Photophysical, electrochemical and solid state properties of diketopyrrolopyrrole based molecular materials: importance of the donor group

Diketopyrrolopyrrole (DPP) based molecular semiconductors have emerged as promising materials for high performance active layers in organic solar cells. It is imperative to comprehend the origin of such a property by investigating the fundamental structure property correlation. In this report we have investigated the role of the donor group in DPP based donor-acceptor- donor (D-A-D) structure to govern the solid state, photophysical and electrochemical properties. We have prepared three derivatives of DPP with varying strengths of the donor groups, such as phenyl (PDPP-Hex), thiophene (TDPP-Hex) and selenophene (SeDPP-Hex). The influence of the donor units on the solid state packing was studied by single crystal X-ray diffraction. The photophysical, electrochemical and density functional theory ( DFT) results were combined to elucidate the structural and electronic properties of three DPP derivatives. We found that these DPP derivatives crystallized in the monoclinic space group P21/c and show herringbone packing in the crystal lattice. The derivatives exhibit weak p-p stacking interactions as two neighboring molecules slip away from each other with varied torsional angles at the donor units. The high torsional angle of 32 degrees ( PDPP-Hex) between the phenyl and lactam ring results in weak intramolecular interactions between the donor and acceptor, while TDPP-Hex and SeDPP-Hex show lower torsional angles of 9 degrees and 12 degrees with a strong overlap between the donor and acceptor units. The photophysical properties reveal that PDPP-Hex exhibits a high Stokes shift of 0.32 eV and SeDPP- Hex shows a high molar absorption co-efficient of 33 600 L mol -1 1 cm -1 1 with a low band gap of similar to 2.2 eV. The electrochemical studies of SeDPP- Hex indicate the pronounced effect of selenium in stabilizing the LUMO energy levels and this further emphasizes the importance of chalcogens in developing new n-type organic semiconductors for optoelectronic devices.

Novel synthesis of carbohydrate fused alpha-amino gamma-lactams and glycopeptides by NIS mediated ring opening of donor-acceptor substituted cyclopropanes

alpha-Amino gamma-lactams have been synthesized from carbohydrate derived cyclopropanecarboxylates using N-iodosuccinimide (NIS) and NaN3. Cyclopropane ring opening with NIS and NaN3 in different solvents has been studied. Reductive cyclization of the intermediate di-azides leads to the carbohydrate fused alpha-amino gamma-lactam and gamma-lactams. Additionally, the methodology has been successfully extended to the synthesis of a glycopeptide. (C) 2014 Elsevier Ltd. All rights reserved.

Substitution-Modulated Anticancer Activity of Half-Sandwich Ruthenium(II) Complexes with Heterocyclic Ancillary Ligands

Ten new organometallic half-sandwich ruthenium complexes with heterocyclic ligands have been synthesized (H1-H10). The substituents on the ancillary heterocyclic ligands were varied to understand the effect of substitution on anticancer activity. The crystallographic characterization of five complexes confirms that they adopt three-legged piano-stool structures and are stabilized by intramolecular hydrogen bonding. Complexes H2 and H3 also exhibit halogen bonding in the solid state. In aqueous media, the complexes form dinuclear ruthenium species. Complex H1 with a noncytotoxic heterocycle, 6-fluoro-2-mercaptobenzothiazole, and complex H11 with the unsubstituted 2-mercaptobenzothiazole are the most active against A2780 and KB cell lines. The substitution of the H atoms on the ancillary ligand with Cl or Br atoms leads to a decrease in the anticancer activity. With the exception of fluorine-substituted H5, the complexes with mercaptobenzoxazole (H6-H9) are inactive against all of the tested cell lines. Ruthenium complexes with mercaptonaphthimidazole (H10) and mercaptobenzimidazole (H13) do not show any anticancer activity. The active complexes show a biphasic melting curve when incubated with calf thymus (CT) DNA. These complexes only inhibit thioredoxin reductase (TrxR) enzyme activity to a small extent. The substitution of hydrogen atoms with fluorine atoms in the aromatic heterocyclic ligands on organometallic half-sandwich ruthenium complexes has the most beneficial effect on their anticancer activity.

