Studies on anticancer properties with varying co-ligands in a Ru(II) arene benzimidazole system.

Recently in the field of chemotherapeutics, to combat the side effects of cisplatin, ruthenium complexes have been investigated extensively. In this work, a bidentate benzimidazole-based ligand, HL [HL = 2-(1H-benzo[d]imidazol-2-yl)-6-methoxyphenol], was utilized to obtain three Ru(II) arene complexes having a generalized formula [Ru(η6-p-cym)(L)(X)] or [Ru(η6-p-cym)(L)(X)]+ (where p-cym = p-cymene). The co-ligand X (X = (i) Cl, (ii) PPh3 = triphenyl phosphine, and (iii) PTA = 1,3,5-triaza-7-phosphaadamantane) was varied in order to study the effect it has on the antitumor activity of the compounds. The synthesized compounds were thoroughly characterized using different analytical techniques, including ESI-MS, NMR, FTIR, UV-Vis, and fluorescence spectroscopy. A fluorescence quenching experiment with serum albumin proteins revealed good interactions between the complexes and HSA and BSA. An analysis of their lipophilic character via the shake flask method and a stability study using UV spectroscopy were conducted as well. The anticancer properties of the synthesized compounds were further explored by conducting a DNA binding study using absorption spectroscopy and fluorometric titration with DAPI to check the mode of binding with DNA. Interestingly, the complexes were also found to catalyze the oxidation of NADH to NAD+, giving rise to radical species in the cells. An immunoblot analysis strongly suggested that all three complexes can remarkably upregulate the expression of cleaved caspase-3 and downregulate the expression of the anti-apoptotic protein BCLXL. It is important to note that such studies are yet to be reported for similar benzimidazole-based ruthenium complexes and therefore present a new direction for the investigation of antitumor ruthenium-based metallodrugs. Furthermore, Hoechst and AO/EtBr staining was used to analyze the morphological changes of the compound-treated cancer cells due to apoptosis, which was also confirmed by the IC50 values obtained from the colorimetric assay (MTT) against different cancer cell lines.

Dinuclear and mononuclear metal(II) polypyridyl complexes against drug-sensitive and drug-resistant Plasmodium falciparum and their mode of action.

BACKGROUND: Malaria remains one of the most virulent and deadliest parasitic disease in the world, particularly in Africa and Southeast Asia. Widespread occurrence of artemisinin-resistant Plasmodium falciparum strains from the Greater Mekong Subregion is alarming. This hinders the national economies, as well as being a major drawback in the effective control and elimination of malaria worldwide. Clearly, an effective anti-malarial drug is urgently needed. METHODS: The dinuclear and mononuclear copper(II) and zinc(II) complexes were synthesized in ethanolic solution and characterized by various physical measurements (FTIR, CHN elemental analysis, solubility, ESI-MS, UV-Visible, conductivity and magnetic moment, and NMR). X-ray crystal structure of the dicopper(II) complex was determined. The in vitro haemolytic activities of these metal complexes were evaluated spectroscopically on B+ blood while the anti-malarial potency was performed in vitro on blood stage drug-sensitive Plasmodium falciparum 3D7 (Pf3D7) and artemisinin-resistant Plasmodium falciparum IPC5202 (Pf5202) with fluorescence dye. Mode of action of metal complexes were conducted to determine the formation of reactive oxygen species using PNDA and DCFH-DA dyes, JC-1 depolarization of mitochondrial membrane potential, malarial 20S proteasome inhibition with parasite lysate, and morphological studies using Giemsa and Hoechst stains. RESULTS: Copper(II) complexes showed anti-malarial potency against both Pf3D7 and Pf5202 in sub-micromolar to micromolar range. The zinc(II) complexes were effective against Pf3D7 with excellent therapeutic index but encountered total resistance against Pf5202. Among the four, the dinuclear copper(II) complex was the most potent against both strains. The zinc(II) complexes caused no haemolysis of RBC while copper(II) complexes induced increased haemolysis with increasing concentration. Further mechanistic studies of both copper(II) complexes on both Pf3D7 and Pf5202 strains showed induction of ROS, 20S malarial proteasome inhibition, loss of mitochondrial membrane potential and morphological features indicative of apoptosis. CONCLUSION: The dinuclear [Cu(phen)-4,4'-bipy-Cu(phen)](NO3)4 is highly potent and can overcome the total drug-resistance of Pf5202 towards chloroquine and artemisinin. The other three copper(II) and zinc(II) complexes were only effective towards the drug-sensitive Pf3D7, with the latter causing no haemolysis of RBC. Their mode of action involves multiple targets.

A binuclear Cu(II) complex as an efficient photocatalyst for N-alkylation of aromatic amines.

Visible-light driven photoreactions using transition metal complexes as catalysts are currently a research hotspot in developing environmentally friendly sustainable processes. To develop a potential copper-based photocatalyst, a binuclear Cu(II) complex has been synthesized using a Mannich base ligand viz. 2,4-dichloro-6-((4-(2-hydroxyethyl)piperazin-1-yl)methyl)phenol (H2L). The photocatalyst has been characterized using ESI-MS and single crystal X-ray diffraction. Under the irradiation of visible light, the catalyst can catalyze hydrogen auto-transfer in N-alkylated amine formation and benzyl alcohol oxidation reactions with excellent conversion. A plausible mechanistic pathway for catalytic reactions has been explored through ESI-MS spectrometric, UV-Vis spectroscopic and computational studies.

Pyrene-based fluorescent Ru(II)-arene complexes for significant biological applications: catalytic potential, DNA/protein binding, two photon cell imaging and in vitro cytotoxicity.

Ruthenium complexes are being studied extensively as anticancer drugs following the inclusion of NAMI-A and KP1019 in phase II clinical trials for the treatment of metastatic phase and primary tumors. Herein, we designed and synthesized four organometallic Ru(II)-arene complexes [Ru(η6-p-cymene)(L)Cl] (1), [Ru(η6-benzene)(L)Cl] (2), [Ru(η6-p-cymene)(L)N3] (3) and [Ru(η6-benzene)(L)N3] (4) [HL = (E)-N'-(pyren-1-ylmethylene)thiopene-2-carbohydrazide] that have anticancer, antimetastatic and two-photon cell imaging abilities. Moreover, in the transfer hydrogenation of NADH to NAD+, these compounds also display good catalytic activity. All the complexes, 1-4, are well characterized by spectroscopic techniques (NMR, mass, FTIR, UV-vis and fluorescence). The single crystal X-ray diffraction technique proved that the ligand L coordinates through an N,O-bidentate chelating fashion in the solid-state structures of complexes 1 and 2. The stability study of the complexes was performed through UV-visible spectroscopy. The cytotoxicities of all the complexes were screened through MTT assay and the results revealed that the complexes have potential anticancer activity against various cancerous cells (HeLa, MCF7 and A431). Studies with spectroscopic techniques revealed that complexes 1-4 exhibit strong interactions with biological molecules i.e. proteins (HSA and BSA) and CT-DNA. The density functional theory (DFT-D) method has been employed in the present study to know the interaction between DNA and complexes by calculating the HOMO and LUMO energy. A plausible mechanism for NADH oxidation has also been explored and the DFT calculations are found to be in accord with the experimental observation. Furthermore, we have investigated intracellular reactive oxygen species (ROS) generation capabilities in the MCF7 breast cancer cell line. The Hoechst/PI dual staining method confirmed the apoptosis mode of cell death. Meanwhile, complexes 1-4 show capabilities to prevent the metastasis phase of cancer cells by inhibiting cell migration.

Pre-arranged building block approach for the orthogonal synthesis of an unfolded tetrameric organic-inorganic phosphazane macrocycle.

Inorganic macrocycles remain challenging synthetic targets due to the limited number of strategies reported for their syntheses. Among these species, large fully inorganic cyclodiphosphazane macrocycles have been experimentally and theoretically highlighted as promising candidates for supramolecular chemistry. In contrast, their hybrid organic-inorganic counterparts are lagging behind due to the lack of synthetic routes capable of controlling the size and topological arrangement (i.e., folded vs unfolded) of the target macrocycle, rendering the synthesis of differently sized macrocycles a tedious screening process. Herein, we report-as a proof-of-concept-the combination of pre-arranged building blocks and a two-step synthetic route to rationally enable access a large unfolded tetrameric macrocycle, which is not accessible via conventional synthetic strategies. The obtained macrocycle hybrid cyclodiphosphazane macrocycle, cis-[µ-P(µ-NtBu)]2(µ-p-OC6H4C(O)O)]4[µ-P(µ-NtBu)]2 (4), displays an unfolded open-face cavity area of 110.1 Å2. Preliminary theoretical host-guest studies with the dication [MeNC5H4]22+ suggest compound 4 as a viable candidate for the synthesis of hybrid proto-rotaxanes species based on phosphazane building blocks.

Group VIII Metal Carbonyl Cluster-Boronic Acid Conjugates: Cytotoxicity and Mode of Action Studies.

A set of metal carbonyl cluster-boronic acid conjugates of the group VIII metals (Fe, Ru, and Os) were synthesized and their antiproliferative effects measured against two breast cancer cell lines (MCF-7 and MDA-MB-231) and a noncancerous breast epithelial (MCF-10A) cell line. The cytotoxicity followed the order Ru > Os > Fe for the MDA-MB-231 cells, although the latter two exhibited similar cytotoxicity against MCF-7 and MCF-10A cells. The osmium species {Os3(CO)10(µ-H)[µ-SC6H4-p-B(OH)2]} (2) could be chemically oxidized to its hydroxy analogue [Os3(CO)10(µ-H)(µ-SC6H4 -p-OH)] (2-OH), which showed comparable cytotoxicity. Mode of action studies pointed to an apoptotic pathway for cell death.

Mechanosynthesis of Higher-Order Cocrystals: Tuning Order, Functionality and Size in Cocrystal Design*.

The ability to rationally design and predictably construct crystalline solids has been the hallmark of crystal engineering research. To date, numerous examples of multicomponent crystals comprising organic molecules have been reported. However, the crystal engineering of cocrystals comprising both organic and inorganic chemical units is still poorly understood and mostly unexplored. Here, we report a new diverse set of higher-order cocrystals (HOCs) based on the structurally versatile-yet largely unexplored-phosph(V/V)azane heterosynthon building block. The novel ternary and quaternary cocrystals reported are held together by synergistic and orthogonal intermolecular interactions. Notably, the HOCs can be readily obtained either via sequential or one-pot mechanochemical methods. Computational modelling methods reveal that the HOCs are thermodynamically driven to form and that their mechanical properties strongly depend on the composition and intermolecular forces in the crystal, offering untapped potential for optimizing material properties.

Synthesis, characterization, theoretical, molecular docking and in vitro biological activity studies of Ru(II) (η6-p-cymene) complexes with novel aniline substituted aroyl selenoureas.

A sequence of aroyl selenourea ligands (L1-L3) substituted by aniline and their Ru(II) (η6-p-cymene) complexes (1-3), [Ru(II) (η6-p-cymene) L] (L = monodentate aroyl selenourea ligand) have been synthesized and characterized the composition of the ligands and their metal complexes. The molecular structures of ligand L1 and complex 3 were also confirmed by single XRD crystal method. The single-crystal XRD study showed that aroyl selenourea ligand coordinates with Ru via Se novel neutral monodentate atom. In vitro DNA interaction studies were investigated by Fluorescence and UV-Visible spectroscopic methods which showed that the intercalative mode of binding is in the order of 1 > 2 > 3 with Ru(II) (η6-p-cymene) complexes. Spectroscopic methods have been used for measuring the binding affinity of bovine serum albumin to complex. Moreover, the cytotoxic study of complexes (1-3) were evaluated against HeLa S3, A549, and IMR90 cells, resulting in complexes 1 and 2 showed promising cytotoxic activity against HeLa S3 cell with IC50 values of 24 and 26 µM, respectively. Also, the morphological changes of HeLa S3 and A549 cells were confirmed by fluorescence microscope in the presence of complexes 1 and 2 using AO (acridine orange, 200 µM) and EB (ethidium bromide, 100 µM). In addition, the docking results strongly support the protein binding studies of the complexes.Communicated by Ramaswamy H. Sarma.

Size-control in the synthesis of oxo-bridged phosphazane macrocycles via a modular addition approach.

Inorganic macrocycles remain largely underdeveloped compared with their organic counterparts due to the challenges involved in their synthesis. Among them, cyclodiphosphazane macrocycles have shown to be promising candidates for supramolecular chemistry applications due to their ability to encapsulate small molecules or ions within their cavities. However, further developments have been handicapped by the lack of synthetic routes to high-order cyclodiphosphazane macrocycles. Moreover, current approaches allow little control over the size of the macrocycles formed. Here we report the synthesis of high-order oxygen-bridged phosphazane macrocycles via a "3 + n cyclisation" (n = 1 and 3). Using this method, an all-PIII high-order hexameric cyclodiphosphazane macrocycle was isolated, displaying a larger macrocyclic cavity than comparable organic crown-ethers. Our approach demonstrates that increasing building block complexity enables precise control over macrocycle size, which will not only generate future developments in both the phosphazane and main group chemistry but also in the fields of supramolecular chemistry.

Tuning the π-π overlap and charge transport in single crystals of an organic semiconductor via solvation and polymorphism.

Polymorphism is a central phenomenon in materials science that often results in important differences of the electronic properties of organic crystals due to slight variations in intermolecular distances and positions. Although a large number of π-conjugated organic compounds can grow as polymorphs, it is necessary to have at disposal a series of several polymorphs of the same molecule to establish clear and predictive structure-property relationships. We report here on the occurrence of two solvates and three polymorphs in single crystalline form of the organic p-type semiconductor 2,2',6,6'-tetraphenyldipyranylidene (DIPO). When grown from chlorobenzene or toluene, the DIPO crystals spontaneously capture solvent molecules to form two pseudopolymorphic 1 : 1 binary solvates. Independently, three solvent-free DIPO polymorphs are obtained either from the vapor phase or from acetonitrile and benzene. Surprisingly, single crystal field-effect transistors (SC-FETs) reveal that the DIPO 1 : 1 binary solvate grown from chlorobenzene possesses a higher hole mobility (1.1 cm2 V-1 s-1) than the three solvent-free polymorphs (0.02-0.64 cm2 V-1 s-1). A refined crystallographic analysis combined with a theoretical transport model clearly shows that the higher mobility of the solvate results from an improved π-π overlap. Our observations demonstrate that solvation allows to tune the π-π overlap and transport properties of organic semiconductors by selecting appropriate solvents.

N-Bridged Acyclic Trimeric Poly-Cyclodiphosphazanes: Highly Tuneable Cyclodiphosphazane Building Blocks.

We have synthesized a completely new family of acyclic trimeric cyclodiphosphazane compounds comprising NH, Ni Pr, Nt Bu and NPh bridging groups. In addition, the first NH-bridged acyclic dimeric cyclophosphazane has been produced. The trimeric species display highly tuneable characteristics so that the distance between the terminal N(H)R moieties can be readily modulated by the steric bulk present in the bridging groups (ranging from ≈6 to ≈10 Å). Moreover, these species exhibit pronounced topological changes when a weak non-bonding NH⋅⋅⋅π aryl interaction is introduced. Finally, the NH-bridged chloride binding affinities have been calculated and benchmarked along with the existing experimental data available for monomeric cyclodiphosphazanes. Our results underscore these species as promising hydrogen bond donors for supramolecular host-guest applications.

Carbodicarbene Ligand Redox Noninnocence in Highly Oxidized Chromium and Cobalt Complexes.

Carbodicarbenes (CDCs) possess two lone pairs of electrons on their central carbone C atom (Ccarbone). Coordination to a transition metal via a σ bond leaves one pair of electrons with appropriate symmetry for π donation to the metal. However, the high energy of the latter also renders the CDC ligand potentially redox-active. Herein, we explore these alternatives in the redox series [Cr(L)2]n+ and [Co(L)2]n+ (n = 2-5), where L is a tridentate ligand comprised of a central CDC and two flanking pyridine donors. To this end, all members of both redox series were synthesized and their electronic structures were investigated by using a combination of 1H NMR, Evans' NMR, IR, UV-vis, and EPR spectroscopies, SQUID magnetometry, X-ray crystallography, and density functional theory studies. Whereas [CoII(L)2]2+ is a straightforward low-spin (S = 1/2) cobalt(II) complex, the corresponding chromium complex was found to feature an electronic structure that is intermediate between the two limiting resonance forms [CrIII(L•-)(L)]2+ and [CrII(L)2]2+. In the case of the tri-, tetra-, and pentacationic complexes, the qualitatively identical electronic structures [MIII(L)2]3+, [MIII(L•+)(L)]4+, and [MIII(L•+)2]5+ were observed for both metals. Thus, the metal ions retain a 3+ oxidation state throughout, and the higher redox states contain oxidized ligands. The majority of the unpaired spin on the cation radical ligands was calculated to be localized in π-symmetry orbitals on the coordinated Ccarbone atoms. Analogous behavior was previously reported for the corresponding iron redox series and, as such, redox noninnocence in oxidized CDC and, more broadly, carbone complexes is likely widely accessible.

Effect of Carbazolyl Groups on Photophysical Properties of Cyanuric Chloride.

Long-lived room temperature organic phosphorescence is highly useful in biological imaging, electroluminescent devices, information security, and security protection on account of its unique photophysical process and long-lived luminescence. In recent years, pure organic phosphorescent materials that do not contain rare precious metals have received increasing attention. Carbazole and its derivatives have been used to develop room temperature organic phosphorescent materials. However, the effect of carbazolyl groups on the photophysical properties of pure organic phosphors has rarely been reported. In this work, three cyanuric chloride phosphors (CzDCIT, BiCzDT, and TCzT) modified with different numbers of carbazolyl groups were synthesized. Several characterization techniques were employed to reveal distinct crystal forms of CzDCIT, BiCzDT, and TCzT. The single crystal diffraction of CzDCIT and BiCzDT showed not only different crystal packing modes, but also the formation of internal H-aggregation. These three phosphor powders exhibited dual emissions of blue fluorescence and yellow phosphorescence at room temperature, with luminescence lifetimes of 0.16-0.34 s. Theoretical calculations indicated that different numbers of effective intersystem crossing channels between CzDCIT, BiCzDT, or TCzT were responsible for the luminescence lifetimes. After doping the phosphors into the polymer matrix, they exhibited good persistent phosphorescence and high recoverability in multiple compression-grinding cycles.

Novel Approach to Generate a Self-Deliverable Ru(II)-Based Anticancer Agent in the Self-Reacting Confined Gel Space.

Finding the most effective method for cancer treatment is one of the thought-provoking tasks. Drug delivery by collapsing of metallogel to the cancer cell is an appealing way out. Cancer cells have an acidic environment due to excessive accumulation of lactic acid. In this work, the novel G5 gelator with a strategically free carboxylic acid arm has been designed and fabricated and characterized by several spectroscopic and microscopic techniques. These experiments suggest the formation of an ordered supramolecular gel with clover-leaf-like morphology. Mechanical properties from rheological measurements suggest the viscoelastic nature of the gel. Furthermore, we have obtained crystals of G5 from the pure dimethyl sulfoxide solution, whereas gelation gets induced by addition of water. This G5 gelator loses its gelation capability once the carboxylate is esterified by layering with methanol, which furnished the crystals of Me-G5' (G5' = G5-H). Further, the G5 gelator is used for the formation of ruthenium metallogel. Interestingly, we obtained the monomeric species [Ru(G5')(η6-p-cymene)Cl] [Ru(II)G5] only in confined gel space upon addition of a [Ru2(η6-p-cymene)2Cl4] dimer to G5. The Ru(II)G5 metallogel has an inherent anticancer property with an IC50 value of 10.53 µM for the A549 cancer cell line. Treatment of the Ru(II)G5 metallogel by lactic acid for mimicking the acidic environment of the malignant cell results in collapsing of the gel by releasing the ruthenium metal ion. This released ruthenium ion binds with the lactic acid derivative making the gelator G5 free and producing a new compound Ru(II)L, which has also shown the anticancer property. The molecular docking study revealed that the released G5 could interact with a monocarboxylate transporter to disrupt the lactate transport chain, which might induce apoptosis.

Cobalt Metallogel Interface for Selectively Sensing l-Tryptophan among Essential Amino Acids.

The development of metallogels widens the span of sensing activity as it opens new opportunities to develop chemosensors through metal-ligand interactions. Herein, a new nitrile-substituted 1,3,5-tricarboxamide-based gelator G4 has been fabricated and shows aggregate-induced enhanced emission (AIEE) after gelation in the presence of water. A dimethylformamide (DMF) solution of the gelator shows rapid crystallization, but addition of water to a DMF solution of gelator G4 leads to gelation at room temperature. In addition, gelator G4 was used for the formation of metallogels, and among them, the cobalt metallogel has been found to be effective for sensing l-tryptophan in the gel state through the quenching of AIEE. Interestingly, the gel is also effective in sensing bovine serum albumin protein at the nanomolar level, which contains an l-tryptophan residue. The limit of detection of Co(II)G4 for selective sensing of tryptophan has been found to be 2.4 × 10-8 M. To the best of our knowledge, there have been no reports to date of a metallogel being utilized to discriminate and selectively sense an amino acid and a protein. The gelation properties of the organic gelator molecule and metallogels have been explored through various spectroscopic tools and physicochemical experiments.

Enantiomeric pairs of ternary copper(ii) complexes and their aldol-type condensation products: synthesis, characterization, and anticancer and epigenetic properties.

Chiral enantiomers [Cu(phen)(l-ser)(H2O)]NO31 and [Cu(phen)(d-ser)(H2O)]NO32 (ser = serinato) underwent aldol-type condensation with formaldehyde, with retention of chirality, to yield their respective enantiomeric ternary copper(ii) complexes, viz. l- and d-[Cu(phen)(OCA)(H2O)]NO3·xH2O (3 and 4; phen = 1,10-phenanthroline; OCA = oxazolidine-4-carboxylate; x = 1/2, 0-2) respectively. These chiral complexes were characterized by FTIR, elemental analysis, circular dichroism, UV-visible spectroscopy, fluorescence spectroscopy (FL), molar conductivity measurement, ESI-MS and X-ray crystallography. The crystal structures of 1 and 3 showed both the cationic complexes to have a square pyramidal geometry. These complexes were about nine fold more potent than cisplatin against metastatic MDA-MB-231 breast cancer cells, inducing apoptotic cell death via ROS generation and a massive drop in mitochondrial membrane potential. The results of monitoring EZH1, EZH2 and H3K27me3 revealed that the mode of action of 1-4 also involved the downregulation of EZH2 and it seemed to be independent of the H3K27me3 status.

Visible Light Driven Hydrogen Evolution by Molecular Nickel Catalysts with Time-Resolved Spectroscopic and DFT Insights.

Hydrogen (H2) is a clean fuel that can potentially be a future solution for the storage of intermittent renewable energy. However, current H2 production is mainly dominated by the energy intensive steam reforming reaction, which consumes a fossil fuel, methane, and emits copious amounts of carbon dioxide as one of the byproducts. To address this challenge, we report a molecular catalyst that produces H2 from aqueous solutions, is composed of affordable, earth-abundant elements such as nickel, and has been incorporated into a system driven by visible light. Under optimized conditions, we observe a turnover number of 3880, among the best for photocatalytic H2 evolution with nickel complexes from water-methanol solutions. Through nanosecond transient absorption, electron paramagnetic resonance, and UV-vis spectroscopic measurements, and supported by density functional theory calculations, we report a detailed study of this photocatalytic H2 evolution cycle. We demonstrate that a one-electron reduced, predominantly ligand-centered, reactive Ni intermediate can be accessed under visible light irradiation using triethylamine as the sacrificial electron donor and reductive quencher of the initial photosensitizer excited state. In addition, the computational calculations suggest that the second coordination sphere ether arms can enhance the catalytic activity by promoting proton relay, similar to the mechanism among [FeFe] hydrogenases in nature. Our study can form the basis for future development of H2 evolution molecular catalysts that incorporate both ligand redox noninnocence and alternative second coordination sphere effects in artificial photosynthetic systems driven by visible light.

Hydrophobic Metal Halide Perovskites for Visible-Light Photoredox C-C Bond Cleavage and Dehydrogenation Catalysis.

Two-dimensional lead and tin halide perovskites were prepared by intercalating the long alkyl group 1-hexadecylammonium (HDA) between the inorganic layers. We observed visible-light absorption, narrow-band photoluminescence, and nanosecond photoexcited lifetimes in these perovskites. Owing to their hydrophobicity and stability even in humid air, we applied these perovskites in the decarboxylation and dehydrogenation of indoline-2-carboxylic acids. (HDA)2 PbI4 or (HDA)2 SnI4 were investigated as photoredox catalysts for these reactions, and quantitative conversion and high yields were observed with the former.

Synthesis and Electronic Properties of Novel 5,7-Diazapentacene Derivatives.

A route to the synthesis of novel 5,7-diazapentacenes and some preliminary studies on their properties is reported. A single crystal X-ray diffraction study of the dihexyl derivative showed it had formed a dimer during the analysis. The materials possess lower lying frontier orbitals than pentacene and may have potential applications in organic electronic devices. This synthetic method may be applicable to the synthesis of other azaacenes.

Two-Dimensional and Emission-Tunable: An Unusual Perovskite Constructed from Lindqvist-Type [Pb6Br19]7- Nanoclusters.

Preparing low-dimensional perovskite materials with novel building units is highly desirable because such materials have already been demonstrated to show unusual physical properties. In this report, we first reported a new and unusual two-dimensional perovskite framework, [B(HIm)4]4Pb13Br38 (1), constructed from novel Lindqvist-type [Pb6Br19]7- nanoclusters. The as-prepared material shows good water resistance and chemical/heat stability. More importantly, 1 has been proven to exhibit temperature/excitation-wavelength-dependent emission. A possible mechanism has been provided.