Search

A series of Cd(II) complexes, [(PPh3)2Cd(SCOf)2] (1), [PPh4]2[Cd(SCOf)2(μ-Br)]2 (2), [(PPh3)2Ag(μ2-SCOf)2Cd(SCOf)] (3), Na2[(PPh3)Cd(MeOH)(SCOf)3]2 (4a) and Na2[(PPh3)Cd(SCOf)3]2.C7H8 (4b) (Where SCOf = furan-2-thiocarboxylate), have been synthesized and characterized by single crystal X-ray analysis and other spectroscopic techniques. Complexes 1 and 2 show distorted tetrahedral and distorted trigonal bipyramidal geometries around Cd(II), respectively. In the case of 3, Cd(II) exhibits a trigonal prismatic structure, whereas, Ag(I) is at the center of a distorted tetrahedron. Complex 4, has a trigonal pyramidal geometry, hitherto unknown for a Cd(II) center. The catalytic activities of complexes for the synthesis of dihydropyrimidinone have been investigated. Out of four complexes, complex 4 is the most efficient catalyst for the one-pot multicomponent Biginelli-type coupling toward the synthesis of dihydropyrimidinone. Excellent yields of the desired products were obtained with very low catalyst loadings (1 mol%). With a few examples, the versatility and scope of the method have also been demonstrated. The catalysts were also tested for their recyclability. [ABSTRACT FROM AUTHOR]

Treatment of copper iodide with 1,1′-bis(diphenylphosphino)ferrocene in 1:1 equivalent ratio afforded centrosymmetric dimer product of composition [{Cu(µ-I)(dppf)}2] (1a). However, similar reactions of 1,1′-bis(diphenylchalcogenophosphoryl)ferrocene (dppfE2) (E = S, Se) with [Cu(CH3CN)4]+ in 1:2 equivalents yielded [{Cu(dppfS2)}n]+ (1b) and [{Cu2(dppfSe2)3}n]2+ (1c) compounds, respectively. These reported compounds have synthesized with slight modifications. All the mentioned complexes were characterized by Uv–Vis, IR, 1H, 31P{1H} NMR spectroscopy and Mass spectrometry. The molecular structure of complex [{Cu(µ-I)(dppf)}2] was established through single crystal X-ray analysis, which suggests distorted tetrahedral geometry around the copper metal center. All the synthesized complexes were studied as a catalyst for synthesis of benzofuran derivatives under an environmentally friendly approach. [ABSTRACT FROM AUTHOR]

Borrowing hydrogenation (BH) is a powerful methodology, which is widely adopted for the N-alkylation of amines with alcohols using homogeneous molecular catalysts. To explore the chemistry, herein two novel monomeric Ru(II) complexes [(η6-p-cymene)Ru(L1)Cl2] [Ru-1] bearing 4-trifluromethoxyaniline (L1) and [(η6-p-cymene)Ru(L2)Cl] [Ru-2] bearing quinaldic acid (L2) were synthesized and their structural features were revealed by utilizing analytical and spectroscopic methods like FTIR, 1H and 13C NMR, ESI-MS, and elemental analysis. The lattice structures of both [Ru-1] and [Ru-2] were elucidated by Single Crystal XRD (SC-XRD). Also, aniline-based complex [Ru-3] was synthesized according to the literature and used for comparison. The catalytic efficacy of [Ru-(1–3)] was examined for N-alkylation of amines utilizing alcohols as alkylating agents in benign and solvent-free conditions. The catalytic performance was monitored by GC–MS and HPLC analyses. The primary amine-based (L1) complex [Ru-1] showed a very impressive and efficient conversion of 96%, whereas –N, O donor ligand based (L2) complex [Ru-2] and the unsubstituted aniline based [Ru-3] were able to achieve 25% and 90% conversion, respectively in similar reaction conditions. This drastic variation in catalytic performance was observed due to the co-operative effect of –NH2 in [Ru-1] and [Ru-3]. Metal–ligand cooperation (MLC) in both the complexes stabilizes the intermediate transition state and also the electron deficient Ru(II) center in [Ru-1] has very good binding affinity towards the substrate, which leads to superior catalytic conversion with [Ru-1] compared to [Ru-2] and [Ru-3]. [ABSTRACT FROM AUTHOR]

Azobenzene-based unnatural amino acid motifs were synthesized via Pd(II)-catalyzed diastereoselective C(sp3)–H arylation of amino acid carboxamides with iodoacetanilides and Mills azo coupling. [ABSTRACT FROM AUTHOR]

Negishi cross‐coupling reaction of organozinc compounds as nucleophiles with aryl halides has drawn immense focus for C−C bond formation reactions. In comparison to the well‐established library of Pd complexes, the C−C cross‐coupling of this particular approach is largely primitive with nickel‐complexes. Herein, we describe the syntheses of Ni(II) complexes, [(MeBICAAC)2NiX2] (X=Cl (1), Br (2), and I (3)) by employing the bicyclic (alkyl)(amino)carbene (MeBICAAC) ligand. The reduction of complexes 1–3 using KC8 afforded the two coordinate low valent, Ni(0) complex, [(MeBICAAC)2Ni(0)] (4). Complexes 1–4 have been characterized by spectroscopic techniques and their solid‐state structures were also confirmed by X‐ray crystallography. Furthermore, complexes 1–4 have been applied in a direct and convenient method to catalyze the Negishi cross‐coupling reaction of various aryl halides with 2,6‐difluorophenylzinc bromide or phenylzinc bromide as the coupling partner in the presence of 3 mol % catalyst. Comparatively, among all‐pristine complexes, 1 exhibit high catalytic potential to afford value‐added C−C coupled products without the use of any additive. The UV‐vis studies and HRMS measurements of controlled stochiometric reactions vindicate the involvement of Ni(I)−NI(III) cycle featured with a penta‐coordinated Ni(III)‐aryl species as the key intermediate for 1 whereas Ni(0)/Ni(II) species are potentially involved in the catalytic cycle of 4. [ABSTRACT FROM AUTHOR]

We report the peculiar characteristics of a polydentate Schiff base towards zinc(II) ions in the presence of pseudohalides (thiocyanate and azide) and the charge transport properties of zinc complex mediated devices in the solid state. The designed polydentate chelator, [HL = (Z)-2-methoxy-6-(((2-methoxy phenyl)imino)methyl)phenol)], was synthesized by coupling of o-anisidine and o-vanillin in ethanol under reflux, and the ligand was isolated in a single-crystalline phase in an orthorhombic system with the Pbca space group. Interestingly, the ligand bears unique structural features towards the coordination with zinc ions in the presence of thiocyanate and azide ions leading to mononuclear and dinuclear zinc–Schiff base–pseudohalide complexes (ZnP11NCS and ZnP11N3), respectively. In the ZnP11NCS complex, the Schiff base ligand becomes protonated to a zwitterionic form, which causes their monodentate/bidentate behaviour towards Zn(II) ions. In contrast, the ligand, P11, under identical reaction conditions, behaves as a tridentate chelating ligand towards Zn(II) ions in the ZnP11N3 complex having a symmetric μ1,1-phenoxo-bridge. In both complexes, NCS and N3 ions coordinate with Zn(II) ions in a terminal coordination mode. Crystal engineering approaches and Hirshfeld surface and energy framework analysis of the complexes delineate the dominant contribution of H⋯S and H⋯N hydrogen bonding and C–H⋯π interactions for a structural assortment of the compounds. Further, the complexes have been employed to construct devices to explore the charge transport properties in the dark and a shower of photons. The ZnP11N3 complex exhibits better charge transport properties than ZnP11NCS as evident from high DC conductivity measurement values and relaxation times caused by optical phonon activation under dark and light conditions. This feature might be utilized to explore their template applications in designing electronic devices as per the industry's needs. [ABSTRACT FROM AUTHOR]

This manuscript demonstrates the synthesis, structural characterization, computational studies, and biomimics of the phenazine oxidase activity of a newly designed cobalt (III) complex, [Co (dpa)(dpa‐H+)(N3)2]Cl2 (1) [dpa = 2,2′‐dipyridylamine] under an aerobic condition. The crystal structure analysis reveals that the cobalt (III) center adopts an octahedral geometry, and the complex forms a beautiful supramolecular framework through noncovalent interactions. The cobalt (III) catalyst turns out to be a promising catalyst for the oxidative coupling of o‐phenylenediamine (OPD) in oxygen‐saturated methanol with an excellent turnover number, kcat = 7.85 × 103 h−1. Spectrophotometric, electrochemical, mass spectrometry, and computational analysis ensure that the course of catalysis undergoes through a catalyst‐substrate complexation, facilitating the development of cobalt‐iminobenzoquinone species in the solution. The computational calculations employing the density functional theory (DFT) throw a light to the mechanistic insights of the phenazine oxidase mimics. ETS‐NOCV (extended transition state‐natural orbitals for chemical valence) plots of the reactive intermediates portray the coordination‐driven depletion of electron density from the nitrogens of OPD to cobalt center leading to the enhancement of electrophilic character on para‐positioned C‐atoms with respect to N‐atoms of OPD, therby catalyzing the nucleophilic attack by second OPD to produce the oxidation product, 2,3‐diaminophenazine (DAP). Interestingly, we are able to isolate the oxidation product of the OPD oxidation reaction as a hydrated chloride salt, DAPH+Cl− ·3H2O (2). The crystal engineering perspectives of 2 attribute the intriguing fate of the secondary chlorides for the stabilization of the oxidation product in crystalline phase. [ABSTRACT FROM AUTHOR]

Twenty-five (Ia–Iu, IIa–IIb, IIIa, and IVa) diarylidene-N-methyl-4-piperidones (DANMPs) were synthesized and characterized via UV, FT-IR, NMR, and MS while Id was characterized also by single crystal XRD. Twenty-one compounds shortlisted after initial in vitro anti-plasmodial activity successive screenings at 100 μM and 10 μM were evaluated for their IC50s against chloroquine-sensitive Pf3D7, chloroquine-resistant PfINDO, and artemisinin-resistant PfMRA-1240 strains. The four most promising compounds were Ie (IC50s μM 0.35MRA, 1.39INDO, 1.923D7), If (IC50s μM 1.07MRA, 1.36INDO, 3.393D7), Ir (IC50s μM 0.74MRA, 2.45INDO, 1.443D7), and In (IC50s μM 1.27MRA, 1.8INDO, 1.73D7). Resistance indices as low as 0.2 to 0.5 for these potent compounds and <1 for most other compounds suggest their greater potency against drug resistant strains than the drug sensitive strain. The parasiticidal action of Ir was seen within 4 h against the trophozoite stage of the parasite, which is known to express the highest levels of PLP synthase. In silico docking scores of −7.0 to −8.0 kcal mol−1 between potent DANMPs and PfPLP synthase, the direct binding of Ir studied by SPR to recombinantly expressed and purified PfPdx-1 and inhibition of Pdx1 enzymatic activity by Ir suggest this vital enzyme to be a probable target for the DANMPs. The non-hemolytic nature of Ir and conformity of most DANMPs to Lipinski's parameters indicate their potential as new anti-plasmodial leads with PfPLP synthase as one of their targets. [ABSTRACT FROM AUTHOR]

This research study reports the synthesis, structural characterization and phenoxazinone synthase‐like activity of two structurally similar copper(II) complexes developed with a benzimidazole functionalized Schiff base (L). The ligand, L, was designed and synthesized in high yield by the reaction of p‐methoxy benzaldehyde with o‐phenylenediamine. The reaction of L with CuCl2 and Cu(NO3)2 leads to the formation of two isostructural complexes, [Cu(L)2Cl2]2 (1) and [Cu(L)2(NO3)2]2 (2). Single crystal X‐ray structural study reveals that both the Cu(II) centre in 1 and 2 adopts a square planar geometry. An attempt has also been made to understand the role of coordinated co‐ligands on the catalytic oxidation of 2‐aminophenol (2‐AP) to 2‐amino‐3H‐phenoxazine‐3‐one (2‐APX) in methanol. The presence of coordinated nitrate to Cu(II) ions imparts a more labile character to complex 2, and the catalytic efficiency (kcat/KM) for complex 2 (1.50 × 107) was determined almost double compared with that of complex 1 (8.78 × 106). Electro‐chemical and electrospray ionization mass spectrometry studies of 1 and 2 with 2‐AP suggests that the square planar geometries of the Cu(II) centres remain the driving force to develop enzyme‐substrate adducts and excellent catalytic performance of the complexes. Electrochemical and EPR spectral analysis of the reaction mixture confirm the presence of active 2‐AP−/2‐AP•− redox species in the course of catalytic oxidation and suggest the radical driven oxidative coupling of 2‐AP in an aerobic environment. Temperature‐dependent kinetic measurements were carried out to evaluate the activation parameters (Ea, ΔH‡, ΔS‡), which favours the higher rate of catalytic oxidation of 2‐AP for complex 2 than complex 1. [ABSTRACT FROM AUTHOR]

In pursuit of the significant contribution of copper ion in different biological processes, this research work describes the synthesis, X‐ray structure, Hirshfeld surface analysis, oxidative dimerization of 2‐aminophenol and antibacterial activity of a newly designed copper (II)‐Schiff base complex, [Cu(L)2] (1), [Schiff base (HL) = 2‐(2‐methoxybenzylideneamino)phenol]. X‐ray structural analysis of 1 reveals that the Cu (II) complex crystallizes in a cubic crystal system with Ia‐3d space group. The Cu (II) centre adopts an unprecedented tetragonal bipyramidal geometry in its crystalline phase. The Schiff base behaves as a tridentate chelator and forms an innermetallic chelate of first order with Cu (II) ion. The copper (II) complex has been tested in the bio‐mimics of phenaxozinone synthase activity in acetonitrile and exhibits good catalytic activity as evident from high turnover number, 536.4 h−1. Electrochemical analysis exhibits the appearance of two additional peaks at −0.15 and 0.46 V for Cu (II) complex in presence of 2‐AP and suggests the development of AP−/AP•− and AP•−/IQ redox couples in solution, respectively. The presence of iminobenzosemiquinone radical at g = 2.057 in the reaction mixture was confirmed by electron paramagnetic resonance and may be considered the driving force for the oxidative dimerisation of 2‐AP. The existence of a peak at m/z 624.81 for Cu (II) complex in presence of 2‐AP in electrospray ionization mass spectrum ensures that the catalytic oxidation proceeds through enzyme‐substrate adduct formation. The copper (II) complex exhibits potential antibacterial properties against few pathogenic bacterial species like Staphylococcus aureus, Enterococcus and Klebsiella pneumonia and scanning electron microscope studies consolidates that destruction of bacterial cell membrane accounts on the development of antibacterial activity. [ABSTRACT FROM AUTHOR]

Two‐coordinate Cu(I) and Au(I) complexes supported by bicyclic (alkyl)(amino)carbene, [BICAAC‐CuCl] (1), [BICAAC‐CuI] (2), [(BICAAC)2Cu]+[PF6]– (3) and [(BICAAC)2Au]+[AuCl2]– (6) have been synthesized. The reaction of cyclic (alkyl)(amino)carbene, CAACcy with CuCl afforded [CAACcy‐CuCl] (4) and its further reaction with KPF6 gave [(CAACcy)2Cu]+[PF6]– (5). Complexes 1–6 have been characterized by multinuclear NMR, IR and UV‐Vis. spectroscopic method and high‐resolution mass spectrometry (HRMS). Single crystal X‐ray structure of heteroleptic complexes 1 and 4 and homoleptic complexes [(BICAAC)2Cu]+[CuI2]– (2'), 3 and 6 have also been determined. The crystal structure of these complexes confirmed linear two‐coordinate geometry around the metal centers. In the solid‐ state, complexes 1, 2', 4 and 6 displayed C−H⋯M (M=Cu, Au) and weak non‐covalent C−H⋯X (X=Cl, I) and C−H⋯H−C interactions. Computational calculations correlate well to the experimentally observed geometry and help elucidate the absorption characteristics type of transitions and the frontier orbitals involved in them. [ABSTRACT FROM AUTHOR]

Recently, an unprecedented observation of polar order, thermochromic behavior, and exotic mesophases in new chiral, bent‐shaped systems with a −CH3 moiety placed at the transverse position of the central core was reported. Herein, a homologous series of compounds with even‐numbered carbon chains from n=4 to 18 were synthesized, in which −Cl was substituted for −CH3 at the kink position and a drastic modification in the phase structure of the bent‐shaped molecule was observed. An unusual stabilization of the cubic blue phase (BP) over a wide range of 16.4 °C has been witnessed. Two homologues in this series (1‐12 and 1‐14) exhibit an interesting phase sequence consisting of BPI/II, chiral nematic, twist grain boundary, smectic A, and smectic X (SmX) phases. The higher homologues (1‐16 and 1‐18) stabilize the SmX phase enantiotropically over the entire temperature range. Crystal structure analysis confirmed the bent molecular architecture, with a bent angle of 148°, and revealed the presence of two different molecular conformations in an asymmetric unit of compound 1‐4. A DFT study corroborated that the −Cl moiety at the central core of the molecule led to an increase in the dipole moment along the transverse direction, which, in turn, facilitated the unusual stabilization of frustrated structures. Crystal polymorphism has been evidenced in three homologues (1‐10, 1‐12, and 1‐14) of the series. On the application of mechanical pressure through grinding, compound 1‐10 transformed from a bright yellow crystalline solid to a dark orange–green amorphous solid, which reversed upon dropwise addition of dichloromethane, indicating reversible mechanochromism in this class of compounds. In addition, excellent thermochromic behavior has been observed for compound 1‐10 with a controlled temperature–color combination. [ABSTRACT FROM AUTHOR]

The reactivity of a bicyclic (alkyl)(amino)carbene (BICAAC) towards different boranes has been examined in the present work. The reactions with boranes BX3·SMe2 (X = H, Cl, Br), BF3·OEt2 and BCl3 yield Lewis adducts [BICAAC·BH3] (1), [BICAAC·BHCl2] (2), [BICAAC·BH2Cl] (3), [BICAAC·BF3] (4), [BICAAC·BCl3] (5) and [BICAAC·BBr3] (6) respectively, whereas more hydridic boranes, 9-borabicyclo[3.3.1]nonane (9-BBN) and catecholborane (HBcat), enable the insertion of the carbene carbon into the B–H bond to form [BICAAC(H)-(9-BBN)] (7) and [BICAAC(H)-Bcat] (8). These complexes are the first examples of BICAAC–boron compounds and have been characterized using IR, multinuclear NMR spectroscopy, HRMS spectrometry and single crystal X-ray diffraction. Computational analyses were also performed to gain insight into the mechanism of B–H bond activation and adduct formation. Furthermore, the reactions of the BICAAC with boranes have been compared with the known reactions of CAACs and NHCs. [ABSTRACT FROM AUTHOR]

The mechanism of fluorescence enhancement of Tb3+ in Tb3+‐trimesic acid‐Gd3+ systems has been explored using dynamic light scattering. In earlier work, the mechanism of fluorescence enhancement of Tb3+ in these systems was proposed to be due to the formation of a polynuclear complex involving Tb3+, trimesic acid and Gd3+. However, no direct experimental evidence was presented for the mechanism in that work. In this work, we have used dynamic light scattering (DLS), to measure changes in the mean hydrodynamic diameter (Zavg) of the Tb3+‐trimesic acid‐Gd3+ complex, as a function of time. The Zavg was found to increase monotonically as a function of time, indicating a continuous growth in the particle size. The Eu3+‐β‐diketones‐Gd3+ system also shows enhancement of Eu3+ fluorescence; though a different mechanism was believed to be operating in this case; namely intermolecular energy transfer. If the two systems followed different mechanisms for fluorescence enhancement, the Eu3+‐β‐diketones‐Gd3+ system, is expected to show a different time evolution of particle size. The DLS study showed that the Zavg increased rapidly to a maximum value and then remained nearly constant throughout our measurements; that is, no gradual increase in Zavg was seen as in the Tb3+‐trimesic acid‐Gd3+ system. These DLS studies of the Tb3+‐trimesic acid‐Gd3+ and Eu3+‐β‐diketones‐Gd3+ systems, therefore confirms that different mechanisms of fluorescence enhancement are operative in the two systems. The study has demonstrated that the increase in fluorescence intensity with time when Gd3+ is added to the Tb3+‐trimesic acid complex is accompanied with an increase in particle size as revealed by dynamic light scattering studies. These observations are explained invoking the role of polynuclear complexes in the mechanism of fluorescence enhancement. [ABSTRACT FROM AUTHOR]

The first examples of group 13 element containing pyridinophanes have been assembled using heteroatom N–E–N bridges (E = B, Al). The presence of B and Al as acceptor atoms in the bridges and their coordination with pyridine nitrogen has a very strong influence on the conformational rigidity of the pyridinophanes. [ABSTRACT FROM AUTHOR]

Abstract: In this present work, we report the synthesis and structural characterization of two copper(II) complexes, [Cu(bpy)Cl2] (1) & [Cu(μ‐Cl)(phen)Cl]2 (2) [bpy=2,2′‐bipyridine; phen=1,10‐phenanthroline]. We have also studied their catalytic fate towards phenoxazinone synthase and catechol dioxygenase activity. X‐ray structural analyses revealed that 1 & 2 crystallize in triclinic & monoclinic system with P 1 and Cc space group respectively. The copper complexes catalyse the oxidative coupling of 2‐amino phenol (2‐AP) to aminophenoxazin‐3‐one with significant turn over number, kcat(h−1)=2.08×103 & 2.16×103 for 1 & 2 resectively. During investigation of catechol dioxygenase activity, stoichiometric addition of 1 & 2 to 3,5‐di‐tert‐butylcatechol (DTBC) in acetonitrile produce in situ catecholate‐to‐Cu(II) absorption bands at 812 and 821 nm respectively. The in situ Cu(II)‐catecholate species for both 1 & 2 react with molecular oxygen at the rate, kobs: 7.95×10−4 and 1.30×10−3 min−1 respectively and produce intradiol cleavage products in exclusive amount. Minor amount of benzoquinone is also found in solution. Intradiol products are found as major product in solution and accounts in favour of substrate activation mechanism. [ABSTRACT FROM AUTHOR]

Syntheses of multi-functional Aggregation-Induced Emission (AIE) active molecules in a simple manner have been drawing great attention in current luminescence materials research. In this report a simple diamine molecule (N1-tritylethane-1,2-diamine(1)) is reacted with salicylaldehyde using a Schiff-base technique which results in a new AIE active organic molecule [2-((2-(tritylamino)ethylideneamino)methyl)phenol (2)]. Computational calculations support that the nature of the transition is intra-molecular charge transfer/twisted intramolecular charge transfer (ICT/TICT). The mechanism of AIE has been attributed to restricted intramolecular rotation (RIR). Packing diagrams support that the nature of the aggregation is J-aggregation. The compound, 2, exhibits an irreversible mechanoluminescence (ML) property with a drastic colour change from blue to green (λmax, 445 nm → 512 nm) upon grinding. However, it undergoes a reversible transition with the same colour change (blue → green) through applying pressure axially (using a hydraulic press). The reversible transition is observed by lowering the temperature of 2 to that of liquid nitrogen. The causes of such transitions showing variations in the emission colour upon different triggers have been investigated. In addition, 2 has been successfully tested for the sensing of Zn(ii) and shows a rare turn-on luminescence change, the mechanism behind which has been explored. The detection limit for Zn(ii) is determined to be 0.064 ppm. [ABSTRACT FROM AUTHOR]

Strong hydrogen bonds play a significant role in crystal packing. In particular, the involvement of interactions involving fluorine in controlling the crystal packing requires appropriate attention, especially in the presence of other strong hydrogen bonds. In the present study, a detailed quantitative assessment has been performed of the nature, energetics and topological properties derived from the electron density in model compounds based on fluorinated benzamides (a total of 46 fluorine-substituted benzamides containing multiple fluorine atoms) in the solid state. The primary motivation in the design of such molecules is to enhance the acidity of the interacting H atoms in the presence of an increasing number of F atoms on the molecular scaffold, resulting in increased propensity towards the formation of intermolecular interactions involving organic fluorine. This exercise has resulted in the identification of new and frequently occurring supramolecular synthons involving F atoms in the packing of molecules in the solid state. The energetics associated with short and directional intermolecular C sp2-H...F-C sp2 interactions with significantly high electrostatic contributions is noteworthy, and the topological analysis reveals the bonding character of these ubiquitous interactions in crystal packing in addition to the presence of C sp2-F...F-C sp2 contacts. [ABSTRACT FROM AUTHOR]

We have demonstrated stepwise functionalization of chlorophosph(III)azane, [ClP(μ-NtBu)]2 with organic azides and chalcogens (S and Se). The in situ 31P{¹H} NMR spectroscopic investigations reveal that conversion of the basic PIII2N2 framework, leading to PV 2N2 proceeds via (PIII/PV)N2 intermediates. Under controlled conditions, the (PIII/PV)N2 intermediate species can be isolated, providing details of the reaction pathway and distribution of the cis and trans isomers of the PV2N2 products. It has also been demonstrated that neat reactions at elevated temperatures expedite the formation of PV2N2 products, without significantly affecting the yields and relative distribution of the cis and trans isomers. All new compounds reported here are potential building blocks for the assembly of inorganic macrocycles and polymers. [ABSTRACT FROM AUTHOR]

Four new Ir(iii) complexes with the general formula [IrHCl(C^N)(PPh3)2] containing different conjugated Schiff base ligands (C^N) have been synthesized and characterized by 1H, 13C, and 31P NMR, HRMS, and IR spectra and one of them by single crystal X-ray diffraction. Their photophysical properties in solution and in the solid state have been analyzed and three main practical results have been obtained: (i) a dual fluorescent and phosphorescent emissive complex in solution, (ii) successful acid/base sensing in the solid state and (iii) quantitative CO2 detection. Quantum chemical calculations have been employed to assign the character of the lowest excited states. A plausible explanation for the observed aggregation induced enhanced emission (AIEE) is given, based on the restriction of intramolecular motions due to the effect of intermolecular C–H…π and C–H…Cl type interactions upon aggregation. [ABSTRACT FROM AUTHOR]

