3D Diamondoid Research Articles

From achiral tetrazolate-based tectons to chiral coordination networks: effects of substituents on the structures and NLO properties

Using a hydrothermal synthesis method, the combination of four tetrazolate-yl acylamide tectons bearing substituents of different sizes, 4-nitro-N-(1H-tetrazol-5-yl)benzamide (H-NTBAN), 4-fluoro-N-(1H-tetrazol-5-yl)benzamide (H-NTBAF), N-(1H-tetrazol-5-yl)isonicotinamide (H-NTINA) and N-(1H-tetrazol-5-yl)thiophene-2-carboxamide (H-NTTCA), with cadmium dichloride led to four crystalline coordination networks, named Cd3(NTBAN)6 (1), Cd(NTBAF)2 (2), Cd(NTINA)2 (3) and Cd(NTTCA)2 (4), respectively. The X-ray diffraction analysis revealed that compounds 2, 3 and 4 possess a 3D non-interpenetrated diamondoid framework, while compound 1 is of a 0D trinuclear structure. Wherein, compounds 2, 3 and 4 crystallized in chiral space groups with significant second harmonic generation (SHG) efficiencies. The effects of substituents in the semirigid tetrazole-yl acylamide tectons on the structural topologies as well as on the nonlinear optical properties of the generated coordination networks are discussed.

Coordination polymers of tetrazole-yl acylamide with octahedrally coordinated divalent transition metals: the effects of metal centers and side-groups on the structural topologies and symmetries

Hydrothermal reactions of divalent transition metal salts with two different-sized tetrazole-yl acylamide ligands, N-(1H-tetrazol-5-yl)acetamide (H-NTAA) and N-(1H-tetrazol-5-yl)propionamide (H-NTPA), led to six crystalline coordination polymers, named Cd(NTAA)2 (1), Zn(NTAA)2·∼H2O (2), Cu(NTAA)2 (3), Mn(NTAA)2 (4), Cd(NTPA)2 (5), Mn(NTPA)2 (6), respectively. The X-ray diffraction analysis revealed that compound 2 is a 1D zigzag chain, compounds 3 and 4 exhibit an interesting 2D 44-sql network, while compounds 1, 5 and 6 possess a 3D non-interpenetrated diamondoid framework. Wherein, compounds 1, 4, 5 and 6 crystallized in an acentric space group with significant second harmonic generation (SHG) efficiencies. The effect of metal ions and that of small aliphatic acyl side-groups in semirigid tetrazole-yl acylamide ligands on the structural topologies and symmetries of generated coordination polymers are discussed.

Metal(II) Coordination Polymers Derived from Bis-pyridyl-bis-amide Ligands and Carboxylates: Syntheses, Topological Structures, and Photoluminescence Properties

Using bis-pyridyl-bis-amide ligands N,N′-bis-(4-pyridyl)phthalamide (L1), N,N′-bis-(4-pyridyl)iso -phthalamide (L2), hexanedioic acid bis-pyridin-4-ylamide (L3), and carboxylates, six metal(II) complexes formulated as Cd2(1,4-chdc)(L1)2·4H2O (1,4-H2chdc = 1,4-cyclohexanedicarboxylic acid) (1), Cd2(L1)2(in)4·3DMF (Hin = isonicotinic acid) (2), Zn(L1)(1,4-bdc) (1,4-H2bdc = 1,4-benzenedicarboxylic acid) (3), Cd(L2)(1,4-chdc) (4), Zn2(L2)2(tdc)2·DMF (H2tdc = thiophene-2,5-dicarboxylic acid) (5), and Zn(2,6-ndc)0.5(L3)0.5(SO4)·(CH3NHCH3) (2,6-H2ndc = 2,6-naphthalene- dicarboxylic acid) (6) have been hydro(solvo)thermally synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 is a uninodal 6-connected noninterpenetrated three-dimensional (3D) network with {44.610.8}-mab topology, complex 2 exhibits a uninodal 6-connected 2-fold interpenetrated 3D framework with {412.63}-pcu topology, complex 3 shows a uninodal 8-fold interpenetrated 3D diamondoid framework, complexes 4 and 5 p...

