Excited Charge Separation in a π-Interacting Phenothiazine-Zinc Porphyrin-Fullerene Donor-Acceptor Conjugate.

We have designed, synthesized, and characterized a donor-acceptor triad, SPS-PPY-C60, that consists of a π-interacting phenothiazine-linked porphyrin as a donor and sensitizer and fullerene as an acceptor to seek charge separation upon photoexcitation. The optical absorption spectrum revealed red-shifted Soret and Q-bands of porphyrin due to charge transfer-type interactions involving the two ethynyl bridges carrying electron-rich and electron-poor substituents. The redox properties suggested that the phenothiazine-porphyrin part of the molecule is easier to oxidize and the fullerene part is easier to reduce. DFT calculations supported the redox properties wherein the electron density of the highest molecular orbital (HOMO) was distributed over the donor phenothiazine-porphyrin entity while the lowest unoccupied molecular orbital (LUMO) was distributed over the fullerene acceptor. TD-DFT studies suggested the involvement of both the S2 and S1 states in the charge transfer process. The steady-state emission spectrum, when excited either at porphyrin Soret or visible band absorption maxima, revealed quenched emission both in nonpolar and polar solvents, suggesting the occurrence of excited state events. Finally, femtosecond transient absorption spectral studies were performed to witness the charge separation by utilizing solvents of different polarities. The transient data was further analyzed by GloTarAn by fitting the data with appropriate models to describe photochemical events. From this, the average lifetime of the charge-separated state calculated was found to be 169 ps in benzonitrile, 319 ps in dichlorobenzene, 1.7 ns in toluene for Soret band excitation, and ∼320 ps for Q-band excitation in benzonitrile.

Phenothiazine functionalized fulleropyrrolidines: synthesis, charge transport and applications to organic solar cells.

A series of phenothiazine-C60/70 dyads containing fulleropyrrolidine tethered to C-3 position (C60-PTZ and C70-PTZ) or to the heteroatom N-position via either phenyl (C60-Ph-PTZ and C70-Ph-PTZ) or phenoxyethyl linkers (C60-PhOEt-PTZ and C70-PhOEt-PTZ) of the phenothiazine were synthesized and light-induced electron transfer events were explored. Optimized studies suggested that the highest molecular orbital (HOMO) resides on donor phenothiazine moiety while lowest molecular orbital (LUMO) on the acceptor fulleropyrrolidine moiety of the dyads. Optical and electrochemical properties suggested no electronic communication between the donor and acceptor moieties in the ground state. However, steady-state emission studies in solvents of varied polarity, involving selective excitation of C60/C70, disclosed that the emission intensity of C60/C70 was quenched in the dyads in the increasing order, C60/70-PTZ > C60/70-Ph-PTZ > C60/70-PhOEt-PTZ as a consequence of the donor-acceptor distance resulted due to spacer lengths. Also, the emission quenching is more pronounced in polar solvents such as DMF compared to a non-polar solvent, toluene. With the support of parallel electrochemical studies, the emission quenching is attributed to intramolecular photo-induced electron transfer occurring from PTZ to (C60/C70)* generating a radical ion pair, PTZ+⋅-C60-⋅/PTZ+⋅-C70-⋅. Finally, bulk heterojunction (BHJ) solar cells devices inverted fashion prepared by employing the dyads as acceptors, and PTB7 as donor, suggested that the devices prepared from C70 derivatives i.e., PTB7:C70-PTZ and PTB7:C70-PhOEt-PTZ exhibited better power conversion efficiency of 2.66% and 2.15%, respectively over C60 derivatives i.e., PTB7:C60-PTZ and PTB7:C60-PhOEt-PTZ with the efficiencies of 1.80 and 1.72%, respectively. AFM studies revealed that the poor performance of PTB7:C60-PTZ- and PTB7:C60-PhOEt-PTZ-based devices can be ascribed to the lower solubility of the dyads in 1,2-DCB solvent leading to rough morphology.

[1]Benzothieno[3,2-b][1]benzothiophene-based dyes: effect of the ancillary moiety on mechanochromism and aggregation-induced emission.

