Ultraviolet Visible Near-infrared Spectroscopy Research Articles

Efficient doping of Spiro-OMeTAD by NO2

Doping of 2,2′,7,7′-tetrakis(N,N-di-4-methoxyphenylamino)-9,9′-spirobifluorene(Spiro-OMeTAD), which is the most common used hole transport material in perovskite solar cells, is widely studied. Especially, bis(trifluoromethane)sulfonamide (Li-TFSI) combined with 4-tert-butylpyridine (TBP) is the most studied dopant to improve the conductivity of Spiro-OMeTAD, with conductivity around 6×10−8 S/cm. In this study, we employed a new oxidizing agent NO2 to dop the Spiro-OMeTAD simply by vapor exposure, showing efficient doping with conductivity up to 2.53×10−3 S/cm and excellent film quality. The doping mechanism was further analyzed by ultraviolet-visible-near infrared spectroscopy (UV-Vis-NIR), electron paramagnetic resonance spectroscopy (EPR), Fourier infrared absorption spectroscopy (TFIR), and X-ray photoelectron spectroscopy. Our findings highlight the potential of molecular doping with NO2 to significantly improve the conductivity of Spiro-OMeTAD, providing a deep understanding of the doping effects on Spiro-OMeTAD.

Mattel's ©Barbie: Preventing Plasticizers Leakage in PVC Artworks and Design Objects through Film-Forming Solutions.

The main conservation problem of p-PVC artworks is phthalate-based plasticizer migration. Phthalate migration from the bulk to the surface of the materials leads to the formation of a glossy and oily film on the outer layers, ultimately reducing the flexibility of the material. This study aimed to develop a removable coating for the preservation of contemporary artworks and design objects made of plasticized polyvinyl chloride (p-PVC). Several coatings incorporating chitosan, collagen, and cellulose ethers were assessed as potential barriers to inhibiting plasticizer migration. Analytical techniques including optical microscopy (OM), ultraviolet/visible/near-infrared spectroscopy (UV/Vis/NIR), Fourier transform infrared spectroscopy with attenuated total reflection (FTIR-ATR), and scanning electron microscopy (SEM) were utilized to evaluate the optical and chemical stability of selected coating formulations applied to laboratory p-PVC sheet specimens. Subsequently, formulations were tested on a real tangible example of a design object, ©Barbie doll, characterized by the prevalent issue of plasticizer migration. Furthermore, the results obtained with the tested formulations were evaluated by a group of conservators using a tailored survey. Finally, a suitable coating formulation capable of safeguarding plastic substrates was suggested.

Optical response and temperature shielding coatings using tri-layer structure composed of titania/silica/titania

The fabrication of metamaterials with inspiration from nature paved the door for the creation of revolutionary passive and active devices. Butterfly wings are one of them, and their multilayered structure motivated nanotechnologists, physicists, and other optoelectronic and photonic engineers to develop photonic crystals, dielectric reflectors, and Bragg reflectors for use in visible light communication, solar cells, and other photonic and optoelectronic applications. We report the sol–gel spin coating of a dielectric reflector on the glass substrate, an optical passive component consisting of titania and silica thin films for infrared radiation reflection. Individual thin films of titania and silica on glass substrates were studied using an x-ray diffractometer, which indicated anatase of titania and the amorphous nature of silica at a Bragg angle of 25° with a sharp and wide peak, respectively. The multilayer structure of titania/silica/titania was further investigated using Fourier transform infrared spectroscopy, which revealed the presence of Ti–O–Ti and Si–O–Si vibrational bonds at wavenumbers 546 and 973 cm−1, respectively, as well as the presence of Ti–O–Si vibrational bond at 1100 cm−1. The thickness of the multilayer titania/silica/titania was measured using a cross-sectional field emission scanning electron microscope (FESEM) and found to be 160/240/160 nm, respectively. Finally, reflection investigation on the multilayer structure using ultraviolet–visible–near-infrared spectroscopy validated the reflection of the infrared spectrum area by around 70% and showed to be beneficial for temperature shielding applications on glass furnishings.