Ligand geometry-driven formation of different coordination polymers from Zn(NO3)2, 1,4-bpeb and phenylenediacetic acids

The hydrothermal reactions of Zn(NO3)2·6H2O with 1,4-bis[2-(4-pyridyl)ethenyl]benzene (1,4-bpeb), NaOH, and 1,4-phenylenediacetic acid (1,4-H2PDA), 1,3-phenylenediacetic acid (1,3-H2PDA) or 1,2-phenylenediacetic acid (1,2-H2PDA) afforded three coordination polymers {[Zn(1,4-PDA)(1,4-bpeb)]·2H2O}n (1), [Zn(1,3-PDA)(1,4-bpeb)]n (2) and [Zn4(μ-OH)2(1,2-PDA)3(1,4-bpeb)2]n (3), respectively. All these compounds were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. 1 exhibits a five-fold interpenetrating 3D diamondoid framework constructed by linking Zn atoms with trans-1,4-PDA and trans-trans-trans-1,4-bpeb ligands. 2 has a 2D (4,4) network formed by connecting dinuclear [Zn2(1,3-PDA)2] (1,3-PDA serving as a trans conformation) units with trans-cis-trans-1,4-bpeb ligands. 3 could be considered as a 2D 5-connected network derived from linking tetranuclear [Zn4(μ-OH)2(1,2-PDA)3] (1,2-PDA acting as cis and trans conformations) units via trans-cis-trans-1,4-bpeb bridges. The results provided some insight into the ligand geometry-driven assembly of coordination polymers. Thermal stability and photoluminescent properties of 1–3 were also investigated.

Construction of a 2D Rectangular Grid and 3D Diamondoid Interpenetrated Frameworks and Their Functionalities by Changing the Second Spacers

AbstractThree new metal–organic ZnII frameworks, {[Zn(bipy)(1,4‐ndc)(H2O)2]·2H2O} (1), {[Zn(bpe)(1,4‐ndc)]2·2DMF} (2), {[Zn(bpee)(1,4‐ndc)]2·2DMF} (3) [bipy = 4,4′‐bipyridyl, 1,4‐ndc = 1,4‐naphthalenedicarboxylate, bpe = 1,2‐bis(4‐pyridyl)ethane, bpee = 1,2‐bis(4‐pyridyl)ethylene], have been synthesized by using mixed‐ligand systems under solvothermal conditions and characterized structurally by single‐crystal X‐ray diffraction. Compound 1 has a 2D structure with 44‐sql net topology, whereas 2 and 3 have a 3D diamondoid structure with interesting fourfold interpenetrated topology. Topological analyses of the diamondoid nets in compounds 2 and 3 reveal a 4‐connected net with 66 topology. Thermogravimetric experiments suggest that the solvent‐free compounds 1–3 are stable up to 370, 330, and 280 °C, respectively. The grids of 1 stack in –ABCD– fashion without any regular channel structure. Desolvated compound 2 (2′) selectively adsorbs CO2 over N2, and such discrimination is regulated by the restricted window dimension of the channels. Solvent vapor (H2O, MeOH, and EtOH) adsorption studies with 2′ suggest a hydrophobic nature of the pore surface. Gas and vapor adsorption studies with 3′ reveal no uptake, which can be correlated to a smaller pore size relative to the kinetic diameter of the respective adsorbates.

Syntheses and Crystal Structures of a Series of Coordination Polymers Constructed From C2‐Symmetric Ligand 1,3‐Adamantanedicarboxylic Acid

