Full Solution Process of a Near-Infrared Light-Emitting Electrochemical Cell Based on Novel Emissive Ruthenium Complexes of 1,10-Phenanthroline-Derived Ligands and a Eutectic Alloy as the Top Electrode.

Near-infrared luminescent materials have recently received considerable attention for a large number of applications, including in solid-state lighting, as bioimaging agents, as photovoltaic cells, and in the telecommunication industry. By adding diverse electron-donating or withdrawing groups on ancillary ligands based on benzenethiol-phenanthroline, we synthesized and optoelectronically characterized a series of novel ionic ruthenium complexes, namely RuS, RuSCl, RuSMe, and RuSNH2, for using in a light-emitting electrochemical cell. The synthesized complexes are intense red emitters in the range of 584-605 nm in solution, which depends on the substitutions of electron donor/acceptor moieties on the ancillary ligands. To find a suitable quantum mechanical approach, benchmark calculations based on time-dependent density functional theory were carried out on these complexes. Our benchmark revealed that the M06-L method has results close to those of the experiment. Furthermore, to gain a deeper insight into electronic transitions, several excitation processes were investigated at the TD-DFT-SMD-MN12-L/gen level. The results showed that in the designed complexes, the dominant transition is between the 4dZ2 electron of Ru (particle) and the π* orbitals of the ancillary ligand (hole). The single-layer devices, including these complexes along with a Ga/In cathode by a facile deposition method without the addition of any electron or hole transport layers, were fabricated and displayed red (678 nm) to near-infrared (701 nm) emission as well as a decrease of turn-on voltage from 3.85 to 3.10 V. In particular, adding a methyl group to the ancillary ligand in the complex RuSNH2 increases the external quantum efficiency to 0.55%, one of the highest observed values in the ruthenium phenanthroline family. This simple structure of the device lets us develop the practical applications of light-emitting electrochemical cells based on injection and screen-printing methods, which are very promising for the vacuum-free deposition of top electrodes.

Two in One: A Dinuclear Ru(II) Complex for Deep-Red Light-Emitting Electrochemical Cells and as an Electrochemiluminescence Probe for Organophosphorus Pesticides.

The emissive properties of two Ru(II) complexes, [Ru(dmbipy)2L1][PF6]2 (1) and [Ru2(dmbipy)4L2][PF6]4 (2), (where L1 and L2 are π-extended phenanthroline-based ligands and dmbipy = 4,4'-dimethyl-2,2'-bipyridine) have been explored for dual applications, namely, deep-red light-emitting electrochemical cells (LECs) and electrochemiluminescence (ECL) sensors for the detection of organophosphorus pesticides (OPs) that include chlorpyrifos (CPS). A simple single-layer deep-red LEC device comprising 2 is reported that outperforms both its mononuclear derivative 1 and all previously reported dinuclear LECs, with a maximum brightness of 524 cd/m2, an external quantum efficiency of 0.62%, and a turn-on voltage of 3.2 V. Optoelectronic studies reveal that the ECL response of 2 is improved when compared to its mononuclear counterpart 1 and benchmark [Ru(bipy)3]2+ (3). Modified glassy carbon electrodes coated with 2 are highly sensitive deep-red ECL sensors that facilitate the detection of CPS directly from river water and fruit samples without any complex pretreatment steps, operating over a broad logarithmic concentration range, with a low detection limit.

Polypyridyl ligands as a versatile platform for solid-state light-emitting devices.

The replacement of inorganic semiconductors with molecule-based compounds for applications in current-to-light conversion has led to a significant increase in interdisciplinary collaborations worldwide, affording new improved organic-light emitting diodes (OLEDs) ripe for commercial applications, as well as light-emitting electrochemical cells (LECs) that have recently started to head to the market. This review highlights the role that transition metal coordination complexes (TMCs) have played in advancing the field of molecular electronics, from early conception to the advanced development of several polypyridyl complexes currently pursued for both OLED and LEC concepts. In this context, the design and synthesis of Ir(iii), Pt(ii), Cu(i) and Ag(i) complexes as the emissive components of OLEDs and LECs are thoughtfully presented. We discuss how molecular design is pivotal for fine-tuning color and optimizing power efficiencies, highlighting the key roles of the metal, cyclometalate, and ancillary polypyridyl ligands. We provide insight into the strategies exploited for the development of new, improved emitters and their fabrication into OLEDs/LECs with high external quantum efficiencies and stabilities. In addition, we have surveyed the remarkable photophysical properties of third generation TMCs capable of undergoing thermally activated delayed fluorescence (TADF). Since previous reviews of TADF materials are strongly biased towards organic-based systems, this overview compliments other synopses of light emitting TADF materials. Finally, we shed light onto the conceptual challenges that still need to be overcome to advance the rational design of TMC-based TADF emitters with tunable ligands and the subsequent fabrication of OLEDs/LECs, which are tailor-made for each specific application.