It is an established fact that [1]benzothieno[3,2-b][1]benzothiophene (BTBT) is a champion molecule for high-mobility OFET devices. Recently, it has also been utilized in dye-sensitized solar cells (DSSCs) and organic photovoltaics (OPVs) as an alternative to fullerene (non-fullerene acceptor). Considering the advantageous features of BTBT, we herein report its aggregation-induced emission (AIE) and mechanofluorochromic (MFC) behaviour for the first time. We have designed and synthesized two new BTBT derivatives: [1]benzothieno[3,2-b][1]benzothiophene-tetraphenylethylene (BTBT-TPE) and [1]benzothieno[3,2-b][1]benzothiophene-phenyl-N,N-dimethylamine (BTBT-NMe). The donor-π-acceptor-π-donor-integrated BTBT-TPE showed AIE whereas BTBT-NMe showed aggregation-caused quenching (ACQ), as evident by their quantum yield and lifetime results. BTBT-NMe was found to possess great interaction, resulting in the halochromic (protonation) effect. The theoretical calculation of the electronic distribution and energy investigation were consistent with the experimental outcomes. The electron contribution of the HOMO is high for BTBT-NMe at the donor, which can be attributed to the weaker donating nature of TPE compared to that of the NMe group. Overall, the results indicate the potential of the mechanical stimuli and aggregation response of the studied compounds for further investigation.

Selection of healthcare waste disposal firms using a multi-method approach.

The aim of this study is to propose a hybrid multi criteria decision making model with a linear programming (LP) model to tackle the issue of safe disposal of hazardous and infectious healthcare waste. For this, ten criteria in this study have been identified from literature and field surveys which are modelled using Decision making trial and evaluation (DEMATEL) and Analytic network process (ANP) methods to select the best disposal firm i.e. single sourcing for a hospital. We found that Experience of the firm, Technology for disposal, and Waste collection infrastructure acts as the most vital criteria in selecting a healthcare waste disposal firm for single sourcing. Furthermore, to optimize the total value of disposal and mitigating the risk involved in disposing waste through single sourcing; the LP model considering constraints such as waste lose constraint and waste processing constraint etc. Is solved for multiple sourcing using Lingo 18.0. The solution to LP results into allocation of 500, 500, and 1000 (kg/day) disposables to healthcare waste disposal firms D1, D2 and D3, respectively. The multi-method approach proposed in this study helps the hospital management in selecting economically, socially, and environmentally sustainable healthcare waste disposal firm.

Near-Infrared (>1000†nm) Light-Harvesters: Design, Synthesis and Applications.

Organic molecules can absorb or emit light in UV, visible and infra-red (IR) region of solar radiation. Fifty percent of energy of solar radiation lies in the IR region of solar spectrum and extended π-conjugated molecules containing low optical band gap can absorb NIR radiations. Recently IR molecules have grabbed the attention of synthetic chemists. Although only few molecules have been reported so far such as derivative of BODIPY, naphthalimide, porphyrins, perylene, BBT etc., they have shown highest absorbing capacity towards greater than 1100 nm. These compounds have potential applications in different fields, such as for biomedical and optoelectronic applications. In this review, we present different classes of light-harvesters with harvesting range above 1000 nm.

Lead-Free, Water-Stable A3 Bi2 I9 Perovskites: Crystal Growth and Blue-Emitting Quantum Dots [A=CH3 NH3 + , Cs+ , and (Rb0.05 Cs2.95 )+ ].

Despite the great success in the increase in the power conversion efficiency of lead halide perovskite solar cells, the toxicity of lead and the unstable nature of the materials are still major concerns for their wider implementation at the industrial level. Herein, large-size single crystals (SCs) are developed in HI solution by using a temperature lowering method and nanocrystals (NCs) of A3 Bi2 I9 perovskites [where A=CH3 NH3 + (MA)+ , Cs+ , and (Rb0.05 Cs2.95 )+ ] are formed in ethanol (EtOH) and toluene (TOL). The stability of A3 Bi2 I9 perovskite is investigated by immersing the SCs for 24 h and pellets for 12 h in water. Moreover, the A3 Bi2 I9 perovskite NCs displays a promising photoluminescence quantum yield of 17.63 % and a long lifetime of 8.20 ns.

Lead-halides Perovskite Visible Light Photoredox Catalysts for Organic Synthesis.

Lead-halide perovskites has grabbed great attention in recent years due to its unique photophysical and electrical properties. It has open new window in organic solar cell application for commercial point. Research has extended its application further towards visible light photoredox catalysts for organic synthesis. Due to intrinsic redox properties, sharp absorption and emissions patterns makes lead-halide perovskites as promising photoredox catalyst. In the presence of light, perovskite absorbs light, generates electrons/holes, which can reduce or oxidize species at reactive centres of organic molecule, leads to organic transformation. Lead-halide perovskites are used as heterogeneous catalysts for small molecules activations like CO, CH4 and NO, also suitable photocatalysts for organic bond formations, oxidations, reductions, polymerizations and dimerization transformations. Recent literatures have set another milestone for perovskite materials in organic synthesis. This review provides information on lead-halides perovskite in visible-light photoredox catalysis such as C-C, C-X (X-halo, hetero atom) bond formations C-H arylation.