Preparation study and simulation of high transmittance W–Sn–Zr Co-doped VO2 thin films prepared by sol-gel method for energy-saving smart windows

The thermochromic properties of vanadium dioxide (VO2) hold great promise for applications in smart glass windows. VO2 films exhibit a high phase transition temperature (Tc), low visible transmission (Tlum), and low solar modulating ability (ΔTsol), making them inadequate for the requirements of smart glass windows. While some improvement in VO2 film performance can be achieved through single-element doping, these limited enhancements still fall short of ideal results. Therefore, there is a pressing need for the improvement of VO2 films. In this study, we utilized the sol-gel method to prepare VO2 samples simultaneously doped with three elements: W, Sn, and Zr. Microscopic characterization confirmed the successful incorporation of these elements. Optical measurements, including ultraviolet–visible–near-infrared spectroscopy, were conducted to assess the optical properties of the films. Ultimately, outstanding Tlum (69%) and ΔTsol (14%) were achieved, along with an appropriate Tc (27.6 °C). Energy consumption simulations were performed using the EnergyPlus model with experimental data, revealing that compared to conventional glass, VO2 glass reduces total cooling energy consumption by 9.8%. In comparison to previous work, the multi-element-doped films push the performance limits of VO2 films, offering a viable approach for fabricating superior VO2 smart glass windows.

One-pot synthesis of near-infrared absorbing silver nanoprisms via a simple photochemical method using an ultraviolet-C light source

This study describes a simple one-pot photochemical method to synthesize triangular silver nanoprisms (T-AgNPs), for which a mixture of silver nitrate (AgNO3) and citrate was irradiated with an ultraviolet-C (UVC) lamp reactor. We successfully synthesized T-AgNPs with edge lengths ranging from 50 to 150 nm, showing a significant localized surface plasmon resonance (LSPR) band over a wavelength of 1200 nm. This photochemical reaction appears to be unrestricted by plasmon resonance conditions, allowing for the formation of colloidal T-AgNPs with an LSPR band in the near-IR region. In addition, this new method does not require any highly reactive reducing agents or initially prepared silver seed solution. The reduction of Ag+ ions by citrate is induced by UVC light, and the nascent Ag first undergoes nucleation to form spherical or quasi-spherical silver nanoparticles (S-AgNPs). Subsequently, continuous irradiation with UVC light facilitates the transformation of these S-AgNPs into T-AgNPs. The growth kinetics of the nanoparticles with different reaction conditions were examined using ultraviolet–visible–near-infrared spectroscopy and transmission electron microscopy. This new method offers a simple, efficient, and cost-effective means to synthesize T-AgNPs with near-IR LSPR, contributing to wider applications in the fields of optoelectronics, spectroscopics, photovoltaics, etc.

Identification of Some Gem Quality Blue to Green Li-Tourmalines

Due to their appealing colors, gem quality tourmalines, particularly the blue to green Cu- and Mn-bearing Li-tourmalines known as the Paraíba type, have been of significant interest since their discovery at the end of 1980s. At the same time, the demand of other similar colored tourmalines increased. Most Paraíba-type tourmalines belong to the elbaite species; however, liddicoatite gems can also be found. Recognizing and classifying various tourmaline species, especially these valued Paraíba-type tourmalines, are important for geologists, mineralogists, mineral collectors, and gemologists. This study explores the application of Raman spectroscopy in random crystal orientations to distinguish between the elbaite and liddicoatite tourmaline species. Raman spectra were collected from faceted blue to green Li-tourmalines alongside chemical analysis using EDXRF (Energy Dispersive X-ray Fluorescence), UV-Vis-NIR (Ultraviolet-Visible-Near InfraRed Spectroscopy), and PL (Photoluminescence spectroscopy) to provide comprehensive characterization. The results show that Raman spectroscopy, particularly in the OH stretching region, is a useful tool for differentiating elbaite from liddicoatite, and this identification remains consistent regardless of crystal orientation. The fingerprint region in the Raman spectra, on the other hand, is orientation-dependent and can only differentiate the two species when detected in specific orientations. Furthermore, Paraíba-type tourmalines can be identified by visible-near infrared (Vis-NIR) spectroscopy, although not by Raman spectroscopy.

