Mixed Ligand System Research Articles

Influence of Metal Ions on the Structural Complexity of Mixed-Ligand Divalent Coordination Polymers

The reactions of the angular ligand 4,4′-oxybis(N-(pyridin-3-yl)benzamide) (L1) and 1,4-naphthalenedicarboxylic acid (1,4-H2NDC) with divalent metal salts yielded three distinct coordination polymers (CPs): {[Zn2(L1)(1,4-NDC)2]·MeOH}n, 1, {[Cu(L1)(1,4-NDC)(H2O)]·3H2O}n, 2, and {[Cd(L1)(1,4-NDC)]·2H2O}n, 3. Complex 1 features a 2-fold interpenetrated 3D framework with the (412·63)-pcu topology, while complex 2 reveals a 1D triple-strained helical chain and complex 3 displays a 3-fold interpenetrated 3D framework with (66)-dia topology. Additionally, the reactions of the flexible ligand N,N′-bis(3-methylpyridyl) adipoamide (L2) afforded {[Co4(L2)0.5(1,4-NDC)3(H2O)3(µ3-OH)2]·EtOH·2H2O}n, 4, {[Zn2(L2)(1,4-NDC)2]·2CH3OH}n, 5, and [Cd(L2)(adipic)(H2O)]n (H2adipic = adipic acid), 6, exhibiting a self-catenated 3D framework with the (420·68)-8T32 topology, a 2D layer with the (413·62) − (4,4)IIb topology, and a 2D layer with the (44·62)-sql topology, respectively. The structural diversity observed in complexes 1–6 highlights the pivotal influence of the metal center on the degree of entanglement in CPs within mixed-ligand systems. The thermal stability and luminescent properties of complexes 1–3, 4, and 6 are also discussed.

Ligand substitution as a strategy to tailor cationic conductivity in all-solid-state batteries

An increased electrification of society calls for a revolution of battery technologies to further improve energy densities, safety and reduce dependencies on critical raw materials. Here we present a new type of fast magnesium electrolytes for all solid-state batteries created as solid solutions of two other fast Mg2+ ionic conductors, Mg(BH4)2 ∙ NH3 and Mg(BH4)2 ∙ CH3NH2. However, the different ligands introduce stacking faults in the structures of the solid solutions, which are eliminated upon heating to T > 40 °C. The stacking faults appear to influence ionic conductivity, as the samples are less conductive after heating. Interestingly, the ionic conductivity does not correlate directly with the relative ligand content, as the highest conductivity is observed for the 1:1 molar composition (σ(Mg2+) = 7.3 ∙ 10−6 S cm−1 at 40 °C), which also has the lowest melting point of 60 °C. Thus, this work demonstrates a new approach to increase cationic conductivity using mixed ligand systems to alter conduction pathways and introduce microstructural strain.

Copper (II) complexes based on the mixed ligand system: Study of synthesis, characterization, and stopped‐flow kinetics of copper oxidase‐mimicking catalytic activity

Two copper (II) complexes based on the mixed ligand system were synthesized and structurally characterized. The molecular formulae for complex (1), [Cu2L1L′] and complex (2), [CuL2L′] were determined based on analytical data, molar conductance, and thermal analysis results. The optimized structures of complexes (1) and (2) were determined by magnetic and spectroscopic measurements (FTIR, UV–Vis, and ESR) and confirmed by processing powder X‐ray diffraction data by Expo 2014 software. The geometry index (τ5), determined by ESR spectra and structural analysis based on powder X‐ray, demonstrates the square pyramidal geometry of the Cu (II) center of [Cu2L1L′] and [CuL2L′]. Cyclic voltammetry measurements were performed to elucidate the relationship between the redox properties of (1) and (2) and their oxidase‐mimicking catalytic activity. Catalytic aerobic oxidation of the polyphenols 3,5‐di‐tert‐butylcatechol (3,5‐DTBCH2), 4‐nitrocatechol, and 2‐aminophenol (2‐APH3) was studied by stopped‐flow technique. Promising catechol oxidase (COX) and phenoxazinone synthase (PHS) mimetic activity have been demonstrated for (1) and (2). Electrochemical data were used to determine the free energy (ΔG°) or driving force (−λ), and their correlation with the oxidase mimetic activity of(1) and (2) was examined. Several experimental procedures have been performed that have helped describe the catalytic mechanisms of the catalytic reactions taking place.