Two equivalents of 1-benzyl-3-bromoethylbenzimidazolium bromide couple with Na2Se to produce the first selenoether bridged bis-benzimidazolium salt (LH2)Br2. The nitrate (LH2)(NO3)2 and tetrafluoroborate (LH2)(BF4)2 salts were also synthesized from (LH2)Br2. The reaction of Hg(OAc)2 with (LH2)Br2 gave the first pseudo pincer carbene mercury complex, [Hg(L-κ2C)][HgBr4] (C1). Different complexes of Pd(ii) with selenoether bridged carbene were obtained using (LH2)Br2 and (LH2)(NO3)2. Syntheses of these complexes were dependent on the counter anion and the temperature. Thus, the pincer type ionic complex [PdBr(L-κ3CSeC)]Br (C2) was isolated at 80 °C and the pseudo pincer type neutral complex cis-[PdBr2(L-κ2C)] (C3) was isolated at room temperature from (LH2)Br2 and Pd(OAc)2 in DMSO. The nitrate precursor (LH2)(NO3)2 on palladation with Pd(OAc)2 afforded [Pd(L-κ4CBzCSeC)]NO3 (C4) showing an unprecedented intramolecular metallation at the ortho position of the benzyl wingtip of the benzimidazole moiety. The ligand salts and metal complexes have been characterized using HRMS, heteronuclear NMR and IR spectroscopy. Single crystal X-ray structures of the ligand salts (LH2)Br2 and (LH2)(BF4)2 and complexes C1–C4 have also been elucidated. Complex C2 showed good activity for C–C coupling in the mono-Heck reaction of methyl acrylate and arylbromides. Interestingly, the less common bis-arylation was also observed with deactivated arylbromides as the result of double-Heck coupling. [ABSTRACT FROM AUTHOR]

A mononuclear iron(II) complex, [Fe(phen)3]Cl2 ( 1) (phen =1,10-phenanthroline), has been synthesized in crystalline phase and characterized using various spectroscopic techniques including single crystal X-ray diffraction. Crystal structure analysis revealed that 1 crystallizes in a monoclinic system with C2/m space group. Complex 1 acts as a functional model for a biomimetic catalyst promoting the aerobic oxidation of 3,5-di- tert-butylcatechol (3,5-DTBC) through radical pathways with a significant turnover number ( kcat =3.55 × 103 h−1) and exhibits catechol dioxygenase activity towards the same 3,5-DTBC substrate at room temperature in oxygen-saturated ethanol medium. The existence of an isobestic point at 610 nm from spectrophotometric data indicates the presence of Fe3+ −3,5-DTBC adduct favouring an enzyme-substrate binding phenomenon. Upon stoichiometric addition of 3,5-DTBC pretreated with two equivalents of triethylamine to the iron complex, two catecholate-to-iron(III) ligand-to-metal bands (575 and 721 nm) are observed and the in situ generated catecholate reacts with dioxygen ( kobs =9.89 × 10−4 min−1) in ethanol medium to afford exclusively intradiol cleavage products along with a small amount of benzoquinone, and a small amount of extradiol cleavage products, which provide substantial evidence for a mechanism. Copyright © 2016 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

The studies of weak interactions involving “organic fluorine” have resulted in a number of conflicts in the literature. Although the involvement of a C–F group in influencing the crystal packing has been demonstrated in various compounds, no one has emphasized the consistency of the synthons formed by C–H…F–C hydrogen bonds. Herein, we have attempted to draw a correlation between the formation of a particular synthon and the positions of the fluorine substitutions from the structural analyses of a model system of tetrafluoro substituted N-benzylideneanilines. A few frequently occurring supramolecular synthons involving C–H…F–C hydrogen bonds have been identified in these and related molecules, and have been quantified by ab initio calculations using the MP2 level of theory and the 6-31+G* basis set in the gas phase. The topological properties of these C–H…F–C hydrogen bonds have been calculated using AIM2000. The nature, strength, directionality and synthon reproducibility of the C–H…F–C hydrogen bonds are the key features presented in this article. [ABSTRACT FROM AUTHOR]

A new one-dimensional (1-D) Pb(II) coordination polymer, [Pb(2,2′-bpy)(NO3)2(H2O)]n(1) (2,2′-bpy = 2,2′-bipyridine), has been synthesized and characterized by different spectroscopic techniques and X-ray single-crystal analysis. From the X-ray crystal structure of1, the Pb2+can be best described as a highly distorted pentagonal bipyramid with O4 (water) and O6 (nitrate) at apical positions (O4–Pb–O6 of 143.7(1)°). Variability in bond distances reveals that Pb2+is unsymmetrically surrounded by two nitrates, one 2,2′-bpy and one water. Nitrates bridge between monomers. The molecule crystallizes in the monoclinicP21/n(14) space group. This is the first example of a 1-D Pb(II) polymer in which nitrates show three different coordination motifs (terminal, chelating, and bridging). Solid state as well as solution phase UV–vis spectral analysis and mass spectrometric studies clearly reveal instability with breakdown of Pb(II) polymer in aqueous solution. The arrangement of the 2,2′-bpy, water, and nitrates leaves a coordination gap at the Pb(II) occupied probably by a stereo-active lone pair of electrons. [ABSTRACT FROM AUTHOR]