Cesium lead iodide-decorated two-dimensional titanium dioxide/reduced graphene oxide nanofiber composites as photoanodes for inorganic perovskite solar cells

In this study, we developed photoanode materials based on inorganic cesium lead iodide (CsPbI3)-decorated two-dimensional titanium dioxide-reduced graphene oxide nanofibers (TiO2/rGO NFs22TiO2/rGO NFs - titanium dioxide-reduced graphene oxide nanofibers.) for perovskite solar cells (PSCs). CsPbI3 was prepared by a two-step solution process and TiO2/rGO NFs were prepared using the electrospinning method. The influence of the as-fabricated TiO2 NFs, TiO2/rGO NFs, and CsPbI3 perovskite on their optical, surface, and morphological properties were characterized using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy, ultraviolet–visible–near-infrared spectroscopy, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, and atomic force microscopy analyses. XRD analysis of the TiO2 NFs, TiO2/rGO NFs, and CsPbI3 perovskite showed a crystalline nature with cubic and anatase crystal faces. The surface morphology of the TiO2 NFs, TiO2/rGO NFs, and CsPbI3 perovskite appeared as a beat-free fiber with a polycrystalline nature. The chemical oxidative states and electronic structures of the electrospun TiO2/rGO NFs were determined by X-ray photoelectron spectroscopy analysis. PSCs device were assembled with TiO2 NFs, TiO2/rGO NFs as photoanode, 2,2′,7,7′-Tetrakis(N,N-di-P-methoxyphenylamine)− 9,9′-spirobifluorene (Spiro–OMeTAD) as hole transport materials, sputtered gold chloride as back electrode (counter electrode). In addition, the CsPbI3 perovskite coated on the electrospun TiO2 and TiO2/rGO NF photoanodes exhibited electrical conductivities of 1.352 × 10−3 and 1.650 × 10−3 S cm−1. Finally, power conversion efficiency of TiO2/rGO NFs (6.38 %) was achieved, which was significantly higher than that of conventional TiO2 NFs (5.54 %)-based devices.

The effect of tin doping on physical properties of cobalt oxide thin films

This work deals with the effect of Sn doping at mole percentages of 1 %, 2 %, 3 % and 4 % on the structural, morphological, and optical properties of Co3O4 thin films. These physical properties were carried out by X-Ray Diffraction (XRD), Raman, Atomic Force Microscopy (AFM), scanning electron microscope (SEM), Ultraviolet-Visible-Near infrared spectroscopy (UV-Vis-NIR) and spectroscopic ellipsometry (SE). Co3O4 thin films were grown on amorphous glass substrates by spray pyrolysis technique. Experimental and modeling rigorous studies using these different techniques particularly SE were achieved in order to determinate the effect of tin doping on physical properties of cobalt oxide thin films. The incorporation of Sn into the Co sites affects drastically the optical transitions values as well as other optical properties such as the dielectric function, the band gap, the refractive index and the extinction coefficient. All doped samples exhibited a relatively higher absorption coefficient compared to the undoped ones, greater than 105 cm−1 over a wide energy range. SE analysis revealed a smaller transition of approximately 0.77 eV considered as fundamental band gap energy that was assigned to a 3d-d type within the Co2+ tetrahedral site.