A Versatile Microfluidic Platform for Extravasation Studies Based on DNA Origami-Cell Interactions.

The adhesion of circulating tumor cells (CTCs) to the endothelial lumen and their extravasation to surrounding tissues are crucial in the seeding of metastases and remain the most complex events of the metastatic cascade to study. Integrins expressed on CTCs are major regulators of the extravasation process. This knowledge is primarily derived from animal models and biomimetic systems based on artificial endothelial layers, but these methods have ethical or technical limitations. We present a versatile microfluidic device to study cancer cell extravasation that mimics the endothelial barrier by using a porous membrane functionalized with DNA origami nanostructures (DONs) that display nanoscale patterns of adhesion peptides to circulating cancer cells. The device simulates physiological flow conditions and allows direct visualization of cell transmigration through microchannel pores using 3D confocal imaging. Using this system, we studied integrin-specific adhesion in the absence of other adhesive events. Specifically, we show that the transmigration ability of the metastatic cancer cell line MDA-MB-231 is influenced by the type, distance, and density of adhesion peptides present on the DONs. Furthermore, studies with mixed ligand systems indicate that integrins binding to RGD (arginine-glycine-aspartic acid) and IDS (isoleucine-aspartic acid-serine) did not synergistically enhance the extravasation process of MDA-MB-231 cells.

A Versatile Microfluidic Platform for Extravasation Studies Based on DNA Origami—Cell Interactions

AbstractThe adhesion of circulating tumor cells (CTCs) to the endothelial lumen and their extravasation to surrounding tissues are crucial in the seeding of metastases and remain the most complex events of the metastatic cascade to study. Integrins expressed on CTCs are major regulators of the extravasation process. This knowledge is primarily derived from animal models and biomimetic systems based on artificial endothelial layers, but these methods have ethical or technical limitations. We present a versatile microfluidic device to study cancer cell extravasation that mimics the endothelial barrier by using a porous membrane functionalized with DNA origami nanostructures (DONs) that display nanoscale patterns of adhesion peptides to circulating cancer cells. The device simulates physiological flow conditions and allows direct visualization of cell transmigration through microchannel pores using 3D confocal imaging. Using this system, we studied integrin‐specific adhesion in the absence of other adhesive events. Specifically, we show that the transmigration ability of the metastatic cancer cell line MDA‐MB‐231 is influenced by the type, distance, and density of adhesion peptides present on the DONs. Furthermore, studies with mixed ligand systems indicate that integrins binding to RGD (arginine‐glycine‐aspartic acid) and IDS (isoleucine‐aspartic acid‐serine) did not synergistically enhance the extravasation process of MDA‐MB‐231 cells.

Synthesis and structural characterization of nickel(II) coordination complexes with mixed-ligand systems: exploring π−π stacking and hydrogen bonding in supramolecular assemblies

Synthesis and structural characterization of nickel(II) coordination complexes with mixed-ligand systems: exploring π−π stacking and hydrogen bonding in supramolecular assemblies

Revolutionizing Wastewater Treatment: Harnessing Metal–Organic Frameworks for Exceptional Photocatalytic Degradation of Azo-Type Dyes

Due to the high stability of azo-type dyes, conventional treatment processes such as adsorption, flocculation, and activated sludge are not efficient for decolorizing wastewater effluents. An alternative to traditional wastewater treatment is photocatalysis, which has gained significant interest because research has shown it to be a viable and cost-effective process that uses sunlight as an inexhaustible energy source. In heterogeneous photocatalysis, a photocatalyst is required, such as TiO2, ZnO, composite materials, and, more recently, metal–organic frameworks (MOFs). MOFs, also known as “coordination polymers”, exhibit photocatalytic properties and have been proven to be promising materials in the photocatalytic degradation of dyes. This study presents recent advances in using MOFs as photocatalysts to degrade recalcitrant contaminants like azo-type dyes. Recent advancements in developing photocatalysts based on MOFs are focused on two strategies. Firstly, the development of new MOFs composed of complex ligands or a mixed ligand system, and secondly, the synthesis of composite materials based on MOFs and metal oxides, metals, sulfides, nitrides, etc. Both strategies have significantly contributed to the search for new semiconductors to degrade some recalcitrate contaminants in wastewater.

