One-dimensional Polymer Research Articles

Synthesis, crystal structure, and magnetic properties of a novel one-dimensional chain polymer based on 1-(4-nitrophenyl)-1,2,4-triazole

ABSTRACTA one-dimensional Co(II) complex [Co(BPDC)(NPT)]n (1) (H2BPDC = benzophenone-2,4′-dicarboxylic acid, NPT = 1-(4-nitrophenyl)-1,2,4-triazole) has been synthesized and characterized using single crystal X-ray diffraction, IR and elemental analysis. Single-crystal X-ray diffraction analysis revealed that complex 1 is a one-dimensional double chain polymer based on [Co2(OCO)2] binuclear motif. The thermal stability and magnetic properties of complex 1 have been investigated, which revealed antiferromagnetic coupling interaction exists between Co(II) ions.

Four Novel Zn (II) Coordination Polymers Based on 4'-Ferrocenyl-3,2':6',3''-Terpyridine: Engineering a Switch from 1D Helical Polymer Chain to 2D Network by Coordination Anion Modulation.

Four novel ZnII coordination polymers, [(ZnCl2)2(L)2]n (1), [(ZnBr2)2(L)2]n (2), and [(ZnI2)2(L)2]n (3) and {[Zn(SCN)2]1.5(L)3}n (4), have been synthesized based on 4′-ferrocenyl-3,2′:6′,3′′-terpyridine with ZnII ions and different coordination anions under similar ambient conditions. Their structures have been confirmed using single crystal X-ray diffraction analysis, showing that complexes 1–3 are one-dimensional (1D) double-stranded metal ion helical polymer chains and complex 4 is of a two-dimensional (2D) network. The structural transformations of them from a 1D polymer chain to a 2D network under the influence of the coordination anions has been systematic investigated. Furthermore, the optical band gaps have been measured by optical diffuse reflectance spectroscopy, revealing that the ligand and the complexes should have semiconductor properties.

Exploring the Relation Between Intramolecular Conjugation and Band Dispersion in One-Dimensional Polymers

Making use of the inherent surface anisotropy of different high index surface planes vicinal to the low index Au(111) orientation, one-dimensional polymers have been synthesized following established procedures from two different precursor molecules. The successful polymerization of both 4,4″-dibromo-p-terphenyl and 5,5′-dibromo-salophenato-Co(II) precursors into poly(p-phenylene) and poly[salophenato-Co(II)], respectively, has been confirmed by scanning tunneling microscopy and low energy electron diffraction. Angle-resolved photoemission spectroscopy data reveal a highly dispersive band in the case of poly(p-phenylene) while no significant dispersion is resolved for poly[salophenato-Co(II)]. On the basis of density functional theory calculations, we explain this observation as a result of a high conjugation along the aromatic phenyl groups in poly(p-phenylene) that is absent in the case of poly[salophenato-Co(II)], where intramolecular conjugation is interrupted in the salophenato-Co(II) unit. Furthermo...

Ultrasonic-assisted synthesis and the structural characterization of novel the zig-zag Cd(II) metal-organic polymer and their nanostructures

A sonochemical method was used to synthesize nano-rods of a novel cadmium(II) metal-organic coordination polymer, [Cd(p-2yeinh)(NO2)]n (1) (p-2yeinh = pyridin-2-yl ethylidene-isonicotinohydrazide). The effect of the synthesis parameters such as time, concentrations and irradiation power has been studied and optimized. It was shown that the thickness of rods has changed from 27 nm to 45 nm. The compounds were characterized by scanning electron microscopy (SEM), elemental analysis, IR spectroscopy, X-ray powder diffraction (XPRD), and single crystal X-ray analysis. The X-ray structure analysis revealed that the Cd(II) atom is coordinated by one oxygen and three nitrogen atoms from two p-2yeinh ligands and two oxygen atoms of single nitrite anion with a CuN3O3 donor set with distorted octahedral geometry. The crystal taking the form of a one-dimensional zig-zag polymer. The adjacent chains connected by π–π of adjacent aromatic rings of p-2yeinh and other weak interactions. Consequently, the weak interactions also allow the 1D zig-zag structure to form a 3D metal-organic coordination polymer. CdO nanoparticles were prepared by thermolysis of compound 1 at 180 °C with oleic acid as a surfactant. The average diameter of the nanoparticles was estimated by XPRD to be 23 nm. The morphology and size of the prepared CdO nanoparticles were further studied using SEM.