Component Selection in the Self-Assembly of Palladium(II) Nanocages and Cage-to-Cage Transformations

Dynamic supramolecular systems involving a tetratopic palladium(II) acceptor and three different pyridine-and imidazole-based donors have been used for self-selection by a synergistic effect of morphological information and coordination ability of ligands through specific coordination interactions. Three different cages were first synthesized by two-component self-assembly of individual donor and acceptor. When all four components were allowed to interact in a reaction mixture, only one out of three cages was isolated. The preferential binding affinity towards a particular partner was also established by transforming a non-preferred cage into a preferred cage by interaction with the appropriate ligand. Computational studies further supported the fact that coordination interaction of imidazole moiety to Pd-II is enthalpically more preferred compared to pyridine, which drives the selection process. Analysis of crystal packing of both complexes indicated the presence of strong hydrogen bonds between nitrate and water molecules and also H-bonded 3D networks of water. Both complexes exhibit promising proton conductivity (10(-5) to ca. 10(-3) Scm(-1)) at ambient temperature under a relative humidity of circa 98% with low activation energy.

Multicomponent Assembly of Fluorescent-Tag Functionalized Ligands in Metal-Organic Frameworks for Sensing Explosives

Detection of trace amounts of explosive materials is significantly important for security concerns and pollution control. Four multicomponent metal organic frameworks (MOFs-12, 13, 23, and 123) have been synthesized by employing ligands embedded with fluorescent tags. The multicomponent assembly of the ligands was utilized to acquire a diverse electronic behavior of the MOFs and the fluorescent tags were strategically chosen to enhance the electron density in the MOFs. The phase purity of the MOFs was established by PXRD, NMR spectroscopy, and finally by singlecrystal XRD. Single-crystal structures of the MOFs-12 and 13 showed the formation of three-dimensional porous networks with the aromatic tags projecting inwardly into the pores. These electron-rich MOFs were utilized for detection of ex- plosive nitroaromatic compounds (NACs) through fluorescence quenching with high selectivity and sensitivity. The rate of fluorescence quenching for all the MOFs follows the order of electron deficiency of the NACs. We also showed the detection of picric acid (PA) by luminescent MOFs is not always reliable and can be misleading. This attracts our attention to explore these MOFs for sensing picryl chloride (PC), which is as explosive as picric acid and used widely to prepare more stable explosives like 2,4,6-trinitroaniline from PA. Moreover, the recyclability and sensitivity studies indicated that these MOFs can be reused several times with parts per billion (ppb) levels of sensitivity towards PC and 2,4,6-trinitrotoluene (TNT).

Hetero-tri-spin 2p-3d-4f] Chain Compounds Based on Nitronyl Nitroxide Lanthanide Metallo-Ligands: Synthesis, Structure, and Magnetic Properties

Employing nitronyl nitroxide lanthanide(III) complexes as metallo-ligands allowed the efficient and highly selective preparation of three series of unprecedented heterotri-spin (Cu Ln-radical) one-dimensional compounds. These 2p-3d-4f spin systems, namely Ln(3)Cu(hfac)II(NitPhOAII)41 (Ln(III)=Gd 1(Gd), Tb 1(Tb), Dy 1(Dy); NitPhOAII=2-(4'-allyloxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3- oxide), Ln(3)Cu(hfac)II(NitPhOPO4] (1-nrn=Gd 2Gd, Tb 2Tb, Dy 2(Dy), Ho 2HOf Yb 2yb; NitPhOPr= 2-(4'-propoxyphenyI)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) and Ln3Cu(hfac)II(NitPhOB441 (LnIm=Gd 3Gd, Tb 3Tb, Dy 3(Dy); NitPhOBz=2-(4'-benzyloxy- phenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) involve O-bound nitronyl nitroxide radicals as bridging ligands in chain structures with a Cu-Nit-Ln-Nit-Ln-Nit-Ln-Nit] repeating unit. The dc magnetic studies show that ferromagnetic metal radical interactions take place in these heterotri-spin chain complexes, these and the next-neighbor interactions have been quantified for the Gd derivatives. Complexes 1Tb and 2Tb exhibit frequency dependence of ac magnetic susceptibilities, indicating single-chain magnet behavior.

Simultaneous co-ordination of three cytosine ligands displaying different binding sites around the copper centres

We report the synthesis and structural characterization of a polymeric ternary copper-cytosine-phenanthroline complex, Cu-4(phen)(3)-(mu(3)-cyt)(2)(mu-OH)(cyt)(OH)Cl-3](n)center dot 16H(2)O, where three cytosine ligands with different binding sites have simultaneously complexed to the four copper metal centres. Interestingly, the complex exhibits two different coordination geometries around the metal centres.

Modulation of Electronic and Self-Assembly Properties of a Donor-Acceptor-Donor-Based Molecular Materials via Atomistic Approach

The performance of molecular materials in optoelectronic devices critically depends upon their electronic properties and solid-state structure. In this report, we have synthesized sulfur and selenium based (T4BT and T4BSe) donor-acceptor-donor (D-A-D) organic derivatives in order to understand the structure-property correlation in organic semiconductors by selectively tuning the chalcogen atom. The photophysical properties exhibit a significant alteration upon varying a single atom in the molecular structure. A joint theoretical and experimental investigation suggests that replacing sulfur with selenium significantly reduces the band gap and molar absorption coefficient because of lower electronegativity and ionization potential of selenium. Single-crystal X-ray diffraction analysis showed differences in their solid-state packing and intermolecular interactions. Subsequently, difference in the solid-state packing results variation in self-assembly. Micorstructural changes within these materials are correlated to their electrical resistance variation, investigated by conducting probe atomic force microscopy (CP-AFM) measurements. These results provide useful guidelines to understand the fundamental properties of D-A-D materials prepared by atomistic modulation.

Polypyridyl iron(II) complexes showing remarkable photocytotoxicity in visible light

Iron(II) complexes of polypyridyl ligands (B), viz. Fe(B)(2)]Cl-2 (1 and 2) of N, N, N-donor 2-(2-pyridyl)-1,10-phenanthroline (pyphen in 1) and 3-(pyridin-2-yl)dipyrido3,2-a:2',3'-c]phenazine (pydppz in 2), are prepared and characterized. They are 1:2 electrolytes in aqueous DMF. The diamagnetic complexes exhibit metal to ligand charge transfer band near 570 nm in DMF. The complexes are avid binders to calf thymus DNA giving binding constant (K (b)) values of similar to 10(6) M-1 suggesting significant intercalative DNA binding of the complexes due to presence of planar phenanthroline bases. Complex 2 exhibits significant photocytotoxicity in immortalized human keratinocyte cells HaCaT and breast cancer cell line MCF-7 giving IC50 values of 0.08 and 13 mu M in visible light (400-700 nm). Complex 2 shows only minor dark toxicity in HaCaT cells but is non-toxic in dark in MCF-7 cancer cells. The light-induced cellular damage follows apoptotic pathway on generation of reactive oxygen species as evidenced from the dichlorofluorescein diacetate (DCFDA) assay.

The crystal structure of a lectin from Butea monosperma: Insight into its glycosylation and binding of ligands

Crystal structure of a lectin purified from Butea monosperma seeds was determined by Molecular Replacement method. Its primary structure was determined by Tandem Mass Spectroscopy and electron density maps from X-ray diffraction data. Its quaternary structure was tetrameric, formed of two monomers, alpha and beta, beta appearing as truncated alpha. The occurrence of two tetramers in the asymmetric unit of the crystal might be a consequence of asymmetric contacts due to difference in glycosylation and variable loops structures, to form an `octamer-structure'. The crystal structure showed binding pockets for gamma Abu, having a proposed role in plant defense, at the interface of canonical dimer-partners. Hemagglutination studies, enzyme kinetics, isothermal titration calorimetry and molecular dynamics showed that the lectin is specific to N-acetyl D-galactosamine, galactose and lactose in decreasing order, and alpha-amylase inhibitor. (C) 2014 Elsevier B.V. All rights reserved.

New dimeric carbazole-benzimidazole mixed ligands for the stabilization of human telomeric G-quadruplex DNA and as telomerase inhibitors. A remarkable influence of the spacer

for selectively targeting cancer cells. Herein, we report the design and evolution of a new kind of carbazole-based benzimidazole dimers for their efficient telomerase inhibition activity. Spectroscopic titrations reveal the ligands high affinity toward the G4 DNA with significantly higher selectivity over duplex-DNA. The electrophoretic mobility shift assay shows that the ligands efficiently promote the formation of 04 DNA even at a lower concentration of the stabilizing K+ ions. The TRAP-LIG assay demonstrates the ligand's potential telomerase inhibition activity and also establishes that the activity proceeds via G4 DNA stabilization. An efficient nuclear internalization of the ligands in several common cancer cells (HeLa, HT1080, and A549) also enabled differentiation between normal HFF cells in co-cultures of cancer and normal ones. The ligands induce significant apoptotic response and antiproliferative activity toward cancer cells selectively when compared to the normal cells.

Conformation-selective coordination-driven self-assembly of a ditopic donor with Pd-II acceptors

Coordination-driven self-assembly of 3-(5-(pyridin-3-yl)-1H-1,2,4-triazol-3-yl)pyridine (L) was investigated with 90 degrees cis-blocked Pd(II) acceptors and tetratopic Pd(NO3)(2). Although the ligand is capable of binding in several different conformations (acting as a ditopic donor through the pyridyl nitrogens), the experimental results (including X-ray structures) showed that it adopts a particular conformation when it binds with 90 degrees cis-blocked Pd(II) acceptors (two available sites) to yield 2 + 2] self-assembled macrocycles. On the other hand, with Pd(NO3)(2) (where four available sites are present) a different conformer of the same donor was selectively bound to form a molecular cubic cage. The experimental findings were corroborated well with the density functional theory (B3LYP) calculations. The tetratopic Pd(NO3)(2) yielded a 6 + 12] self-assembled Pd6L12 molecular cube, which contains a potential void occupied by nitrate and perchlorate ions. Being a triazole based ligand, the free space inside the cage is enriched with several sp(2) hybridised nitrogen atoms with lone pairs of electrons to act as Lewis basic sites. Knoevenagel condensation reactions of several aromatic aldehydes with active methylene compounds were successfully performed in reasonably high yields in the presence of the cage.

Template-free coordination-driven self-assembly of discrete hexanuclear prismatic cages employing half-sandwich octahedral Ru-2(II) acceptors and triimidazole donors

Coordination-driven self-assembly of dinuclear half-sandwich p-cymene ruthenium(II) complexes Ru-2(mu-eta(4)-C2O4)(CH3OH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1a) and Ru-2(mu-eta(4)-C6H2O4)(CH3OH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1b) separately with imidazole-based tritopic donors (L-1-L-2) in methanol yielded a series of hexanuclear 3+2] trigonal prismatic cages (2-5), respectively L-1 = 1,3,5-tris(imidazole-1-yl) benzene; L-2 = 4,4',4 `'-tris(imidazole-1-yl) triphenylamine]. All the self-assembled cages 2-5 were characterized by various spectroscopic techniques (multinuclear NMR, Infra-red and ESI-MS) and their sizes, shapes were obtained through geometry optimization using molecular mechanics universal force field (MMUFF) computation. Despite the possibility due to the free rotation of donor sites of imidazole ligands, of two different atropoisomeric prismatic cages (C-3h or C-s) and polymeric product, the self-selection of single (C(3)h) conformational isomeric cages as the only product is a noteworthy observation. (C) 2015 Elsevier B.V. All rights reserved.

Photocytotoxic ternary copper(II) complexes of histamine Schiff base and pyridyl ligands

Ternary copper(Il) complexes of salicylaldehyde-histamine Schiff base (HL) and pyridyl ligands, viz. Cu(bpy)(L)](ClO4) (1) and Cu(dppz)(L)](C104) (2), where bpy is 2,2'-bipyridine (in 1) and dppz is dipyrido3,2-a:2',3'-c]phenazine (in 2), were synthesized, characterized and their DNA binding, photo-activated DNA cleavage activity and photocytotoxicity studied. The 1:1 electrolytic one-electron paramagnetic complexes showed a d-d band near 670 nm in aqueous DMF (1:1 v/v). The crystal structure of complex 1 showed the metal in CuN4O distorted square-pyramidal geometry. Complex 2 intercalatively binds to calf-thymus (ct) DNA with a binding constant (K-b) of similar to 10(5) M-1. It exhibited moderate chemical nuclease activity but excellent DNA photocleavage activity in red light of 647 nm forming (OH)-O-center dot radicals. It showed remarkable photocytotoxicity in human cervical cancer cells (HeLa) giving IC50 of 1.6 mu M in visible light (400-700 nm) with low dark toxicity. The photo-induced cell death is via generation of oxidative stress by reactive oxygen species.

Visualisation of charge-transfer excitations in donor-acceptor molecules using the particle-hole map: a case study

Charge-transfer (CT) excitations are essential for photovoltaic phenomena in organic solar cells. Owing to the complexity of molecular geometries and orbital coupling, a detailed analysis and spatial visualisation of CT processes can be challenging. In this paper, a new detail-oriented visualisation scheme, the particle-hole map (PHM), is applied and explained for the purpose of spatial analysis of excitations in organic molecules. The PHM can be obtained from the output of a time-dependent density-functional theory calculation with negligible additional computational cost, and provides a useful physical picture for understanding the origins and destinations of electrons and holes during an excitation process. As an example, we consider intramolecular CT excitations in Diketopyrrolopyrrole-based molecules, and relate our findings to experimental results.