Density Functional Theory Study of Synergistic Gas Sensing Using an Electrically Conductive Mixed Ligand Two-Dimensional Metal-Organic Framework.

Two-dimensional conductive metal-organic frameworks (2D-cMOFs) have been adopted in electrochemical sensing applications owing to their superior electrical conductivity and large surface area. Here, we performed a density functional theory (DFT) analysis to study the synergistic impact of introducing a secondary organic ligand to the 2D-cMOF system. In this study, cobalt-hexaiminobenzene (Co-HIB) and cobalt-2,3,6,7,10,11-hexaiminotriphenylene (Co-HITP) were combined to form a mixed ligand MOF named, Co-HIB-HITP. A DFT-level comparative study was designed to access stability, synergistic gas adsorption capability, and gas adsorption mechanism, important factors in sensing material development. A potential energy surface calculation predicted the structural stability of Co-HIB-HITP at larger interlayer displacements around 3.6-4.2 Å regions along the ab-plane than its unmixed states, Co-HIB and Co-HITP, indicating the tunability of the stacking mode using the mixed ligand system. Furthermore, the adsorption capabilities toward toxic gases, NH3, H2S, NO, and NO2, were investigated, and Co-HIB-HITP revealed superiority over unmixed 2D-cMOFs in H2S and NH3 gas adsorption energies by showing 158 and 170% improvement, respectively. Finally, an electron charge density analysis revealed Co-HIB-HITP's unique stacking mode and Co-metal density as contributing factors to its gas-selective synergy effect. The AB stacked layers and an intermediate metal density (5.25%) significantly improved the electrostatic interactions with H2S and NH3 by inducing a change in the chemical environment of the gas binding sites. This work proposes the dual-ligand 2D-cMOF as the promising design strategy for the next-generation sensing material.

Self-organization of metallo-supramolecular polymer networks by free formation of pyridine-phenanthroline heteroleptic complexes.

Nature employs spontaneous self-organization of supramolecular bonds to create complex matter capable of adaptation and self-healing. Accordingly, the self-sorting of unlike ligands towards a cooperative heteroleptic complex or narcistic homoleptic association in a mixed ligand system is frequently employed to form interchangeable stimuli-responsive complex geometries with a wide range of applications. This notion is however just rarely employed in the organization of polymer networks. In this paper, we report the free-formation of heteroleptic complexes between tetra-am poly(ethylene glycol) (tetraPEG) precursors functionalized either with pyridine (tetraPy) or phenanthroline (tetraEPhen). Among a wide range of studied metal ions, tetraPy could form a network only in combination with Pd2+, presumably with a square-planar geometry, highlighting the importance of complex strength and stability in forming gels with monodentate ligands. Also, mixed networks with tetraEPhen form only in combination with Pd2+ and Fe2+, with strengths surpassing those of individual components and stabilities incomparable to those of parent networks, indicative of heteroleptic complexation. Extensive rheological, UV-vis, and DFT simulation studies revealed the coexistence of different coordination geometries, with an octahedral arrangement prevailing in the presence of Fe2+ and a square-planar geometry in the presence of Pd2+. Therefore, this study offers new opportunities for the development of stimuli-responsive topology-switching polymer networks.

On the importance of π-stacking interactions in the complexes of copper and zinc bearing pyridine-2,6-dicarboxylic acid N-oxide and N-donor auxiliary ligands

Using N- and O-donor ligands in a mixed-ligand system, three new coordination complexes have been X-ray characterized, exhibiting strong π–π stacking interactions.

From a Well-Defined Organozinc Precursor to Diverse Luminescent Coordination Polymers Based on Zn(II)-Quinolinate Building Units Interconnected by Mixed Ligand Systems.