Preparation of high near-infrared reflectance mica/(Ni, Sb)-co-doped rutile yellow composite pigment via mechanochemical pretreatment and sintering

Mica/(Ni, Sb)-co-doped rutile yellow composite pigment with a high near-infrared reflectance was prepared via mechanochemical pretreatment and subsequent sintering. (Ni, Sb)-co-doped rutile yellow pigment was synthesized by a solid-phase method in the presence of sodium fluoride (NaF) as a mineralizer, and mica was peeled by ultrafine grinding. The pigment, mica and mica/pigment composite were characterized by X-ray diffraction, laser diffraction particle size analysis, nitrogen gas adsorption method, scanning electron microscopy, energy dispersive spectroscopy, ultraviolet–visible–near-infrared spectroscopy, CIEL*a*b* color scales, and infrared irradiation image, respectively. The results show that the temperature of synthesizing a pure rutile pigment in solid-phase reaction is reduced by 100°C due to the addition of mineralizer NaF. (Ni, Sb)-co-doped rutile pigment has better color rendering performance and near-infrared (NIR) reflectance. Ultrafine grinding produces the finer flatty mica particles with fresh reflective surfaces, thus improving NIR reflectance of peeled mica. In mica/pigment composite prepared via mechanochemical pretreatment and subsequent sintering, peeled mica has a synergistic effect on (Ni, Sb)-co-doped rutile pigment particles to further scatter near-infrared radiation through the multiple layer reflections, leading to a better heat insulation. The high near-infrared reflectance of composite pigment increases to 97.72%, and the b* value of the pigment synthesized with 1 wt% NaF is 37.77. For the irradiation infrared lamp, the surface temperature of aluminum plate coated with mica/(Ni, Sb)-co-doped rutile yellow composite pigment is 40.1 ± 0.2°C, which is lower than that of aluminum plate uncoated determined by thermal camera and thermocouple. When aluminum plate coated with mica/(Ni, Sb)-co-doped rutile yellow composite pigment is under sunshine, its surface temperature is 38.6 ± 0.2°C. In addition, the mechanism of preparing the composite pigment via mechanochemical pretreatment and subsequent sintering and the multiple structure reflection effect on peeled mica surface coated with (Ni, Sb)-co-doped rutile yellow pigment particles were also discussed.

Electrical Conductivities of Narrow-Bandgap Polymers with Two Types of π-Conjugated Post-Crosslinking.

Bandgap energy is one of the most important properties for developing electronic devices because of its influence on the electrical conductivity of substances. Many methods have been developed to control bandgap, one of which is the realization of conducting polymers using narrow-bandgap polymers; however, the preparation of these polymers is complex. In this study, water-soluble, narrow-bandgap polymers with reactive groups were prepared by the addition–condensation reaction of pyrrole (Pyr), benzaldehyde-2-sulfonic acid sodium salt (BS), and aldehyde-containing reactive groups (aldehyde and pyridine) for post-crosslinking. Two types of reactions, aldehyde with p-phenylenediamine and pyridine with 1,2-dibromoethylene, were carried out for the π-conjugated post-crosslinking between polymers. The polymers were characterized by proton nuclear magnetic resonance (1H-NMR), thermogravimetric/differential thermal analysis (TG/DTA), UltraViolet-Visible-Near InfraRed spectroscopy (UV-Vis-NIR), and other analyses. The bandgaps of the polymers, calculated from their absorption, were less than 0.5 eV. Post-crosslinking prevents resolubility and develops electron-conducting routes between the polymer chains for π-conjugated systems. Moreover, the post-crosslinked polymers maintain their narrow bandgaps. The electrical conductivities of the as-prepared polymers were two orders of magnitude higher than those before the crosslinking.

Effects of aging time in hydrogen peroxide-glycine-based Cu CMP slurry

Hydrogen peroxide is widely used as an oxidizer in metal chemical mechanical planarization (CMP) slurry due to its strong oxidizing ability and being a non-metal product. However, hydrogen peroxide is unstable and easily decomposes into water and oxygen molecules. In this experiment, the aging of a hydrogen peroxide-glycine-based Cu CMP slurry was investigated in terms of the chemical concentration and CMP performance. Ultraviolet–visible–near-infrared spectroscopy was used to measure the change of hydrogen peroxide concentration with slurry aging. As the slurry aging time was increased, the removal rate decreased for several reasons. With slurry aging, not only decreases of hydrogen peroxide concentration but also decreases of pH and glycine decomposition were observed. Therefore, the removal rate was suppressed due to complex factors, including the decreased oxidizing ability with decreased hydrogen peroxide concentration, decomposition of the glycine chelating agent, and decrease in pH. This study suggests the necessity of monitoring slurry aging and management for optimizing CMP process performance.