Influence of Ancillary Ligands in Dye-Sensitized Solar Cells.

Dye-sensitized solar cells (DSSCs) have motivated many researchers to develop various sensitizers with tailored properties involving anchoring and ancillary ligands. Ancillary ligands carry favorable light-harvesting abilities and are therefore crucial in determining the overall power conversion efficiencies. The use of ancillary ligands having aliphatic chains and/or π-extended aromatic units decreases charge recombination and permits the collection of a large fraction of sunlight. This review aims to provide insight into the relationship between ancillary ligand structure and DSSC properties, which can further guide the function-oriented design and synthesis of different sensitizers for DSSCs. This review outlines how the new and rapidly expanding class of chelating ancillary ligands bearing 2,2'-bipyridyl, 1,10-phenanthroline, carbene, dipyridylamine, pyridyl-benzimidazole, pyridyl-azolate, and other aromatic ligands provides a conduit for potentially enhancing the performance and stability of DSSCs. Finally, these classes of Ru polypyridyl complexes have gained increasing interest for feasible large-scale commercialization of DSSCs due to their more favorable light-harvesting abilities and long-term thermal and chemical stabilities compared with other conventional sensitizers. Therefore, the main idea is to inspire readers to explore new avenues in the design of new sensitizers for DSSCs based on different ancillary ligands.

Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation.

Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn(3+)/Mn(4+) ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states.

Improving the performance of perovskite solar cells by extending π-conjugation system.

In perovskite solar cells (PSCs), hole transporting materials (HTMs) play a critical role in determining the stability and efficiency of the devices. However, the high cost and complex synthesis processes associated with conventional HTMs can hinder their widespread applications. This work presents a low-cost and efficient HTM, namely N,N'-(naphthalene-1,5-diyl)bis(1-(dibenzo[a,c]phenazin-11-yl)-1-phenylmethanimine) (PEDN), based on a naphthalene core with an extended π-conjugation system for improving the performance of PSCs. The PEDN was synthesized via a facile two-step condensation method, eliminating the need for expensive catalysts such as BINAP. The newly developed HTM with an extended π-conjugation length was compared with BEDN and spiro-OMeTAD as the benchmark HTM, in terms of their optical, electrochemical, hole mobility properties, and efficiency in PSCs. The PEDN showed suitable highest occupied molecular orbital levels (HOMOs), good hole mobilities, as well as strong hydrophobicities. The extended π-conjugation system in PEDN contributes to the stability of the solar cells. The PSCs fabricated with PEDN achieved a high efficiency of 18.61%, comparable to the efficiency obtained using the commonly used HTM spiro-OMeTAD (19.68%). Furthermore, the cost-effectiveness of PEDN makes it a suitable alternative to spiro-OMeTAD for PSC applications.

Urinary bio-monitoring of aromatic amine derivatives by new needle trap device packed with the multi-component adsorbent.

Aromatic amines are a large group of chemical compounds that have attracted the attention of researchers due to their toxicity and carcinogenicity. This study aimed to develop an efficient method for sampling and analysis of aromatic amines (Aniline, N, N-dimethylaniline, 2-chloroaniline, and 3-chloroaniline) from the vapour phase (headspace) of urine samples. For the implementation of this plan, a needle trap device packed with the three-component adsorbent consisting of nano-Hydroxy Apatite (nHA), Zeolite (Ze), and Metal-Organic Framework (MOF) equipped with GC-FID was employed for the first phase. Examination of the prepared adsorbents was performed by FT-IR, PXRD, and FE-SEM techniques. The optimal value of considerable parameters such as time and temperature of extraction, salt content, and pH were established using the Response Surface Methodology-Central Composite Design (RMS-CCD) method. In this way, the optimal extraction of targeted analytes was accomplished in 41 min at 41 °C with NaCl content of 33.0% (w/v) and pH: 13.0, respectively. Also, the repeatability and reproducibility of the method were calculated to be in the range of 2.2-7.1% and 3.9-8.1%, respectively, which indicates the acceptable precision of the method. Also, the limit of detection (LOD) and limit of quantification (LOQ) were determined in the range of 0.3-32.0 ng.L-1 and 0.8-350.0 ng.L-1, respectively, which proves the high sensitivity of the proposed method. Furthermore, the recovery percent of the extracted analytes was concluded in the range of 97.0-99.0% after 6 and 30 days of the sampling and storage at 25 °C and 4 °C, respectively. Finally, the designed procedure was employed in the analysis of the above-mentioned aromatic amines in the real urine samples. The achieved results illustrate that the three-component absorbent system (nHA;Ze;MOF@NTD) can be introduced as an efficient, fast-response, sensitive, and versatile procedure for trace analysis of the different aromatic amine compounds in public and occupational health.