Introduction of photoactive building blocks into mixed-ligand coordination polymers appears to be a promising way to produce new advanced luminescent materials. However, rational design and self-assembly of the multi-component supramolecular systems is challenging from both a conceptual and synthetic perspective. Here, we report exploratory studies that investigate the potential of [Zn(q)2]2[tBuZn(OH)]2 complex (q = deprotonated 8-hydroxyquinoline) as an organozinc precursor as well as a mixed-ligand synthetic strategy for the preparation of new luminescent coordination polymers (CPs). As a result we present three new 2D mixed-ligand Zn(II)-quinolinate coordination polymers which are based on various zinc quinolinate secondary building units interconnected by two different organic linker types, i.e., deprotonated 4,4′-oxybisbenzoic acid (H2obc) as a flexible dicarboxylate linker and/or selected bipyridines (bipy). Remarkably, using the title organozinc precursors in a combination with H2obc and 4,4′-bipyridine, a novel molecular zinc quinolinate building unit, [Zn4(q)6(bipy)2(obc)2], was obtained which self-assembled into a chain-type hydrogen-bonded network. The application of the organometallic precursor allowed for its direct reaction with the selected ligands at ambient temperature, avoiding the use of both solvothermal conditions and additional base reagents. In turn, the reaction involving Zn(NO3)2, as a classical inorganic precursor, in a combination with H2obc and bipy led to a novel 1D coordination polymer [Zn2(q)2(NO3)2(bipy)]. While the presence of H2obc was essential for the formation of this coordination polymer, this ditopic linker was not incorporated into the isolated product, which indicates its templating behavior. The reported compounds were characterized by single-crystal and powder X-ray diffraction, elemental analysis as well as UV-Vis and photoluminescence spectroscopy.

Little Adjustments Significantly Simplify the Gram-Scale Synthesis of High-Quality Iron Oxide Nanocubes.

This work presents a facile one-step protocol for the gram-scale synthesis of iron oxide nanocubes with adjustable sizes ranging from 13 to 20 nm and with size distributions between 7 and 12%. As X-ray diffraction indicated the initial formation of the wüstite phase, a formation mechanism of the nanocubes based on the wüstite crystal structure is proposed. When exposed to ambient conditions, the nanoparticles rapidly oxidize to magnetite/maghemite with a remaining wüstite core. The cubic morphology is attributed to the thermodynamic stability of the exposed {100} facets and the control over the growth rate via the use of a sodium oleate/oleic acid mixed ligand system. In contrast to previously reported procedures, the described synthetic approach does not require the initial preparation and isolation of iron oleate. Therefore, the amount of work and the consumption of hazardous solvents are significantly reduced. Thus, the method presented is much more efficient and environmentally more friendly while maintaining excellent control over the particles' shape, size, and size distribution.

Coupled Organic-Inorganic Nanostructures with Mixed Organic Linker Molecules.

The electronic properties of semiconducting inorganic lead sulfide (PbS) nanocrystals (NCs) and organic linker molecules are dependent on the size of NCs as well as the used ligands. Here, we demonstrate that a weakly binding ligand can be successfully attached to PbS NCs to form a coupled organic-inorganic nanostructure (COIN) by mixing with a strong binding partner. We use the weakly binding zinc β-tetraaminophthalocyanine (Zn4APc) in combination with the strongly binding 1,2-ethanedithiol (EDT) as a mixed ligand system and compare its structural, electronic, and (photo-)electrical properties with both single-ligand COINs. It is found that binding of Zn4APc is assisted by the presence of EDT leading to improved film homogeneity, lower trap density, and enhanced photocurrent of the derived devices. Thus, the mixing of ligands is a versatile tool to achieve COINs with improved performance.

Isolable 1-Butene Copper(I) Complexes and 1-Butene/Butane Separation Using Structurally Adaptable Copper Pyrazolates.

Non-porous small molecule adsorbents such as {[3,5-(CF3 )2 Pz]Cu}3 (where Pz=pyrazolate) are an emerging class of materials that display attractive features for ethene-ethane separation. This work examines the chemistry of fluorinated copper(I) pyrazolates {[3,5-(CF3 )2 Pz]Cu}3 and {[4-Br-3,5-(CF3 )2 Pz]Cu}3 with much larger 1-butene in both solution and solid state, and reports the isolation of rare 1-butene complexes of copper(I), {[3,5-(CF3 )2 Pz]Cu(H2 C=CHC2 H5 )}2 and {[4-Br-3,5-(CF3 )2 Pz]Cu(H2 C=CHC2 H5 )}2 and their structural, spectroscopic, and computational data. The copper-butene adduct formation in solution involves olefin-induced structural transformation of trinuclear copper(I) pyrazolates to dinuclear mixed-ligand systems. Remarkably, larger 1-butene is able to penetrate the dense solid material and to coordinate with copper(I) ions at high molar occupancy. A comparison to analogous ethene and propene complexes of copper(I) is also provided.

