PCM) to modulate the sensing properties. The multi-gas detection process is designed in the range of 650 nm to 2500 nm. Ge2Sb2Te5 (GST) is employed as a phase change material with significant optical property variations. It can exist in two self-sustaining, bi-stable phases: a crystalline GST (CGST) and an amorphous GST (AGST). The dielectrics (i.e., Si, SiO2, GST, and Au) are used in various combinations, such as Au-Si, Au-Si-SiO2, Au-GST-SiO2, and GST-Au. Plane light waves are used to model the nanoporous structures over a broad wavelength range (650 nm to 2500 nm). The optical spectral response of the structures, including the reflectivity spectrum, power absorption spectrum, and electric field distribution, is investigated by varying the GST thickness, dimension, and geometry of the nanoholes. Liquid ammonia has the highest selectivity of any gas from 650 nm to 1000 nm, at about 29%, whereas carbon monoxide has the maximum sensitivity of 32%. The interchanging of layers increases the sensitivity of all the gases. With a sensitivity and selectivity of 78% and 40%, respectively, carbon monoxide exhibits the greatest values.

Crystal structure, optical properties, Hirshfeld surface analysis and antibacterial activity of a new organic-inorganic metal halide: 4-nitrobenzyl-4-methylpyridinium tetrachlorocobaltate(II)

This paper presented the synthesis, composition analysis, and structural characterization of a new organo-inorganic metal halide, 4-nitrobenzyl-4-methylpyridinium tetrachlorocobaltate(II) [4NO2Bz-4-MePy]2[CoCl4](1). The single-crystal X-ray diffraction analysis displayed that the compound crystallized in the monoclinic space group P21/c, consisting of two [4NO2Bz-4-MePy]+ cations and a [CoCl4]2− anion. The energy gap between the HOMO and LUMO orbitals, the polarizability, and the first hyperpolarizability were carried out based on the DFT calculation. The HOMO-LUMO energy gap and UV-visible diffuse reflectance spectrum illustrated the charge transfer interactions between the [CoCl4]2− anions and the [4NO2Bz-4-MePy]+ cations. In addition, the low band gap values (1.64 eV for the Tauc formula, 1.62 eV for the truncated line method, and 2.73 eV for the calculated value) indicated that the crystal was appropriate for optical applications. The first hyperpolarizability (βtot) was 342 times higher than that of standard KDP crystal (βKDP = 6.85 × 10−31 esu), suggesting that crystal 1 was a premium material for NLO applications. The scanning electron microscopy and energy dispersive spectrometer determined the morphology and elemental distribution of the crystal. Hirshfeld surface analysis was performed to quantify the contributions of the different intermolecular interactions. The result of antimicrobial experiments displayed that the compound had excellent antimicrobial activity against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli).