Coordination-Driven Self-Assembly of M3L2 Trigonal Cages from Preorganized Metalloligands Incorporating Octahedral Metal Centers and Fluorescent Detection of Nitroaromatics

The design and preparation of novel M3L2 trigonal cages via the coordination-driven self-assembly of preorganized metalloligands containing octahedral aluminum(III), gallium(III), or ruthenium(II) centers is described. When tritopic or dinuclear linear metalloligands and appropriate complementary subunits are employed, M3L2 trigonal-bipyramidal and trigonal-prismatic cages are self-assembled under mild conditions. These three-dimensional cages were characterized with multinuclear NMR spectroscopy (H-1 and P-31) and high-resolution electrospray ionization mass spectrometry. The structure of one such trigonal-prismatic cage, self-assembled from an arene ruthenium metalloligand, was confirmed via single-crystal X-ray crystallography. The fluorescent nature of these prisms, due to the presence of their electron-rich ethynyl functionalities, prompted photophysical studies, which revealed that electron-deficient nitroaromatics are effective quenchers of the cages' emission. Excited-state charge transfer from the prisms to the nitroaromatic substrates can be used as the basis for the development of selective and discriminatory turn-off fluorescent sensors for nitroaromatics.

Liquid-Liquid Interphase (Biphasic) as the Reaction Medium in the Assembly of a Hierarchy of Structures of 4,4 `-Azodibenzoic Acid with Zinc and Cadmium

The compounds Zn(C12H8N2)](2)C12N2H8(COO)(2)](2)center dot(C6H12O)center dot(H2O), I, Zn(C12H8N2)]C12N2H8(COO)(2)], II, Cd(C12H8N2)(H2O)]C12N2H8(COO)(2)]center dot(H2O), III, Zn(C10N2H8)]C12N2H8(COO)(2)]center dot 0.5(C10N2H8), IV, Cd(C12N2H8(COO)(2)center dot H2O], V, and Zn-3(mu(2)-O)(mu(3)-O)(3)]C12N2H8(COO)(2)], VI, have been synthesized by using a biphasic approach (I, III, V, VI) or regular hydrothermal method (II, IV). The compounds exhibit one (I and II), two (In), and three dimensionally (IV, V, VI) extended structures. The flexible azodibenzoate ligand gives rise to a 3-fold interpenetration (IV) when the synthesis was carried out using normal hydrothermal methods. The biphasic approach forms structures without any interpenetrations, especially in the three-dimensional structures of V and VI. Formation of Cd2O2 dimers in V and extended M-O(H)-M two-dimensional layers in VI suggests the subtle structural control achieved by the biphasic method. Transformation studies indicate that it is possible to transform I to II. Lewis acid catalytic studies have been performed to evaluate the role of the coordination environment in such reactions. All the compounds have been characterized by a variety of techniques that includes powder X-ray diffraction, infrared, thermogravitric analysis, UV-vis, photoluminescence studies.

Hydrogen-bond-directed self-assembly of D-(+)-dibenzoyltartaric acid and 4-aminopyridine: optical nonlinearities and stoichiometry-dependent novel structural features

Attempts to prepare hydrogen-bond-directed nonlinear optical materials from a 1:1 molar mixture Of D-(+)-dibenzoyltartaric acid (DBT, I) and 4-aminopyridine (4-AP, II) resulted in two salts of different stoichiometry. One of them crystallizes in an unusual 1.5:1 (acid:base) monohydrate salt form III while the other one crystallizes as 1:1 (acid:base) salt IV. Crystal structures of both of the salts were determined from single-crystal X-ray diffraction data. The salt III crystallizes in a monoclinic space group C2 with a = 30.339(l), b = 7.881(2), c = 14.355(1) angstrom, beta = 97.48(1)degrees, V = 3403.1(9) angstrom3, Z = 4, R(w) = 0.058, R(w)= 0.058. The salt IV also crystallizes in a monoclinic space group P2(1) with a = 7.500(1), b = 14.968(2), c = 10.370(1) angstrom, beta = 102.67(1)degrees, V = 1135.9(2) angstrom3, Z = 2, R = 0.043, R(w) = 0.043. Interestingly, two DBT molecules with distinctly different conformation are present in the same crystal lattice of salt III. Extensive hydrogen-bonding interactions are found in both of the salts, and both of them show SHG intensity 1.4-1.6 times that of urea.