Exploring the electrochemical properties of mixed ligand Fe(II) complexes as redox couples

Redox flow batteries are a promising technology for large scale energy storage systems. Although some types of the battery have been commercialized, the narrow working voltage ranges in the aqueous electrolytes limit their further applications. Organic solvents have shown to allow the use of a wider range of redox couples and the idea of non-aqueous redox flow batteries has been proposed. However, the low solubilities and poor electrochemical properties including stability and reversibility of the redox couples in the organic electrolytes remain a significant issue. In this work, a series of heteroleptic (mixed ligand) iron(II) complexes based on a combination of 2,2′-bipyridine, 1,10-phenanthroline and 4,4′-dimethyl-2,2′-bipyridine ligands were synthesized and their chemical and electrochemical properties investigated. For Fe (II) complexes, it was confirmed that ligand equilibration occurs in solution. The electrochemical properties of the complexes were studied by cyclic voltammogram and chronoamperometric methods. The mechanism of the redox processes of these complexes are proposed and how the mixed ligands will affect the redox potentials of the Fe (II) complexes is discussed. Furthermore, we show that the mixed ligand system can improve the total solubility of redox active species. The mixed ligand approach will also be beneficial for designing other new high solubility redox materials for non- aqueous flow batteries.

Coordination polymers driven by 2,5-dibromoterephthalic acid and chelating co-ligands: Syntheses, structures and luminescent properties

Four coordination polymers, namely, [Zn (DBT) (4,4′-dmbpy) (H2O)]n (1), [Co(DBT) (2,2′-bpy) (H2O)]n (2), [Zn (DBT) (2,2′-bpy)]n (3), [Zn (DBT)0.5 (2,2′-bpy)2·(HDBT−)]n (4) (H2DBT ​= ​2,5-dibromoterephthalic acid, 4,4′-dmbpy ​= ​4,4′-dimethyl-2,2′-bipyridyl and 2,2′-bpy ​= ​2,2′-bipyridyl) have been synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR and thermogravimetric (TG) analysis. These four compounds remained stable until 150 ​°C, and the major quality loss (83–90%) occurred between 150 and 700 ​°C. In mixed ligands system, the main ligand H2DBT exhibits monodentate or bidentate bridging coordination modes and the auxiliary ligands 4,4′-dmbpy and 2,2′-bpy both possess bidentate chelate coordination modes. An objective of this study was to investigate the pivotal role of chelating ligands in the formation of low dimensional structures. As the bipyridyl ligands occupy the coordination site, compounds 1–3 all display two dimensional structures and 4 shows 1D chains, of which compounds 1 and 2 are isomorphic. The hydrogen bonds and π-π stacking work together in the formation of 3D supramolecular structure of these four compounds. Besides, we investigated their photoluminescence properties in the solid state at room temperature. The compounds 1, 3 and 4 exhibited good fluorescence performance, and their strong emission peaks were located at 447 ​nm (λex ​= ​285 ​nm) for 1, 427 ​nm (λex ​= ​330 ​nm) for 3, and 412 ​nm (λex ​= ​310 ​nm) for 4.

Two New Entangled Zn and Cd Coordination Polymers Based on a Rich “Mix” Feature of the O- and N-Donor Ligand System: Synthesis, Structure, and Fluorescent Properties

A prominent mixed-ligand system with rich “mix” features, which are rigid multicarboxylate O-donor ligands cooperating with flexible bisazole N-donor linkers, is explored to coordinate with Zn2+/Cd2+ centers. Two new entangled coordination polymers ([Cd(Hbtc)(bbi)] (1) and [Zn(btec)0.5(dtp)]·5H2O (2)) are gained. Complex 1 exhibits a fascinating 3D (3,5)-connected net with a Schlafli symbol of the (63.610) topology, and 3D nets penetrate into each other to give rise to twofold interpenetrations. Complex 2 displays a 2D layer with similar 9.9×12.0 A2 hexagonal channels, the adjacent layers stacking with each other to form a 3D supramolecular structure. The effects and functions of the ligands in the complexes are discussed. Moreover, the thermal stabilities and fluorescence properties of complexes 1 and 2 are investigated.