Spoof surface plasmonic transmission line with high isolation and low propagation loss.

A novel compact spoof surface plasmonic (SSP) transmission line (TL) consisting of a stem-shaped periodic structure is proposed to achieve high field confinement in the higher frequency range (microwave to terahertz). The dispersion characteristic of the proposed stem-shaped SSP unit cell exhibits much lower asymptotic frequency and higher field confinement than the conventional coplanar waveguide (CPW) and the rectangular SSP unit cell structure without increasing the overall transverse dimension, i.e., improved signal propagation performance with reduced cross-sectional area. The numerical study of the multi-conductor line based on the proposed stem-shaped SSP unit cell shows that it has improved propagation and isolation features in comparison to the conventional TL structures. Here, the improved isolation is characterized in terms of the mutual coupling (MC) between the two adjacent lines designed using the stem-shaped SSP unit cell, which is not found to significantly increase with an increase in the coupling length unlikely in the conventional TLs. For the proposed SSP-based multi-conductor line, the MCs for 1.6, 2.25, and 4.15λ coupling lengths with fixed separation of 0.175λ are found to be 22, -19.8, and -17.55dB, respectively.

Impact of A-D-A-Structured Dithienosilole- and Phenoxazine-Based Small Molecular Material for Bulk Heterojunction and Dopant-Free Perovskite Solar Cells.

Herein, the synthesis of the novel acceptor-donor-acceptor (A-D-A)-structured small molecule Si-PO-2CN based on dithienosilole (DTS) as building block flanked by electron-rich phenoxazine (POZ) units, which are terminated with dicyanovinylene, is presented. Si-PO-2CN showed unique electrochemical and photophysical properties and has been successfully employed in perovskite solar cells (PSCs) as well as in bulk heterojunction organic solar cells (OSCs). The PSCs fabricated with dopant-free Si-PO-2CN as hole-transport material (HTM) exhibited a power conversion efficiency (PCE) of 14.1 % (active area=1.02 cm2 ). Additionally, a PCE of 5.6 % has been achieved for OSCs, which employed Si-PO-2CN as p-type donor material when blended with a [6,6]-phenyl C71 butyric acid methyl ester (PC71 BM) acceptor. The versatile application of Si-PO-2CN provides a pathway for further implementation of DTS-based building blocks in solar cells for designing new molecules.

Ni-Doped CsPbBr3 Perovskite: Synthesis of Highly Stable Nanocubes.

A nanocube of Ni-doped CsPbBr3nanocrystals (NCs) has been successfully synthesized and characterized by various spectroscopy techniques such as High-resolution transmission electron microscopy (HR-TEM), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), etc. The optoelectronic properties of NCs have been investigated with different solvents. HR-TEM and FE-SEM reveal that the obtained Ni-doped CsPbBr3NCs exhibit cubic-rectangular morphologies with different sizes. Furthermore, the radiative exciton kinetics of NCs was examined using the time-correlated single photon counting (TCSPC) technique. The present study ravels that synthesized nanocubes are highly stable.

Reactions in Water - A Greener Approach Using Ruthenium Catalysts.

Reactions using transition metals as catalysts have emerged as an efficient method in the recent times. However, the selection of solvent plays a crucial role in this regard. Several solvents used traditionally suffer majorly with problems of toxicity; high boiling point etc. leading to drastic reaction conditions. Water being a non-toxic, non-inflammable and environmentally benign can replace the hazardous organic solvents in laboratory as well as industry. Maintaining a minimum catalyst loading percentage we can advantageously avail high levels of selectivity. Water was found to be a good solvent medium for several metal catalysed reactions. An intramolecular deprotonation mechanism is followed by the ruthenium (II) catalysts in water; thereby, facilitating the catalytic action of the metal. These studies can help the industrial chemists to utilize water as a solvent for their reactions towards improvement of their waste management procedure. This review mainly focuses on the several recent developments in the above direction.

Simple diphenylamine based D-π-A type sensitizers/co-sensitizers for DSSCs: a comprehensive study on the impact of anchoring groups.

Herein, we report the design, synthesis and characterization of a new series of simple donor-π spacer-acceptor/anchor (D-π-A) type diphenylamine based metal-free organic dyes possessing three different anchoring groups, viz. 4-aminobenzoic acid (DTP), 2-(4-nitrophenyl)acetonitrile (DTN), and barbituric acid (DTB), connected with 2-(thiophene-2-yl)-acetonitrile, as effective sensitizers and co-sensitizers in Dye Sensitized Solar Cells (DSSCs). They were subjected to photophysical, electrochemical and theoretical studies. The dyes exhibited characteristic λabs and λemi in the range of 445-485 and 545-570 nm, respectively. Both optical and electrochemical band gaps were found to be in the range of 2.2 to 2.35 eV. The driving forces for injection (ΔGinj), recombination (ΔGrec) and regeneration (ΔGreg) processes were evaluated to understand their feasibility. Finally, the DSSC devices were fabricated employing the new dyes as sensitizers as well as co-sensitizers along with the Ru(ii) based N3 dye. Interestingly, DTP carrying 4-aminobenzoic acid as the anchoring group shows the best photoelectrochemical performance, viz. photovoltaic conversion efficiency (PCE) = 4.4%, open circuit potential (VOC) = 0.577 V, and short-circuit current density (JSC) = 9.06 mA cm-2 with a broad incident photon conversion efficiency (IPCE) spectrum. Co-sensitization of the dyes brought about enhanced VOC values, compared to the N3 dye alone. Finally, different interface resistance values obtained from the electrochemical impedance spectroscopy (EIS) circuit fitting were used to study the fundamental processes of energy conversion.

Solvent-Assisted Tuning of the Size and Shape of CsPbBr3 Nanocrystals via Redispersion Process at Ambient Condition.

All-inorganic CsPbBr3 perovskite nanocrystals are emerging as a new class of semiconductors with outstanding optoelectronic properties and great potential for various applications, such as, lasing, photon detection, photovoltaics, etc. This article provides the effect of solvents on the reprecipitation of CsPbBr3 perovskite at room temperature. The results observed for CsPbBr3 perovskite in various antisolvents showed various cubes (nano- to microsized), self-assembly of nanocubes and nanorods. In addition, all of the various sizes (nano to micro) of cubes and self-assembly of nanocubes and shape-controlled nanorods exhibited band gap tuning at the green light region. The corresponding microscopy (field emission scanning electron microscopy and high-resolution transmission electron microscopy) images and photoluminescence quantum yield as well as lifetime decay are presented. To the best of our literature knowledge, this is the first report on various solvent-assisted studies on CsPbBr3 perovskite nanocrystals.

Highly Directional 1D Supramolecular Assembly of New Diketopyrrolopyrrole-Based Gel for Organic Solar Cell Applications.

A new thermoreversible organogel based on diketopyrrolopyrrole dye (DPP-NCO) is reported for the first time and evolved as a new building block for the fabrication of 1D supramolecular assembly. AFM analysis illustrated that its gel state is composed of different sized 1D rods. DPP-NCO gel used as an additive in organic solar cells yields high efficiency of 7.9% owing to better nanophase separation of its active layer.

Near-infrared unsymmetrical blue and green squaraine sensitizers.

Two novel panchromatic asymmetrical squaraine sensitizers (SPSQ1 and SPSQ2) have been synthesized, characterized and effectively used for TiO2-based dye sensitized solar cells. In a solution, both dyes display a highly intense near-IR absorption (SPSQ1; 651 nm and SPSQ2; 692 nm), the red shifted absorption of SPSQ2 was attributed to the incorporation of the auxiliary acceptor dicyanovinyl unit on the squaraine moiety. Interestingly, the dicyanovinyl unit lowered the LUMO level of SPSQ2, which decreased the band gap and red shifted the absorption when compared to SPSQ1. These dyes possess suitable HOMO and LUMO levels to work as efficient sensitizers in DSSCs. The experimental trends in their optical and electrochemical properties are well matched with the theoretical calculations modeled by TDDFT. The blue and green color of the devices showed their complementary absorption and harvest a greater number of photons from solar flux. Under standard global AM 1.5 G solar conditions, the DSSC based on SPSQ2 exhibited a high power conversion efficiency of 3.1% with a high short circuit current density (JSC) attributed to the broadening of the IPCE spectra in the UV-vis and near-IR regions when compared to SPSQ1 (2.5%).

Synthesis and Spectroscopic Investigation of Diketopyrrolopyrrole - Spiropyran Dyad for Fluorescent Switch Application.