This article systematically investigates the influence of the properties of inhomogeneous N-auxiliary ligands and pH value on the helical structures of complexes based on C(2)-symmetric ligand 1,3-adamantanedicarboxylic acid (H(2)ADC). Five kinds of neutral ligands (phen=1,10-phenanthroline, bipy=4,4'-bipyridine, bpa=1,2-bis(4-pyridyl)ethane, bpe=1,2-bis(4-pyridyl)ethane, and bpp=1,3-bis(4-pyridyl)propane) were selected, and a series of new Zn(II)/Co(II) dicarboxylates have been synthesized by slow diffusion, namely, [Zn(phen)(ADC)(H(2)O)](2).CH(3)OH (1), {[Zn(ADC)(bpe)].H(2)O}(n) (2), {[Zn(ADC)(bipy)].2H(2)O}(n) (3), {[Zn(ADC)(bpa)](2).5H(2)O}(n) (4), {[Zn(ADC)(bpp)](2).CH(3)OH}(n) (5), {[Zn(ADC)(bpp)]}(n) (6), {[Co(ADC)(bpp)(CH(3)OH)(H(2)O)].CH(3)OH2 H(2)O}(n) (7), and {[Co(ADC)(bpp)]}(n) (8). Single-crystal X-ray structural analysis shows that complex 1 forms a 0D dinuclear with closed-loop unit. The complex 2 is a 2D layer framework. Compounds 3 and 4 are isomorphous with a small discrepancy and present one-dimensional chainlike structures. It is interesting that the 2D organic-inorganic hybrid frameworks containing meso-helical chains have been observed. Compound 5 is a 2D interpenetrated network with (4,4) topology, in which homochiral left-handed helical chains are arranged in an ABAB sequence parallel to the plane defined by (a,c), and right-handed helical chains running along the a axis are also observed in the solid state, resulting in a meso-helical structure. Compounds 6, 7, and 8 crystallize in a chiral space group P212121. Highly dimensional 6 and 8 are essentially isostructural and present a threefold interpenetrated 3D diamondoid network containing three helical chains, whereas 7 exhibits a 2D grid layer with a left-handed helical chain. Furthermore, thermal stability, X-ray powder diffraction, and the luminescent properties of 1-6 are also discussed.

Structural variation from 1D to 3D: effect of metal centers on the construction of metal–organic coordination polymers with N-(1H-tetrazol-5-yl)benzamide ligand

A new multifunctional semirigid acylamide ligand comprising a tetrazole ring, N-(1H-tetrazol-5-yl)benzamide (HL), has been synthesized, with which five coordination polymers of different metal ions, namely, CdL2 (1), AgL (2), MnL2 (3), CuL2 (4), PbL2 (5), have been prepared and characterized by elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction. The X-ray diffraction analysis reveals that compound 1 crystallized in a chiral space group and is a 3D non-interpenetrated diamondoid framework with Cd(II) centers in tetrahedral geometry. Compound 2 is a 2D coordination polymer with a 3-connected 4·82-fes topology. Compounds 3 and 4 are isomorphous, and both of them exhibit an interesting 2D 44-sql network while compound 5 shows 1D zigzag chains. Thermal stabilities, photoluminescence and NLO properties have also been studied.

A spontaneously resoluted zinc–organic framework with nonlinear optical and ferroelectric properties generated from tetrazolate-ethyl ester ligand

A homochiral 3D diamondoid metal–organic framework [Zn2(etza)4] (1, named JUC-81, JUC = Jilin University, China, Hetza = ethyl 1H-tetrazole-5-acetate) has been prepared through spontaneous resolution. The bulk crystals have enantiomeric excess observed by vibrational circular dichroism (VCD) spectra, and also show second-order nonlinear optical effects and ferroelectric feature.

A chiral diamondoid 3D lanthanum metal–organic framework displaying blue-greenish long lifetime photoluminescence emission

The compound [La(pmtz)(TzC)(H2O)3](H2O) (pmtz = 5-(pyrimidyl)-tetrazolato, TzC = 5-carboxylato-tetrazolato) has been prepared under hydrothermal conditions and exhibits a 3D diamondoid network. This three-dimensional metal–organic framework has channels with hosted water molecules inside and shows an intense blue-greenish long lifetime photoluminescence emission at room temperature in the solid state with two lifetime decay values of 0.26 and 27 ms.

Three new coordination polymers based on 4-oxo-1(4H)quinolineacetate: Synthesis, structures and luminescent properties

Reactions of Hoqa and varied metal salts resulted in the formation of three new coordination polymers, which exhibit two structure features, such as a 3D diamondoid network and 1D chain. Reactions of 4-oxo-1(4H)-quinolineacetic acid (Hoqa) and varied metal salts of Zn(II), Cd(II) and Ag(I) resulted in the formation of three new coordination polymers, namely, [Zn(oqa) 2 ]·H 2 O ( 1 ), [Cd(bpy)(oqa) 2 (H 2 O) 2 ]·4H 2 O ( 2 ) and [Ag(bpy)(oqa)]·2H 2 O ( 3 ) (bpy = 4,4′-bipyridine). Complex 1 has a three-dimensional (3D) polymeric network with diamondoid topology; compounds 2 – 3 exhibit one-dimensional (1D) chain structure characteristics, which are further assembled through π–π stacking attractions and hydrogen bonds, forming the 3D supramolecular frameworks. In addition, the solid-state luminescent properties of the ligand Hoqa and complexes 1 – 2 have been investigated at room temperature.

Five Metal(II) Coordination Polymers Constructed from Two Vanillin Derivatives: From Discrete Structure to 3D Diamondoid Network

Two vanillin derivatives, 4-hydroxy-3-methoxybenzaldehyde nicotinoylhydrazone (L1) and 4-hydroxy-3-methoxybenzaldehyde salicyloylhydrazone (L2), were synthesized. The two flexible ligands have been employed to assemble with Pb(II), Cu(II), or Co(II) ion, leading to the formation of five coordination polymers varying from zero- to three-dimensional structures. Complex [Pb2(L1)2(NO3)2]·3H2O (1) features a novel 3D diamond-like coordination network based on binuclear units as binodes and hydrazone ligands, L1, as linkers. However, complex Pb2(L1)2(OAc)2(H2O)2 (2) presents a 1D double-strand chain structure. Two factors, the second ligand (acid ligand) and different coordination ability of water molecules, are investigated to further explore its relationship with the resultant crystalline architectures in complexes 1 and 2. The donor atoms in the two lead(II) complexes 1 and 2 can cluster to one side leaving an “open” coordination site to accommodate the stereochemically active 6s2 lone pair. Complex Cu(L2)2 ...

Sixfold interpenetrated diamondoid network of Cu(I): Synthesis, structure, selective anion exchange and luminescence properties

A novel metal-organic framework of Cu(I), {[Cu(bphz)2] · 2BF4}n (1) (bphz = 1,2-bis(4-pyridylmethylene)hydrazine) has been synthesized and structurally characterized. Structure determination reveals a 3D diamondoid network with 1D channels filled with the BF4- anions which undergoes F⋯F interactions forming 1D (BF4-)n chains in the crystallographic c-axis. The six independent 3D diamondoid networks are sixfold interpenetrating, forming a rare example of sixfold interpenetrated 3D diamondoid network. The framework also exhibits photoluminescence properties and selective reversible anion exchange ability with the NO3- anions, but not with the ClO4- and PF6- anions. The highly selective anion exchange ability is correlated with the size and shape of the anions compare to the channel aperture.

Construction of Three-Dimensional Metal−Organic Frameworks with Helical Character through Coordinative and Supramolecular Interactions

Self-assemblies of the semirigid dipolar ligand 1,4-bis(benzimidazol-1-ylmethyl)benzene (L) with zinc and cobalt salts have led to six new complexes, namely, {[M(L)(DMF)2(H2O)2]·2(NO3)}n [M = Zn (1) and Co (2)], {[M(L)2Cl2]·DMF·S}n [M = Zn(3), S = C2H5OH; Co(4), S = CH3OH + H2O], [Zn(L)2]·(ClO4)2·4DMF·3H2O]n (5), and {[Co(L)2(DMF)2](ClO4)2}n (6), respectively. Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric analyses. Compounds 1 and 2 are isomorphous and present one-dimensional chain-like structures. It is interesting that three-dimensional (3D) organic−inorganic hybrid frameworks containing meso-helical chains (P + M) have been observed in the solid-state of 1 and 2, in which meso-helical chains are alternately trapped by the cooperative association of coordination interactions as well as hydrogen bonds. With the replacement of ZnII/CoII nitrate salts with ZnCl2 or CoCl2 in the above reactions, the resulting complexes 3 and 4 contain P-helical and M-helical chains with 21 screw axis but crystallize as a racemate. Through π···π stacking interactions between two well-overlapping benzimidazoleyl rings from two adjacent chains, the 3D racemic supramolecular network is further assembled. However, reaction of M(ClO4)2 (M = Zn(5), Co(6)) and L yields two high dimensional compounds 5 and 6 with helical character, in which compound 5 has a two-dimensional (2D) (4,4) wave-like layer constructed by vertical crossing of the left-(M) and right-(P)-handed helical chains with the central ZnII ions as the hinge nodes, and similarly, the final 3D supramolecular structure is assembled via weak π···π interactions between two central benzene rings from two adjacent ligands L of two neighboring 2D layers. Compound 6 presents a four-connected 3-fold interpenetrated 3D diamondoid network containing meso-helical chains along two mutually perpendicular directions, respectively. Furthermore, the photoluminescent properties of compounds 1, 3, and 5 were studied.

A novel 3D microporous metal-organic framework of cadmium(II) oxalate with diamondoid network

A three-dimensional (3D) metal-organic framework of cadmium(II) oxalate, [Cd(C2O4)2(H2O)](H2O)(H3O)2(C2H5OH) 1, has been created by decomposition of pyridine-2,4,6-tricarboxylic acid under solvothermal reaction condition. Single crystal X-ray diffraction analysis shows that complex 1 self-assembles into a 3D noninterpenetrated diamondoid network with open channels accommodating guest ethanol and water molecules. The thermostability and nitrogen adsorptive property of 1 were investigated.

Copper(i) and silver(i) coordination frameworks involving extended bipyridazine bridges

1,4-(Pyridazin-4-yl)benzene (bpph), a new N-donor tetradentate ligand, was prepared by inverse electron demand cycloaddition reacting 1,4-diethynylbenzene and 1,2,4,5-tetrazine. In combination with Cu(I) and Ag(I) ions, it affords coordination framework topologies that were dominated by assembly of dinuclear metal–pyridazine “secondary building blocks” [M2(μ-pdz)2] supporting further polymeric connectivity. In structures [Cu2(bpph)(CH3CN)2{S2O6}] (1) and [Ag6(bpph)3(H2O)6{C6H4(COO)2}2]C6H4(COO)2·4H2O (8) interconnection of the dinuclear nodes occurs with anionic dithionate and isophthalate bridges, while [Ag2(bpph){C6H5CO2}2]·2H2O (7) adopts a linear chain structure incorporating disilver(I) pyridazine units and terminal benzoate anions. [Cu4(bpph)5](BF4)4·4CHCl3 (2) has a 3D supramolecular structure involving polycatenation of the 2D “bilayer” metal–organic topologies built up of five-connected dinuclear nodes. Frameworks of [Ag(bpph){NO3}]·CHCl3 (3) and [Ag(bpph){C2F5COO}] (5) exist as 2D square-grids nets supported with sets of tetra- and bidentate bipyridazine bridges, while closely related [Ag4(bpph)3{CF3COO}4]·CH3CN (4) is a 1D “ladder” polymer. The three-fold interpenetrated 3D diamondoid framework of [Ag4(bpph)3{CH3SO3}4]·2CHCl3 (6) was based upon more complicated tetranuclear nodes [Ag4(μ-pdz)4(pdz)2].

Tuning framework formation by flexible ligand elongation and second ligating spacer variation: increasing dimensionality and macrocycle size

An investigation on the dependence of the framework formation of coordination polymers is reported based on the self-assembly of copper(I) halide or pseudohalide and two relating nitrogen-containing heterocyclic thioether ligands, L1 and L2 [L1 = bis(2-pyrimidinylthio)methane, L2 = 1,2-bis(2-pyrimidinylthio)ethane]. Four new metal–organic frameworks, namely [Cu2I2(L1)2]n (1), [CuCN(L1)]n (2), [Cu2I2(L2)2]n·nL2 (3) and [CuCN(L2)]n (4) have been synthesized and characterized by X-ray crystallography. Structural diversities of these frameworks can be adjusted by elongation of flexible dithioether ligands and the selection of second ligating spacers, resulting in increasing structural dimensionality from a 1D linear chain (1), 2D layers (2,3) to a 3D diamondoid network (4). There exist fused macrocyclic rings with increasing sizes in these frameworks, ranging from 16-, 22-, 40- to 42- membered rings, respectively. The repeating “square” 40-membered macrocycle [Cu6I2(L2)4] in 3 is so large that two free L2 molecules occupy the voids of the macrocycle, stabilizing the channel-like assembly through intermolecular N⋯S interactions between the pyrimidyl rings of the L2 guest and the macrocycle-based host, whereas large macrocycles lead to two-fold interpenetration of the diamondoid nets of 4. Complexes 1–4 all show yellow photoluminescence in the solid state at room temperature.