Tetrathiafulvalene Schiff base Cu(II) 1D coordination polymer upon a metallo-ligand approach

TTF-salicylaldehyde 1 has been prepared by Stille coupling between TTF-SnMe3 and 5-bromo-salicylaldehyde and characterized by single crystal X-ray structure analysis. A set of S⋯S, π-π and donor–acceptor intermolecular interactions is observed in the solid state architecture of this precursor. Its condensation reaction with 2-ethanolamine provided the chelating electroactive ligand 4-TTF-2-((2-hydroxyethyl)iminomethyl)-phenol 2 (H2L1). Reaction with Cu(OAc)2 in a 2:1 stoichiometry afforded the one-dimensional coordination chain-like polymer [Cu(HL1)2]n 3 for which the solid state structure has been determined. The Cu(II) coordination sphere contains in the equatorial plane a N2O2 motif arising from two chelating imino-phenol units, while the axial positions are occupied by hydroxo ligands from the pendant hydroxy-ethyl arms of top and bottom neighbouring intra-chain complexes with quite larger Cu–O distances indicative of Jahn-Teller elongation. The TTF units form regular stacks within the chains and further interact laterally through short S⋯S contacts. Cyclic voltammetry measurements on ligand 2 and complex 3 indicate excellent electron donating properties of these multifunctional precursors.

3-(Pyridin-4-yl)acetylacetone: a donor ligand towards mercury(II) halides and a versatile linker for complex materials.

The ditopic organic molecule 3-(pyridin-4-yl)acetylacetone (HacacPy) acts as a pyridine-type ligand towards HgX2 (X = Cl, Br, I). The nature of the anion and the ligand-to-cation ratio dominate the outcome of the reaction. Two different coordination compounds form with HgCl2, namely a ligand-rich mononuclear complex, HgCl2(HacacPy)2, and a ligand-deficient one-dimensional chain polymer, [Hg(μ-Cl)2(HacacPy)]1∞, with five-coordinated HgII cations. Two compounds are also observed for HgBr2, a molecular complex isomorphous to the chloride derivative and a chain polymer with the composition [Hg(μ-Br)Br(HacacPy)]1∞, in which the cations are four-coordinated. The ligand-rich mononuclear and ligand-deficient polymeric chloride and bromide complexes may be interconverted via thermal degradation and mechanochemical synthesis. In contrast to the chloride and bromide compounds, the reaction product with HgI2 does not depend on the ligand-to-cation ratio but corresponds to [Hg(μ-I)I(HacacPy)]1∞, isomorphous to the bromide derivative. The N-coordinated HacacPy complexes could not be deprotonated and further crosslinked with a second cation. Synthesis of mixed-metal products could be achieved, however, by deprotonation of the acetylacetone moiety in HacacPy and formation of tris-chelated Fe(acacPy)3 and Al(acacPy)3 complexes in the first step. These mononuclear building blocks act as bridging poly(pyridine) ligands towards HgII halides and form two structure types. The first represents a one-dimensional ladder, with the tris(ligand) complexes acting as triconnected nodes and the HgII halides acting as linkers. In the alternative unprecedented product, both the tris(ligand) complexes and the [HgX2(μ-X)HgX] groups act as equivalent triconnected nodes. They form a uninodal two-dimensional coordination network with vertex symbol 4.82 and fes topology.

3-(Pyridin-4-yl)acetylacetone: CdII and HgII compete for nitrogen coordination.