Methane oxidation to methanol over copper-containing zeolite

Methane oxidation to methanol over copper-containing zeolite

Engineering the Thermoelectrical Properties of PEDOT:PSS by Alkali Metal Ion Effect

Engineering the electrical properties of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) holds great potential for various applications such as sensors, thermoelectric (TE) generators, and hole transport layers in solar cells. Various strategies have been applied to achieve optimal electrical properties, including base solution post-treatments. However, the working mechanism and the exact details of the structural transformations induced by base post-treatments are still unclear. In this work, we present a comparative study on the post-treatment effects of using three common and green alkali base solutions: namely LiOH, NaOH, and KOH. The structural modifications induced in the film by the base post-treatments are studied by techniques including atomic force microscopy, grazing-incidence wide-angle X-ray scattering, ultraviolet–visible–near-infrared spectroscopy, and attenuated total reflectance Fourier-transform infrared spectroscopy. Base-induced structural modifications are responsible for an improvement in the TE power factor of the films, which depends on the basic solution used. The results are explained on the basis of the different affinity between the alkali cations and the PSS chains, which determines PEDOT dedoping. The results presented here shed light on the structural reorganization occurring in PEDOT:PSS when exposed to high-pH solutions and may serve as inspiration to create future pH-/ion-responsive devices for various applications.

Photoconductive Coordination Polymer with a Lead-Sulfur Two-Dimensional Coordination Sheet Structure.

Coordination polymers with metal-sulfur (M-S) bonds in their nodes have interesting optical properties and can be used as photocatalysts for water splitting. A wide range of inorganic-organic hybrid materials with M-S bonds have been prepared in recent years. However, there is a dearth of structural information because of their low crystallinity, which has hampered the understanding of their underlying chemistry and physics. Thus, we conducted a structural study of a novel, highly crystalline coordination polymer with M-S bonds. Theoretical calculations were performed to elucidate its photoconductivity mechanism. The photoconductive, three-dimensional coordination polymer [Pb(tadt)]n (denoted as KGF-9; tadt = 1,3,4-thiadiazole-2,5-dithiolate) was synthesized and confirmed to have a three-dimensional structure containing a two-dimensional Pb-S framework by single-crystal X-ray diffraction. We also performed diffuse-reflectance ultraviolet-visible-near-infrared spectroscopy, time-resolved microwave conductivity, and photoelectron yield spectroscopy measurements on the bulk powder samples, as well as first-principles calculations. Additionally, direct-current photoconductivity measurements were conducted on a single-crystal sample.

Comparison of characteristics of Bi2Te3 and Bi2Te2.7Se0.3 thermoelectric materials synthesized by hydrothermal process

In this research, a simple approach based on hydrothermal method was developed for the synthesis of high purity Bi2Te2.7Se0.3 polyhedral nanoflakes and Bi2Te3 spherical nanoparticles. The synthesized Bi2Te3 and Bi2Te2.7Se0.3 nanopowders were characterized by X-ray diffraction, Fourier transform infrared spectrometry, field emission electron microscopy, photoluminescence (PL) and ultraviolet–visible near-infrared spectroscopy. The results showed that the produced powders (Bi2Te3 and Bi2Te2.7Se0.3) exhibit no chemical impurity formed during hydrothermal synthesis process. Besides, the ternary Bi2Te2.7Se0.3 alloy showed less oxide bond versus the Bi2Te3 alloy. The results showed that Bi2Te2.7Se0.3 powders possess a uniform nano-flake shape with an average size of 48 nm along with bandgap energy of 0.6 eV. Moreover, Bi2Te3 powders were characterized with a uniform spherical shape and an average size of 43 nm along with bandgap energy of 0.9 eV. The Bi2Te2.7Se0.3 nanoplate powders exhibited a favorable bandgap and lower PL intensity due to the larger particle size compared with the spherical Bi2Te3 nanopowders. In conclusion, the obvious specifications of Bi2Te3-based materials were improved by the incorporation of selenium using a hydrothermal procedure. It is strongly believed that this synthesis approach and characterization methods will be important for the development of thermoelectric performance and applications of these groups of materials, such as sensors, laser diode, cooling system, fiber-optic systems.

