Factors that regulate the conformation of m-benziporphodimethene complexes: agostic metal-arene interaction, hydrogen bonding, and η2,π coordination

Group 12 and silver(I) tetramethyl‐m‐benziporphodimethene (TMBPDM) complexes with phenyl, methylbenzoate, or nitrophenyl groups as meso substituents were synthesized and fully characterized. The dimeric silver(I) complex displays an unusual η²,π coordination from the β‐pyrrolic C?C bond to the silver ion. All of the complexes displayed a close contact between the metal ion and the inner C(22)? H(22) on the m‐phenylene ring. The downfield chemical shifts of H(22) and large coupling constants between Cd^II and H(22) strongly support the presence of an agostic interaction between the metal ion and inner C(22)–H(22). Crystal structures revealed that the syn form is the predominant conformation for TMBPDM complexes. This is distinctively different from the exclusive anti conformation observed in m‐benziporphyrin and tetraphenyl‐m‐benziporphodimethene (TPBPDM) complexes. Evidently, intramolecular hydrogen‐bonding interactions between axial chloride and methyl groups stabilize syn conformations. Unlike the merely syn conformation observed in the solid‐state structures of TMBPDM complexes that contain an axial chloride, in solution these complexes display highly solvent‐ and temperature‐dependent syn/anti ratio changes. The observation of dynamic ¹H NMR spectroscopic scrambling between syn and anti conformations from the titration of chloride ion into the solution of the TMBPDM complex suggests that axial ligand exchange is a likely pathway for the conversion between syn and anti forms. Theoretical calculations revealed that intermolecular hydrogen‐bonding interactions between the axial chloride and CHCl₃ stabilizes the anti conformation, which explains the increased ratio for the anti form when dichloromethane or chloroform was used as the solvent.     

Density functional studies on dinuclear {Ni(II)Gd(III)} and trinuclear {Ni(II)Gd(III)Ni(II)} complexes: magnetic exchange and magneto-structural maps

Theoretical calculations using density functional methods have been performed on two dinuclear {Ni(II)-Gd(III)} and two trinuclear {Ni(II)-Gd(III)-Ni(II)} complexes having two and three μ-OR (R = alkyl or aromatic groups) bridging groups. The different magnetic behaviour, having moderately strong ferromagnetic coupling for complexes having two μ-OR groups and weak ferromagnetic coupling for complexes having three μ-OR groups, observed experimentally is very well reproduced by the calculations. Additionally, computation of overlap integrals MO and NBO analysis reveals a clear increase in antiferromagnetic contribution to the net exchange for three μ-OR bridged {Ni-Gd} dimers and also provides several important clues regarding the mechanism of magnetic coupling. Besides, MO and NBO analysis discloses the role of the empty 5d orbitals of the Gd(III) ion on the mechanism of magnetic coupling. Magneto-structural correlations for Ni-O-Gd bond angles, Ni-O and Gd-O bond distances, and the Ni-O-Gd-O dihedral angle have been developed and compared with the published experimental {Ni-Gd} structures and their J values indicate that the Ni-O-Gd bond angles play a prominent role in these types of complexes. The computation has then been extended to two trinuclear {Ni(II)-Gd(III)-Ni(II)} complexes and here both the {Ni-Gd} and the {Ni-Ni} interactions have been computed. Our calculations reveal that, for both structures studied, the two {NiGd} interactions are ferromagnetic and are similar in strength. The {Ni-Ni} interaction is antiferromagnetic in nature and our study reveals that its inclusion in fitting the magnetic data is necessary to obtain a reliable set of spin Hamiltonian parameters. Extensive magneto-structural correlations have been developed for the trinuclear complexes and the observed J trend for the trinuclear complex is similar to that of the dinuclear {Ni-Gd} complex. In addition to the structural parameters discussed above, for trinuclear complexes the twist angle between the two Ni-O-Gd planes is also an important parameter which influences the J values.     

Thiacalix[4]arene based reconfigurable molecular switches: set-reset memorized sequential device

The fluorescent chemosensors 3, 5 and 7 based on thiacalix[4]arene bearing naphthyl groups have been designed and synthesized. The optical chemosensor 3 based on a thiacalix[4]arene of cone conformation behaves as "turn-on" optical chemosensor for Fe(3+) and F(-) ions. However, chemosensors 5 and 7 based on a thiacalix[4]arene of 1,3-alternate conformation demonstrate "turn-on" optical behaviour for Hg(2+), F(-) ions (with receptor 5 as turn-on for K(+) ions also) and "turn-off" behaviour for Fe(3+) ions. The simultaneous presence of Fe(3+) and Hg(2+) or K(+) or F(-) ions results in formulation of reversible "on-off" switches. Various molecular logic gates developed in response to molecular switching between these chemical inputs have been integrated into sequential logic circuits with memory function in a feedback loop which mimics "set-reset" molecular level information processing device.     