Molecularly engineered hole-transport material for low-cost perovskite solar cells.

Triphenylamine-N-phenyl-4-(phenyldiazenyl)aniline (TPA-AZO) is synthesized via a facile CuI-catalyzed reaction and used as a hole transport material (HTM) in perovskite solar cells (PSCs), as an alternative to the expensive spiro-type molecular materials, including commercial 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-OMeTAD). Experimental and computational investigations reveal that the highest occupied molecular orbital (HOMO) level of TPA-AZO is deeper than that of spiro-OMeTAD, and optimally matches with the conduction band of the perovskite light absorber. The use of TPA-AZO as a HTM results in PSC prototypes with a power conversion efficiency (PCE) approaching that of the spiro-OMeTAD-based reference device (17.86% vs. 19.07%). Moreover, the use of inexpensive starting reagents for the synthesis of TPA-AZO makes the latter a new affordable HTM for PSCs. In particular, the cost of 1 g of TPA-AZO ($22.76) is significantly lower compared to that of spiro-OMeTAD ($170-475). Overall, TPA-AZO-based HTMs are promising candidates for the implementation of viable PSCs in large-scale production.

Molecularly engineered electroplex emission for an efficient near-infrared light-emitting electrochemical cell (NIR-LEC).

Electroplex emission is rarely seen in ruthenium polypyridyl complexes, and there have been no reports from light-emitting electrochemical cells (LECs) to date. Here, for the first time, near-infrared (NIR) emission via the electroplex mechanism in a LEC based on a new blend of ruthenium polypyridyl complexes is described. The key factor in the design of the new complexes is the 0.4 V decrease in the oxidation half-potential of Ru(ii)/Ru(iii) in [Ru(DPCO)(bpy)2]ClO4 (DPCO = diphenylcarbazone, bpy = 2,2 bipyridine), which is about one-third of the value for benchmark [Ru(bpy)3](ClO4)2, as well as the long lifetime of excited states of 350-450 ns. The LEC based on the new blend with a narrow band gap (≈1.0 eV) of a Ru(DPCO) complex and Ru(bpy)3 2+ can produce an electroluminescence spectrum centred at about 700 nm, which extends to the NIR region with a high external quantum efficiency (EQE) of 0.93% at a very low turn-on voltage of 2.6 V. In particular, the very simple LEC structure was constructed from indium tin oxide (anode)/Ru(DPCO):Ru(bpy)3 2+/Ga:In (cathode), avoiding any polymer or transporting materials, as well as replacing Al or Au by a molten alloy cathode. This system has promising applications in the production of LECs via microcontact or inkjet printing.

On how ancillary ligand substitution affects the charge carrier dynamics in dye-sensitized solar cells.

With respect to N3, a champion sensitizer in dye-sensitized solar cells (DSSCs), S3 which contained a phenTz (1,10-phenanthroline 5-tetrazole) ancillary ligand showed outstanding improvements in molar extinction coefficient (ε) from 10 681.8 to 12 954.5 M cm-1 as well as 0.92% and 0.9% increases in power conversion efficiency (PCE) and incident photon-to-electron conversion efficiency (IPCE), reaching 8.46% and 76.5%, respectively. To find the origin of the high performance of the DSSC based on a phenTz ancillary ligand, transient absorption spectroscopy (TA) was carried out and indicated that the rate of the regeneration reaction is about 100 times faster than the rate of recombination with the dye which is very exciting and surely a good reason to promote the phenTz ligand as a promising ancillary ligand in DSSCs.

Low-Turn-On-Voltage, High-Brightness, and Deep-Red Light-Emitting Electrochemical Cell Based on a New Blend of [Ru(bpy)3]2+ and Zn-Diphenylcarbazone.