Molecular self-assembly of cadmium-triazolate complexes via hydrogen bonding: Synthesis, structures and photoluminescent properties

Two new cadmium coordination polymers namely Cd(HAmTrz-COO)(4)(NH4+)(2)] 1; and Cd(HAmTrz)(2)I-2](n) 2; (HAmTrz-COOH = 3-amino-1,2,4-triazole-5-carboxylic acid), have been prepared based on HAmTrz-COOH as ligand. The crystal structures of 1 and 2 have been determined by single-crystal X-ray diffraction technique. In coordination-complex 1 four triazole ligands coordinate via N1 nitrogen leading to a tetrahedral geometry around cadmium ion, while in 2 the ligand prefers to coordinate to the metal in a bidentate bridging mode. The structures of both the coordination polymers can be envisaged as 3D hydrogen bonded networks. Thermogravimetric analysis shows that 2 is more stable than 1 owing to different coordination numbers of cadmium atoms. Photoluminescence properties of both the compounds have been investigated in the solid state. (C) 2011 Elsevier B.V. All rights reserved.

Synthesis and Self-Assembly of Donor-Acceptor-Donor Based Oligothiophenes and Their Optoelectronic Properties

In this work, the synthesis of an oligothiophene having a donor acceptor donor (D-A-D) chromophore with hydrogen bonding groups is described. The D-A-D molecule was demonstrated to self-organize via intermolecular H-bonding between barbituric acid units. Interactions between the oligothiophene subunits were also found to be important, affording nanoribbons that could be observed by atomic force and transmission electron microscopy. The applicability of the oligothiophene for organic electronic applications was investigated by fabricating organic field-effect transistors (OFETs) and organic photovoltaic devices. The OFET measurements yielded p-type mobility of 7 x 10(-7) cm(2)/(Vs), and when blended with C(60)-PCBM, the photovoltaic efficiency was observed to be 0.18%.

Spontaneous self-assembly of designed cyclic dipeptide (Phg-Phg) into two-dimensional nano- and mesosheets

In this study, we present the spontaneous self-assembly of designed simplest aromatic cyclic dipeptides of (L-Phg-L-Phg) and (D-Phg-L-Phg) to form highly stable two-dimensional (2D) nano- and mesosheets with large lateral surface area. Various microscopy data revealed that the morphology of 2D mesosheets resembles the hierarchical natural materials with layered structure. Solution and solid-state NMR studies on cyclo(L-Phg-L-Phg) revealed the presence of strong (N-H-O) hydrogen-bonded molecular chains supported by aromatic pi-pi interactions to form 2D mesosheets. Interestingly, cyclo(D-Phg-L-Phg) self-assembles to form single-crystalline as well as non-crystalline 2D rhomboid sheets with large lateral dimension. X-ray diffraction analysis revealed the stacking of (N-H-O) hydrogen-bonded molecular layers along c-axis supported by aromatic pi-pi interactions. The thermogravimetric analysis shows two transitions with overall high thermal stability attributed to layered hierarchy found in 2D mesosheets.

Self-Assembly of Manganese(I)-Based Molecular Squares: Synthesis and Spectroscopic and Structural Characterization

Syntheses of manganese(I)-based molecular squares have been accomplished in facile one-pot reaction conditions at room temperature. Self-assembly of eight components has resulted in the formation of M4L4-type metallacyclophanes [Mn(CO)(3)Br(mu-L)(4) (1-3) using pentacarbonylbromomanganese as metal precursor and rigid azine ligands such as pyrazine, 4,4'-bipyridine, and trans-1,2-bis(4pyridyl)ethylene, respectively, as bridging ligands. The metallacyclophanes have been characterized on the basis of IR, NMR, and UV-vis spectroscopic techniques and single-crystal X-ray diffraction methods.

Aza-heterocyclic ligand assisted assembly of new cobalt MOFs with pcu and graphite related structures

A hydrothermal reaction of a mixture of cobalt salt, 5-nitro isophthalic acid and triazole (compound I), 3-aminotriazole (3-AT) (compound II) and 3,5-diaminotriazole (compound III) at 220 degrees C for a day resulted in the isolation of three different, but related, compounds containing cobalt clusters. The three-dimensional compounds have Co-5 (compound-I) and Co-4 (compound-II and compound-III) clusters connected through the carboxylate and triazolate forming structures with pcu net (compound-I and compound-II) and a graphite-related net (compound-III). The water molecules (coordinated and lattice) can be readily re-adsorbed by the structure of compound-I, whereas the removal of the water molecule leads to a collapse of the structures of compound-II and compound-III. The TGA studies suggest the possibility of an intermediate structure for compound-1, which was investigated using in situ single crystal to single crystal (SCSC) transformations. The identification of an intermediate structure during the dehydration/hydration cycle in compound-I is important and provides important pointers about the dynamics of the water molecules in these compounds. Compound-I was also investigated in detail using a variety of spectroscopic techniques such as IR, UV-Vis spectroscopy etc. Magnetic studies on the synthesized compounds indicate anti-ferromagnetic behavior.