Preparation of few-layer black phosphorus by wet ball milling exfoliation

The wet ball milling (WBM) method is, for the first time, used for the exfoliation of bulk black phosphorus (BP) to obtain few-layer black phosphorus (FBP). Before that, the rational solid–liquid ratio of raw material is determined to be 1:1 (mg/mL) for the popular ultrasound liquid exfoliation (ULE). Obviously, the high proportion of organic solvent used in ULE will lead to serious environmental pollution. Compared with ULE, the solid/liquid ratio for WBM exfoliation is 100:1 (mg/mL) showing its advantage of less demand for organic solvent. In addition, different types of organic solvents are used to determine the proper organic solvent for WBM exfoliation. Ultraviolet–visible–near-infrared spectroscopy, X-ray diffraction, transmission electron microscopy, and laser particle size analyzer are used to comprehensively characterize the layer numbers, morphology size, and phase structure of FBP yielded by WBM exfoliation. The results show that dimethyl sulfoxide (DMSO) is the suitable organic solvent for BP exfoliation; FBP flakes with 3–5 layers and micron size are obtained by WBM exfoliation.

Preparation and Applications of Metal-Organic Frameworks (MOFs): A Laboratory Activity and Demonstration for High School and/or Undergraduate Students.

The chemistry of metal-organic frameworks (MOFs), a new class of emerging crystalline porous solids with three-dimensional (3D) networks composed of metals and multidentate organic molecules, was introduced by using three differently-shaped crystals. We reported new and mild MOF synthesis methods that are simple and devised to be performed in high school or primarily undergraduate school settings. MOF applications were demonstrated by use of our synthesized MOFs in the capture of iodine as a potentially hazardous molecule from solution and as a drug delivery system. These applications can be visually confirmed in minutes. Students can gain knowledge on advanced topics, such as drug delivery systems, through these easy-to-prepare MOFs. Furthermore, students can gain an understanding of powder X-ray analysis and ultraviolet-visible near-infrared spectroscopy. This laboratory experience is practical, including synthesis and application of MOFs. The entire experiment has also been recorded as an educational video posted on YouTube as a free public medium for students to watch and learn. In this article we first report the steps we took to synthesize and analyze the MOFs, followed by a description of a simple demonstration that we verified to effectively exhibit adsorption by MOFs. We conclude with a description of how the laboratory activity and demonstration was implemented in an undergraduate chemistry laboratory.

Solvothermal Synthesis and Near-Infrared Shielding Properties of Cs0.3WO3/WO3Composites

The Cs[Formula: see text]WO3/WO3composite with near-infrared shielding properties was synthesized by the solvothermal method using tungstic acid and cesium salt as raw materials. The as-prepared composites were tested by X-ray powder diffraction, scanning electron microscopy, energy spectrum analysis, transmission electron microscopy, electron energy loss spectroscopy, and ultraviolet-visible near-infrared spectroscopy. The effects of different reaction conditions on the structure and near-infrared shielding properties of the synthesized composites were investigated. The best near-infrared light transmittance of as-prepared composites can reach up to 9%, which provides a feasible solution for the near-infrared shielding material. The new homogeneous composites of cesium tungsten bronze and tungsten oxide are good candidates for solar filters.

Thiophene-Based Aldehyde Derivatives for Functionalizable and Adhesive Semiconducting Polymers.