Deep red light-emitting electrochemical cells were prepared based on a blend of [Ru(bpy)3]2+, a cationic complex, and a neutral Zn(II)-complex based on diphenylcarbazone ligands, named Zn(DPCO). The crystal structure of the Zn(DPCO)2 (bpy)] molecule revealed that the DPCO ligand has been deprotonated to form DPCO- and coordinated to the Zn center metal through the C=O and N=N moieties of DPCO. From the cyclic voltammetry results and controlled potential coulometry data of the diphenylcarbazide (DPC) ligand, it is possible to establish that DPC is oxidized in an irreversible process at +0.77 V, giving DPCO and later oxidized at a higher potential (+1.32 V) to produce diphenylcarbadiazone (DPCDO). A detailed assignment of UV-vis spectra futures to determine the origin of ground- and excited-state transitions was achieved by time-dependent density functional theory calculations, which showed good agreement with the experimental results. Using a simple device architecture, we obtained deep red electroluminescence (EL) with high brightness (740 cd m-2) and luminous efficiency of 0.39 cd/A at a low turn-on voltage of 2.5 V. The favorable configuration of the cell consists of only a blend of complexes of indium tin oxide as the anode electrode and molten alloy cathode (Ga/In) without any polymer as the transporting layer. The comparison between [Ru(bpy)3]2+ and [Ru(bpy)3]2+/Zn(DPCO) demonstrates a red shift in the EL wavelength from 625 to 700 nm in the presence of Zn(DPCO), revealing the importance of using blends for future systems.

A ruthenium tetrazole complex-based high efficiency near infrared light electrochemical cell.

We report on the exploitation of a new tetrazole-substituted 1,10-phenanthroline and a 2,2'-bipyridine (bpy) ancillary ligand modified with an electron-donating group in cationic ruthenium complexes. This complex, placed in between two electrodes without any polymer, demonstrates high efficiency near-infrared (NIR) electroluminescence (EL). The comparison between bpy and its methyl-substituted ancillary ligand shows that the cationic Ru tetrazolate complex containing methyl groups exhibits a red shift in the EL wavelength from 620 to 800 nm compared to [Ru(bpy)3]2+ and an almost twofold reduction in the turn-on voltage, i.e., from 5 to 3 V, with respect to 5-tetrazole-1,10-phenanthroline. An external quantum efficiency of 0.95% for the dimethyl derivative is demonstrated, which is a remarkable result for non-doped NIR light electrochemical cells based on ruthenium polypyridyl.

Photodamage of the manganese-calcium oxide: a model for UV-induced photodamage of the water oxidizing complex in photosystem II.

The Mn-Ca cluster is proposed to play an important role in the ultraviolet (UV) photoinhibition of photosystem II, but the mechanism is still unknown. Here, we used Mn-Ca oxide as an important structural and functional model for the Mn-Ca cluster in photosystem II, and report the effect of UV radiation on the decomposition of the structure in the presence of organic groups. Our results show similarities between the reactions of the Mn-Ca oxide and the WOC of PSII in the presence of UV radiation.

Nanoscale manganese oxide within Faujasite zeolite as an efficient and biomimetic water oxidizing catalyst.

Nanoscale manganese oxides within Faujasite zeolite have been synthesized with a simple method and characterized by scanning electron microscopy, X-ray diffraction spectrometry, N(2) adsorption-desorption isotherms, transmission electron microscopy, and atomic absorption spectroscopy. These oxides showed efficient water oxidizing activity in the presence of cerium(IV) ammonium nitrate as a non-oxo transfer oxidant.

Calcium manganese(IV) oxides: biomimetic and efficient catalysts for water oxidation.

CaMnO(3) and Ca(2)Mn(3)O(8) were synthesized and characterized by SEM, XRD, FTIR and BET. Both oxides showed oxygen evolution activity in the presence of oxone, cerium(IV) ammonium nitrate and H(2)O(2). Oxygen evolution from water during irradiation with visible light (λ > 400 nm) was also observed upon adding these manganese oxides to an aqueous solution containing tris(2,2'-bipyridyl) ruthenium(II), as photosensitizer, and chloro pentaammine cobalt(III) chloride, as electron acceptor, in an acetate buffer. The amounts of dissolved manganese and calcium from CaMnO(3) and Ca(2)Mn(3)O(8) in the oxygen evolving reactions were reported and compared with other (calcium) manganese oxides. Proposed mechanisms of oxygen evolution and proposed roles for the calcium ions are also considered.

Nano-sized layered aluminium or zinc-manganese oxides as efficient water oxidizing catalysts.

Nano-sized layered aluminium or zinc-manganese oxides were synthesized and characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction spectrometry, dynamic light scattering and atomic absorption spectroscopy. These oxides showed efficient water oxidizing activity in the presence of cerium(IV) ammonium nitrate as a non-oxo transfer oxidant. Amounts of dissolved manganese, zinc or aluminium, and water oxidation activities of these oxides were reported and compared with other manganese oxides. A mechanism for oxygen evolution and possible roles for zinc or aluminium ions are also proposed.

Nano-size amorphous calcium-manganese oxide as an efficient and biomimetic water oxidizing catalyst for artificial photosynthesis: back to manganese.

A nano-size amorphous calcium-manganese oxide shows efficient water oxidation activity in the presence of cerium(IV) ammonium nitrate.