Three-Component Self-Assembly of a Series of Triply Interlocked Pd12 Coordination Prisms and Their Non-Interlocked Pd6 Analogues

Template-assisted formation of multicomponent Pd6 coordination prisms and formation of their self-templated triply interlocked Pd12 analogues in the absence of an external template have been established in a single step through Pd?N/Pd?O coordination. Treatment of cis-[Pd(en)(NO3)2] with K3tma and linear pillar 4,4'-bpy (en=ethylenediamine, H3tma=benzene-1,3,5-tricarboxylic acid, 4,4'-bpy=4,4'-bipyridine) gave intercalated coordination cage [{Pd(en)}6(bpy)3(tma)2]2[NO3]12 (1) exclusively, whereas the same reaction in the presence of H3tma as an aromatic guest gave a H3tma-encapsulating non-interlocked discrete Pd6 molecular prism [{Pd(en)}6(bpy)3(tma)2(H3tma)2][NO3]6 (2). Though the same reaction using cis-[Pd(NO3)2(pn)] (pn=propane-1,2-diamine) instead of cis-[Pd(en)(NO3)2] gave triply interlocked coordination cage [{Pd(pn)}6(bpy)3(tma)2]2[NO3]12 (3) along with non-interlocked Pd6 analogue [{Pd(pn)}6(bpy)3(tma)2](NO3)6 (3'), and the presence of H3tma as a guest gave H3tma-encapsulating molecular prism [{Pd(pn)}6(bpy)3(tma)2(H3tma)2][NO3]6 (4) exclusively. In solution, the amount of 3' decreases as the temperature is decreased, and in the solid state 3 is the sole product. Notably, an analogous reaction using the relatively short pillar pz (pz=pyrazine) instead of 4,4'-bpy gave triply interlocked coordination cage [{Pd(pn)}6(pz)3(tma)2]2[NO3]12 (5) as the single product. Interestingly, the same reaction using slightly more bulky cis-[Pd(NO3)2(tmen)] (tmen=N,N,N',N'-tetramethylethylene diamine) instead of cis-[Pd(NO3)2(pn)] gave non-interlocked [{Pd(tmen)}6(pz)3(tma)2][NO3]6 (6) exclusively. Complexes 1, 3, and 5 represent the first examples of template-free triply interlocked molecular prisms obtained through multicomponent self-assembly. Formation of the complexes was supported by IR and multinuclear NMR (1H and 13C) spectroscopy. Formation of guest-encapsulating complexes (2 and 4) was confirmed by 2D DOSY and ROESY NMR spectroscopic analyses, whereas for complexes 1, 3, 5, and 6 single-crystal X-ray diffraction techniques unambiguously confirmed their formation. The gross geometries of H3tma-encapsulating complexes 2 and 4 were obtained by universal force field (UFF) simulations.

Self-Assembly and Catalytic Activity of Metal Nanoparticles Immobilized in Polymer Membrane Prepared via Layer-by-Layer Approach

Densely packed nanoparticles distributed in a stable and robust thin film is a highly preferred system for utilizing the various applications of nanoparticles. Here, we report covalent bond mediated layer-by-layer (LbL) self-assembled thin films of nanoparticles embedded in polymer membrane. Polymer with complementary functional group is utilized for fabrication of thin film via covalent bonding. UV-visible spectroscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to monitor the growth of LbL thin film. Subsequently, the composite thin film is used for catalysis of an organic electron transfer reaction of p-nitrophenol to p-aminophenol by sodium borohydride. The catalytic activity of these composite films is assayed multiple times, proving its applicability as a catalyst. The kinetic data obtained by monitoring reduction of p-nitrophenol suggest that the reaction rates are directly related to the sizes of the nanoparticle and porosity of the membrane.