Design and syntheses of 'aggregation induced emission (AIE)' active blue-emitting bis-cyclometalated iridium(III) complexes with appended diphosphine ligands [Ir(F2ppy)2(L1/L2)2(Cl)] (F2ppy = 2-(2′,4′-difluoro) phenylpyridine; L1 = 1,2-bis(diphenylphosphino)ethane; L2 = bis(diphenylphosphino)propane) have been realized on a suitable route. The free phosphorous donor atom present on the appended diphosphine is shown to provide selective binding to the mercuric ion (Hg2+). The selective binding ability of the probe molecule towards mercuric ions results in a detectable signal due to complete quenching of their AIE properties. The quenching effect of the probe molecule has been explored and found to be the result of the degradation of the probe iridium(III) complex triggered by the presence of mercuric ions due to an interplay of a soft-soft interaction between the free phosphorous atom of the probe molecule and mercuric ions. These complexes were modelled to obtain deeper understanding of excited state properties and the results were tentatively correlated with the experimental data. [ABSTRACT FROM AUTHOR]

Two iridium(III) diimine complexes [mono(1,10-phenanthroline)bis(triphenylphosphine)(dihydrido)iridium(III) hexafluorophosphate ( 1) and mono(1,10-phenanthroline)bis(triphenylphosphine)(hydrido)(chloro)iridium(III) hexafluorophosphate ( 2)] have been synthesized from a single two-step reaction. The structures of 1 and 2 both adopt distorted octahedral geometries, as established by single-crystal X-ray diffraction. The complexes, upon irradiation with UV light at 365 nm, emit faint light in solution and bright light in the solid state. The ground- and excited-state properties of these complexes were investigated through density functional theory (DFT) and time-dependent DFT calculations. The calculated energies for the transitions from the ground state to the singlet and triplet excited states were close to those determined from the experimental absorption and emission. Their molecular orbitals were also exploited to compute the ground-state dipole moments and redox potentials. Several experiments were performed to demonstrate the 'aggregation-induced emission' (AIE) activity of these complexes. AIE was triggered by the restricted intramolecular rotation of the rotating units (phenyls in triphenyphosphines) in these molecules in the solid state. The solid thin films of 1 and 2 exhibit solvent-polarity-dependent vapour-responsive emission properties (vapoluminescent). The rationale for the different emission behavior in the solid state has been thoroughly investigated. The packing diagrams of 1 and 2 show that there is enough space available to accommodate small organic solvent molecules inside the crystal lattices. [ABSTRACT FROM AUTHOR]

Abstract: In this work, we have synthesised and structurally characterized a mononuclear cobalt(III) complex, [Co(2-O-pn)2]Cl.2H2O (1), (2-O-pn = 1,3-diamino-2-propanolate). From the X-ray structure of the cobalt complex, it is revealed that Co(III) ion in 1 adopts an octahedral geometry and crystallizes in the monoclinic system with C2 / c space group. The lattice aqua molecule in combination with chloride ion in 1 forms a water-chloride cluster, (H2O)2⋯(Cl)2 through strong H-bonding interaction mediated via cobalt(III) complex in a unique binding motif. This cobalt(III) complex has been tested as an effective catalytic system towards the oxidative coupling of 2-aminophenol (2-AP) in the MeCN medium. In situ mass spectral analysis confirms that 2-AP forms an adduct with cobalt ion and the course of catalysis proceeds through catalyst-substrate binding followed by oxidative coupling of 2-AP with iminobenzoquinone. This cobalt(III) catalyst affords exclusively aminophenoxazinone species with a significant turnover number, kcat:6.37×102h-1 in the MeCN medium. This cobalt(III) complex is able to screen out the growth of some bacteria and fungi species. Quantum chemical calculations employing density functional theory is used to model structural parameters and spectroscopic behaviour. The theoretical findings corroborate well with the experimental results.GRAPHICAL ABSTRACT: SYNOPSIS A mononuclear cobalt(III) complex exhibits significant catalytic efficacy towards oxidative coupling of 2-aminphenol (2-AP) in MeCN medium and predominantly produces aminophenoxazinone species with a significant turn over number, kcat:6.37×102h-1 in presence of molecular oxygen. [ABSTRACT FROM AUTHOR]