Manipulation of molecular aggregation and supramolecular structure using self-assembled lithium mixed-anion complexes

A set of zero-, one-, two-, and three-dimensional materials have been synthesized by systematically varying the stoichiometry of the two components 2,4,6-Me3-C6H2OLi (ArOLi) and Me2N(CH2)(2)OLi (ROLi) within single aggregates, while using 1,4-dioxane (diox) as a ditopic linker. The homoleptic complex [{(ArOLi)4 x (diox)2} superset3(diox)](infinity) 1 forms a 3D diamondoid extended structure, where Li4O4 cubanes act as tetrahedral nodes. Attempts to rationally alter the dimensionality of the network through the sequential replacement of ArOLi vertices by potentially chelating ROLi units have succeeded. The mixed-anion complexes [{(ROLi)(ArOLi)3 x (diox)(1.5)} superset1/2(C6H14)](infinity) 2 and [(ROLi)4(ArOLi)2 x (diox)](infinity) 4 , adopt 2D hexagonal net and 1D chain structures respectively. Furthermore, the two complexes [{(ROLi)3(ArOLi)3 x (diox)(0.5)}(C6H14)](infinity) 3 and [(ROLi) 5(ArOLi) x (diox)(0.5)](infinity) 5 both form unusual 0D molecular dumbbell structures in the solid state. Incorporation of multiple ROLi units in the mixed-anion complexes not only results in reducing the number of possible sites for polymer extension through chelation, but also changes the aggregation state of the building block from tetrametallic Li4O4 units to hexametallic Li6O6 units.

Molecular networks. Design and serendipity

The supramolecular assembly of a 2D honeycomb network viacarboxylic acid–pyrimidinone-dimer synthon and the unexpected occurrence of 3D diamondoid net in the crystal structure of a dipyridyl urea hydrate illustrate the title theme.

The First Homochiral Diamond‐Like Coordination Polymer Containing Cubane Cluster (Cu4I4) as Connecting Node and Cinchonine as Donor‐Acceptor (or Push‐Pull Electronic Effect) Building Block

AbstractThe reaction of CuI with cinchonine (an organic donor‐acceptor chromophore) afforded a homochiral 3D diamondoid network [Cu4I4(cinchonine)2]n (1) containing a cubane cluster (Cu4I4) as a connecting node. This is the first homochiral coordination polymer with diamondoid nets containing a cluster as a connecting note. Its thermal stability and solid state optical properties such as fluorescence, circular dichroism and second‐harmonic generation response were also reported.

Metal-Directed Supramolecular Architectures: From Mononuclear to 3D Frameworks Based on In Situ Tetrazole Ligand Synthesis

This work focuses on the investigation of the influence of metal ions and supramolecular interactions on the self-assembly of in situ generated tetrazolate coordination architectures. A series of new metal−organic complexes, [Zn(pzta)2(H2O)2] (1), [Cu(pzta)2](H2O)3 (2), [Cd(pzta)2]n (3), [Ag(pzta)]n (4), and [Cd2(pzta)(OH)(SO4)]n (5) [pzta = pyrazinyl tetrazolate], have been achieved by the in situ hydrothermal reactions of pyrazinecarbonitrile, sodium azide, and different metal ions. Complexes 1 and 2 have similar mononuclear structures bearing distinct intermolecular hydrogen-bond interactions to form two different 3D supramolecular networks based on 44-subnets. Complex 3 features a 1D crossed-shape chain structure. Complex 4 is a coordination polymer comprised of mildly undulated 2D layers with a (4.82) topological network. Complex 5 is a 3D diamondoid framework constructed by pentanuclear cadmium cluster nodes and pzta linkers. The configurations of complexes 1−5 span from mononuclear (1, 2), to one-d...