From Molecular to Supramolecular: An Exploration into the Modes of Self-assembly in Conformationally Locked Polycyclitols

This brief account highlights the notable findings of our investigation into the supramolecular chemistry of conformationally locked polycyclitols in the solid state. The study was aimed at analyzing the crystal packing and unraveling the modalities of non-covalent interactions (particularly, intramolecular vis-a-vis intermolecular OH center dot center dot center dot O hydrogen bonds) in polyols. The know-how obtained thereof, was successfully utilized to engineer self-assemblies of designer polycyclitols, having hydrogen bond donors and acceptors fettered onto a trans-decalin scaffold. The results seek to draw particular attention to the intrinsic attribute of this rigid carbocyclic framework to lock functional groups into spatially invariant positions and bring potential intramolecular hydrogen bonding partners into favorable interaction geometry to engender predictability in the self-assembly patterns.

Coordination self-assembly of tetranuclear Pt(II) macrocycles with an organometallic backbone for sensing of acyclic dicarboxylic acids

Coordination self-assembly of a series of tetranuclear Pt(II) macrocycles containing an organometallic backbone incorporating ethynyl functionality is presented. The 1 : 1 combination of a linear acceptor 1,4-bistrans-Pt(PEt3)(2)(NO3)(ethynyl)]benzene (1) with three different dipyridyl donor `clips' (L-a-L-c) afforded three 2 + 2] self-assembled Pt-4(II) macrocycles (2a-2c) in quantitative yields, respectively L-a = 1,3-bis-(3-pyridyl)isothalamide; L-b = 1,3-bis(3-pyridyl)ethynylbenzene; L-c = 1,8-bis(4-pyridyl)ethynylanthracene]. These macrocycles were characterized by multinuclear NMR (H-1 and P-31); ESI-MS spectroscopy and the molecular structures of 2a and 2b were established by single crystal X-ray diffraction analysis. These macrocycles (2a-2c) are fluorescent in nature. The amide functionalized macrocycle 2a is used as a receptor to check the binding affinity of aliphatic acyclic dicarboxylic acids. Such binding affinity is examined using fluorescence and UV-Vis spectroscopic methods. A solution state fluorescence study showed that macrocycle 2a selectively binds (K-SV = 1.4 x 10(4) M-1) maleic acid by subsequent enhancement in emission intensity. Other aliphatic dicarboxylic acids such as fumaric, succinic, adipic, mesaconic and itaconic acids caused no change in the emission spectra; thereby demonstrating its potential use as a macrocyclic receptor in distinction of maleic acid from other aliphatic dicarboxylic acids.

Diaminotriazine substituted diphenyl ether: reversible structural transformation and solvent dependent solid state fluorescence

The effect of molecular shape and position of hydrogen bonding functionality in the solid state structural self-assembly was investigated using diaminotriazine substituted diphenyl ether based positional isomers (1-5). The molecular shape was modulated by changing diaminotriazine position that produced channel supramolecular structures in 1, 3 and 5. There exists a direct correlation between the molecular shape and three dimensional structures; more linear molecules resulted in close-packing whereas molecules with a labyrinthine topology formed a channel structure. Supramolecular aspects pertaining to the influence of solvent of crystallization in structure formation and reversible structural transformation in solid state were also explored. 1-5 exhibited tunable solid state fluorescence (lambda(max) = 437-496 nm) depending on the diaminotriazine substitutional position and 3 showed solvent-dependent solid state fluorescence. The present study describes the generation of a supramolecular channel structure with functional properties such as tunable fluorescence by varying the position of hydrogen bond functionality and solvent of crystallization.

C-H center dot center dot center dot O-nitrate synthon assisted molecular assembly of hydrogen bonded Ni(II) and Cu(II) complexes

Two Schiff base metal complexes Cu-SPETNNO3 (1) and Ni-SPETNNO3 (2) SPETN=2,2-propane,1,3-diylbis(nitrilomethyldyne)pyridyl,phenolate] ] with hydrogen bonding groups have been synthesized and characterized by single-crystal X-ray diffraction. In both of the compounds nitrates occupy a crystallographic general position. In 1 the lattice nitrates are on the 2(1) screw axis while in 2 they are at the crystallographic inversion center. C-HOnitrate synthons (formed by the nitrate anions and peripheral hydrogen bonding groups of the metal complexes) are non-covalent building blocks in molecular-assembly and packing of the cationic Schiff base metal complexes (M=Ni2+, Cu2+), resulting in 2-D hydrogen bonded networks. The CuCu non-bonding contact in 1 is 3.268 angstrom while the Ni-Ni bonding distance in 2 is 3.437 angstrom.