We report the synthesis and characterization of a new fluorescent dyad SP-DPP-SP(9) via efficient palladium-catalyzed Sonogashira coupling of prop-2-yn-1-yl 3-(3',3'dimethyl-6-nitrospiro[chromene-2,2'-indolin]-1'-yl)propanoatespiropyran, SP(8), a well known photochromic accepter, with 3,6-bis(5-bromothiophen-2-yl)-2,5-bis((R)-2-ethylhexyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione, DPP(4), a highly fluorescent donor. Under visible light exposure the SP unit is in a closed hydrophobic form, whereas under UV irradiation it converts to a polar, hydrophilic open form named Merocyanine (MC), which is responsible for functioning of photo-switch application. The photochemistry pertaining to fluorescence switch, 'on/off' behaviour, of model dyad SP-DPP-SP(9) is experimentally analyzed in solution as well as in solid state in polymer matrices by photoluminescence(PL) and absorption spectroscopy. After absorption of UV light the spiropyran unit of the dyad under goes the rupture of the spiro C-O bond leading to the formation of MC. The absorption band of MC fairly overlaps to the fluorescence of DPP unit resulting quenching of fluorescence via fluorescence resonance energy transfer from exited DPP unit to ground state MC. In contrary, the fluorescence of DPP is fully regained upon transformation of MC to SP by exposure to visible light or thermal stimuli. Hence, the fluorescence intensity of dyad 9 is regulated by reversible conversion among the two states of the photochromic spiropyran units and the fluorescence resonance energy transfer (FRET) between the MC form of SP and the DPP unit. Conversely, these scrutiny of the experiment express that the design of dyad 9 is viable as efficient fluorescent switch molecule in many probable commercial applications, such as, logic gates and photonic and optical communications.

Near-infrared squaraine co-sensitizer for high-efficiency dye-sensitized solar cells.

A combination of squaraine-based dyes (SPSQ1 and SPSQ2) and a ruthenium-based dye (N3) were chosen as co-sensitizers to construct efficient dye-sensitized solar cells. The co-sensitization of squaraine dyes with N3 enhanced their light-harvesting properties as a result of the broad spectral coverage in the region 350-800 nm. The co-sensitized solar cells based on SPSQ2 + N3 showed the highest short circuit current density of 17.10 mA cm(-2), an open circuit voltage of 0.66 V and a fill factor of 0.73, resulting in the highest power conversion efficiency of 8.2%, which is higher than that of the dye-sensitized solar cells based on the individual SPSQ1 and SPSQ2 dyes. The high power conversion efficiency of SPSQ2 + N3 was ascribed to its good light-harvesting properties, which resulted from its broader incident photon current conversion spectrum than that of the individual dyes. The high electron life time and electron recombination, which were the main causes of the higher efficiency of the device, were successfully analysed and correlated using transient absorption spectrometry and intensity-modulated photovoltage spectrometry.

An Organic Dyad Composed of Diathiafulvalene-Functionalized Diketopyrrolopyrrole-Fullerene for Single-Component High-Efficiency Organic Solar Cells.

A new low-band gap dyad DPP-Ful, which consists of covalently linked dithiafulvalene-functionalized diketopyrrolopyrrole as donor and fullerene (C60 ) as the acceptor, has been designed and synthesized. Organic solar cells were successfully constructed using the DPP-Ful dyad as an active layer. This system has a record power-conversion efficiency (PCE) of 2.2 %, which is the highest value when compared to reported single-component organic solar cells.

Osmium polypyridyl complexes and their applications to dye-sensitized solar cells.

Dye-sensitized solar cells (DSSCs) have received much attention in recent years owing to their efficient conversion of sunlight to electricity. DSSCs became successful alternatives to silicon photovoltaic devices by virtue of their low fabrication costs and easy preparation methods. In DSSCs the dye plays the key role. This review summarizes the applications of osmium sensitizers in DSSCs. We also briefly discussed their synthesis and the effect of various electrolyte systems on device efficiencies.

Carbon Dots: The Newest Member of the Carbon Nanomaterials Family.

Carbon nanomaterials have been extensively researched in the past few years owing to their interesting properties. The massive research efforts resulted in the emergence of carbon dots, which belong to the carbon nanomaterials family. Carbon dots (C-dots) have garnered the attention of researchers mainly due to their convenient availability from organic as well as inorganic materials and also due to the novel properties they exhibit. C-Dots have been said to overcome the era of quantum dots, referring to their levels of toxicity and biocompatibility. In this review, we focus on the discovery of C-dots, their structure and composition, surface passivation to enhance their optical properties, the various synthetic methods used, their applications in different areas, and future perspectives. Emphasis has been given to greener approaches for the synthesis of C-dots in order to make them cost effective as well as to improve their biocompatibility.