A 2-Fold Interpenetrated Nitrogen-Rich Metal-Organic Framework for Rapid and Selective Adsorption of Congo Red.

A new metal-organic framework was prepared based on a mixed ligand system of the designed nitrogen-rich 3,6-bis(2-methylimidazole)pyrimidine (b2mpm) and benzophenone 4,4'-dicarboxylic acid (H2bpndc). The prepared material shows a three-dimensional 2-fold interpenetrated pcu framework and features rectangular channels decorated with nitrogen sites. Thanks to the abundant hydrogen bonding and π-π stacking interactions, the titled material can rapidly adsorb Congo red (CR) and presents ultrahigh adsorption capacity (2348 mg g-1). Moreover, this material has an adsorptive selectivity toward CR and can be regenerated by simply washing it with ethanol. The adsorption kinetic and isotherm of the titled material were also determined, indicating that the adsorption kinetic conforms to the pseudo-second-order model and the adsorption isotherm obeys the Langmuir model. Additionally, the titled material exhibits the suitable adsorption ability toward CO2 (15.2 cm3 g-1 under 1 atm at 298 K). These results demonstrate that the titled material would be an effective and easily regenerated adsorbent for CR removal from wastewater.

Functional wheat bread with calcium chelate complexes

Bakery products are promising objects for enrichment with functional food ingredients, as they are mass consumption products. The problem of hypo-elementosis in people makes it advisable to develop functional food ingredients based on easily digestible and safe forms of essential biometals, including calcium. In this study, it has been shown that wheat bread can be enriched with calcium chelate complexes. This functional food ingredient was obtained by complexation of Ca2+ with bioligands of probiotic origin, followed by immobilizing the complexes on dietary fiber of wheat bran. Mixed-ligand systems were obtained by combining a metabolite (lactic acid) and degradation products of peptidoglycans of Lactobacillus delbrueckii subsp. Bulgaricus B-3964. The peptidoglycans of the biomass autolysate were degraded by enzymatic hydrolysis with papain. This resulted in obtaining a mixture that contained amino acids, low molecular weight peptides, and muropeptides, in the concentrations 12.44 mg/cm3, 6.85 mg/cm3, and 2.76 mg/cm3, respectively. The nephelometric method has shown that this mixed-ligand system binds calcium ions in an amount of 18 mg/cm3. The soluble complexes obtained were immobilized on the dietary fiber to solve the problem of concentrating, drying, and dosing these ingredients. It has been proved that immobilization only occurs due to physical sorption that completely releases the active component from the dietary fiber matrix under conditions that simulate the gastrointestinal environment. The functional ingredient developed was added to the classic wheat bread recipe, where it replaced 1 %, 3 %, and 5 % of the flour. Bread was made without pre-fermentation to reduce the total production time and to prevent the ingredient’s biologically active components from being assimilated by yeast during long fermentation. The study of the experimental and control samples of wheat bread has shown that the introduction of chelate complexes of calcium immobilized on dietary fiber causes no deterioration of the physico-chemical parameters of the finished bread: they are all within the limits approved by the regulatory documentation. The sensory properties of the samples with 1 % and 3 % of flour replaced are close to those of the control sample. So 3 % of the ingredient is the recommended amount to be added, as it provides 98 % of the daily requirement of calcium as a functional ingredient and covers about 25 % of the daily allowance of dietary fiber.

C–H···π(metal–ligand ring) interaction in a mesaconate bridged Cd(II) 1-D coordination polymer: structural elucidation, theoretical study, and photophysical properties

A Cd(II)-based one-dimensional coordination polymer (1-D CP), [Cd2(mes)2(4-phpy)4] (1), was prepared using mesaconic acid (H2mes) and 4-phenyl pyridine (4-phpy) mixed ligand system. Compound 1 has been characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) pattern and single crystal X-ray diffraction (SCXRD) techniques. Structural elucidation reveals a 1-D chain which contains a 14-membered metal-ligand ring composed of two mes ligands and two Cd(II) centers. Further, the 1-D chains are assembled into a two-dimensional (2-D) supramolecular network by C–H···π(metal-ligand ring) interactions. The fluorescence lifetime of 1 shows a good range of average lifetime. The theoretical band gap has also been calculated by density functional theory (DFT) computations, which shows that 1 may possess semiconducting properties.