The pursuit for novelty in the field of (bio)electronics demands for new and better-performing (semi)conductive materials. Since the discovery of poly(3,4-ethylenedioxythiophene) (PEDOT), the ubiquitous golden standard, many studies have focused on its applications but only few on its structural modification and/or functionalization. This lack of structural variety strongly limits the versatility of PEDOT, thus hampering the development of novel PEDOT-based materials. In this paper, we present a short and simple strategy for introducing an aldehyde functionality in thiophene-based semiconducting polymers. First, through a two-step synthesis, an EDOT-aldehyde derivative was prepared and polymerized, both chemically and electrochemically. Next, to overcome the inability of thiophene-aldehyde to be polymerized by any means, we synthesized a trimer in which thiophene-aldehyde is enclosed between two EDOT groups. The successful chemical and electrochemical polymerization of this new trimer is presented. The polymer suspensions were characterized by ultraviolet-visible-near-infrared spectroscopy, while the corresponding films were characterized by Fourier transform infrared and four-point-probe conductivity measurements. Afterward, insoluble semiconducting films were formed by using ethylenediamine as a cross-linker, demonstrating in this way the suitability of the aldehyde group for the easy chemical modification of our material. The efficient reactivity conferred by aldehyde groups was also exploited for grafting fluorescent polyamine nanoparticles on the film surface, creating a fluorescent semiconducting polymer film. The films prepared by electropolymerization, as shown by means of a sonication test, exhibit strong surface adhesion on pristine indium tin oxide (ITO). This property paves the way for the application of these polymers as conductive electrodes for interfacing with living organisms. Thanks to the high reactivity of the aldehyde group, the aldehyde-bearing thiophene-based polymers prepared herein are extremely valuable for numerous applications requiring the facile incorporation of a functional group on thiophene, such as the functionalization with labile molecules (thermo-, photo-, and electro-labile, pH sensitive, etc.).

Redox, transmetalation, and stacking properties of tetrathiafulvalene-2,3,6,7-tetrathiolate bridged tin, nickel, and palladium compounds.

Here we report that capping the molecule TTFtt (TTFtt = tetrathiafulvalene-2,3,6,7-tetrathiolate) with dialkyl tin groups enables the isolation of a stable series of redox congeners and facile transmetalation to Ni and Pd. TTFtt has been proposed as an attractive building block for molecular materials for two decades as it combines the redox chemistry of TTF and dithiolene units. TTFttH4, however, is inherently unstable and the incorporation of TTFtt units into complexes or materials typically proceeds through the in situ generation of the tetraanion TTFtt4−. Capping of TTFtt4− with Bu2Sn2+ units dramatically improves the stability of the TTFtt moiety and furthermore enables the isolation of a redox series where the TTF core carries the formal charges of 0, +1, and +2. All of these redox congeners show efficient and clean transmetalation to Ni and Pd resulting in an analogous series of bimetallic complexes capped by 1,2-bis(diphenylphosphino)ethane (dppe) ligands. Furthermore, by using the same transmetalation method, we synthesized analogous palladium complexes capped by 1,1′-bis(diphenylphosphino)ferrocene (dppf) which had been previously reported. All of these species have been thoroughly characterized through a systematic survey of chemical and electronic properties by techniques including cyclic voltammetry (CV), ultraviolet-visible-near infrared spectroscopy (UV-vis-NIR), electron paramagnetic resonance spectroscopy (EPR), nuclear magnetic resonance spectroscopy (NMR) and X-ray diffraction (XRD). These detailed synthetic and spectroscopic studies highlight important differences between the transmetalation strategy presented here and previously reported synthetic methods for the installation of TTFtt. In addition, the utility of this stabilization strategy can be illustrated by the observation of unusual TTF radical–radical packing in the solid state and dimerization in the solution state. Theoretical calculations based on variational 2-electron reduced density matrix methods have been used to investigate these unusual interactions and illustrate fundamentally different levels of covalency and overlap depending on the orientations of the TTF cores. Taken together, this work demonstrates that tin-capped TTFtt units are ideal reagents for the installation of redox-tunable TTFtt ligands enabling the generation of entirely new geometric and electronic structures.