Phytochemical investigation and antifeedant activity of Premna latifolia leaves

The essential oil of Premna latifolia Roxb. was obtained by hydrodistillation of fresh leaves of the plant having an oil yield of 0.05%, both non-polar and essential oil were analysed by GC and GC-MS. Hexane fraction of the leaves of P. latifolia was transesterified and analysed by GC and GC-MS, 40 non-polar components were identified comprising 89.3%. The most abundant fatty acid constituents were hexadecanoic acid (25.04%), 8,11,14-docosatrienoic acid (13.62%), octadecanoic acid (6.82%), 9,12-octadecadienoic acid (4.19%) and 29 components were investigated in the essential oil which comprises 78.1%. The most abundant oil constituents were 1-octen-3-ol (35.69%), terpendiol II (7.19%), δ-guaiene (7.49%) 2-undecanone (4.80%) and α-pinene (3.27%). Different extracts were also tested against polyphagous crop pest Spodoptera litura for antifeedant activity. Essential oil showed maximum growth reduction of 56.83% followed by chloroform extract of 43.93%.     

Photophysical behavior of acridine with amines within the micellar microenvironment of SDS: a time-resolved fluorescence and laser flash photolysis study

The photophysical behavior of acridine (Acr) shows a facilitated water assisted protonation equilibrium between its deprotonated (Acr* ～ 3.4 ns) and protonated forms (AcrH(+)* ～ 33 ns) within a confined environment of sodium dodecyl sulphate (SDS) micelles above the critical micellar concentration of 8 mM. The acidic interface of the micelles is capable of protonating Acr whereas deprotonated Acr is partitioned into the hydrophobic core. The time-resolved-area-normalized-emission spectra confirm the presence of both Acr* and AcrH(+)*, while time-resolved-emission spectra depict time evolution between them. Quenching of AcrH(+)* with triethylamine (TEA) results in a linear Stern-Volmer (S-V) plot, whereas non-linearity arises with N,N-dimethylaniline (DMA). Both steady-state and time-resolved quenching results with TEA are explained on the basis of excited state proton transfer (ESPT), however the reasons behind the quenching of excited Acr with DMA are proposed as ESPT followed by a photoinduced electron transfer. Partitioning of DMA at the interface makes it accessible for both Acr* and AcrH(+)* in hydrophobic and hydrophilic regions of micelles respectively. The rate of electron transfer at the interface is found to be slower compared to that in the hydrophobic core. Characterization of transient intermediates formed during ESPT and PET between Acr and amines by laser-flash photolysis also supports the observation obtained during fluorescence studies. The mode of interactions between Acr and amines inside micelles is controlled by the localization of the proton/electron donors and acceptors in different hydrophobic or hydrophilic regions of such nano-confined environments.     

Catalyst free,regioselective one-pot three-component synthesis of thiazol-2-imine derivatives in ionic liquid

A one-pot three-component approach for the synthesis of thiazol-2-imines has been described by the reaction of amine, phenyl isothiocyanate and β-nitroacrylate in [Hbim]BF₄ ionic liquid. The method is applicable for aromatic, benzylic, aliphatic and cyclic amines. Reusable reaction media, regioselectivity, mild reaction condition, catalyst free and high yield of products are the salient features of this protocol.     

Domino reactions in water for the stereoselective synthesis of novel spiro dihydro-2′H-[indene-2,3′-thiophen]-1(3H)-ones with three contiguous stereocenters

The domino reactions of (E)-2-(aryl)-2,3-dihydro-1H-inden-1-ones and 1,4-dithiane-2,5-diol in the presence of triethylamine in water stereoselectively afforded a library of 2′-(aryl)-4′-hydroxy-4′,5′-dihydro-2′H-spiro[indene-2,3′-thiophen]-1(3H)-ones. This transformation presumably proceeds via the generation of 2-mercaptoacetaldehyde from 1,4-dithiane-2,5-diol followed by Michael addition–intramolecular aldol sequence with C–C and C–S bond formations and creation of three contiguous stereocenters in a one-pot operation.     

Synthesis and characterization of cobalt(II), nickel(II), copper(II), palladium(II) and dioxouranium(VI) complexes of the antipyrine Schiff base of 3-formylsalicylic acid

A new Schiff base has been synthesized from 4-aminoantipyrine and 3-formylsalicylic acid. The ligand has a dianionic tetradentate compartmental OONO donor system. The cobalt(II), nickel(II), copper(II) and dioxouranium(VI) complexes exist in phenolato-bridged dinuclear species, while palladium(II) gives a mononuclear complex with free –COOH groups. The complexes have been characterized by elemental analyses, i.r., u.v.-vis, thermal and magnetic measurements.     

Isomeric ruthenium terpyridine complexes [Ru(trpy)(L)Cl]n+ containing the unsymmetrically bidentate acceptor L=3-amino-6-(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine. Synthesis, structures, electrochemistry, spectroscopy and DFT calculations

The isomeric title complexes were obtained in almost equimolar ratio from the reaction of Ru(trpy)Cl3 and L. Crystal structure analyses of the perchlorate hemihydrates, electrochemical and spectroscopic (NMR, UV/VIS, EPR) studies, supported by DFT calculations, reveal distinct differences between the isomeric redox series [1]n+(tetrazine-Nt trans to Cl) and [2]n+(pyrazolyl-Np trans to Cl; n= 0, 1, 2). The latter system with the pi acceptors trpy and tetrazine in the equatorial plane and the pyrazolyl and chloride donors in the axial positions exhibits facilitated oxidation, lower energy MLCT transitions, more balanced chelate coordination, and a higher g anisotropy in the oxidised (RuIII) state. According to partially resolved EPR spectra of one-electron reduced neutral compounds and they have the unpaired electron predominantly in the tetrazine ring of L.