3-(Pyridin-4-yl)acetylacetone (HacacPy) acts as a pyridine-type ligand towards CdII and HgII halides. With CdBr2, the one-dimensional polymer [Cd(μ-Br)2(HacacPy)Cd(μ-Br)2(HacacPy)2]∞ is obtained in which five- and six-coordinated CdII cations alternate in the chain direction. Reaction of HacacPy with HgBr2 results in [Hg(μ-Br)Br(HacacPy)]∞, a polymer in which each HgII centre is tetracoordinated. In both compounds, each metal(II) cation is N-coordinated by at least one HacacPy ligand. Equimolar reaction between these CdII and HgII derivatives, either conducted in ethanol as solvent or via grinding in the solid state, leads to ligand redistribution and the formation of the well-ordered bimetallic polymer catena-poly[[bromidomercury(II)]-μ-bromido-[aquabis[4-hydroxy-3-(pyridin-4-yl)pent-3-en-2-one]cadmium(II)]-di-μ-bromido], [CdHgBr4(C10H11NO2)2(H2O)]n or [{HgBr}(μ-Br){(HacacPy)2Cd(H2O)}(μ-Br)2]∞. HgII and CdII cations alternate in the [100] direction. The HacacPy ligands do not bind to the HgII cations, which are tetracoordinated by three bridging and one terminal bromide ligand. The CdII centres adopt an only slightly distorted octahedral coordination. Three bromide ligands link them in a (2+1) pattern to neighbouring HgII atoms; two HacacPy ligands in a cis configuration, acting as N-atom donors, and a terminal aqua ligand complete the coordination sphere. Classical O-H...Br hydrogen bonds stabilize the polymeric chain. O-H...O hydrogen bonds between aqua H atoms and the uncoordinated carbonyl group of an HacacPy ligand in a neighbouring strand in the c direction link the chains into layers in the (010) plane.

Sequence-specific fluorometric recognition of HIV-1 ds-DNA with zwitterionic zinc(II)-carboxylate polymers

Four water-stable zwitterionic zinc-carboxylate polymers are prepared by reacting N-carboxymethyl-(3,5-dicarboxy)-pyridinium bromide (H3CmdcpBr) with zinc(II) nitrate in the presence of NaOH, through adjusting the solvents and ancillary ligands. With H2O as the solvent and the absence of an ancillary ligand, a two-dimensional (2D) polymer network [Zn(Cmdcp)(H2O)]n (1) is formed. In a mixed H2O/DMF solvent and with the presence of chelating ligands 2,2′-bipyridine (bipy), 1,10-phenanthroline (phen) and 2-(4-pyridyl)benzimidazole (pbz), a one-dimensional (1D) polymer of {[Zn2(Cmdcp)(bipy)2(H2O)5](NO3)2·3H2O}n (2), a mononuclear ionic species of [Zn(phen)(H2O)4][Cmdcp] (3), and a 2D polymer of {[Zn(Cmdcp)(pbz)][pbz]·7H2O}n (4) are accordingly formed. Compounds 1–4 are characterized by IR, elemental analyses and single crystal X-ray crystallography. Compound 2 strongly adsorbs single-stranded DNA (ss-DNA) probe (denoted as P-DNA) labeled with carboxyfluorescein (FAM) and quenches its fluorescence via a photo-induced electron transfer process. If, however, a double-stranded DNA (ds-DNA) of the human immunodeficiency virus 1 (HIV-1 ds-DNA) is further present, the P-DNA interacts with the major groove in HIV-1 ds-DNA via Hoogsteen hydrogen bonding to form a rigid triplex structure. This results in partial or complete fluorescence recovery depending on the concentration of HIV-1 ds-DNA. The findings are applied in fluorometric sensing of HIV-1 ds-DNA. The calibration plot is linear in the 0–60nM target DNA concentration range, with a 7.4nM detection limit (at a signal-to-noise ratio of 3). The assay is highly specific and not interfered by one base pair mutated for complementary target HIV-1 ds-DNA, complementary ss-DNA, single-base pair mutated for complementary ss-DNA, non-specific ss-DNA sequences, and higher-order dimeric G-quadruplexes.

A new hemidirected lead(II) complex extended in holodirected one-dimensional polymer by secondary Pb–O interactions: A precursor for preparation of PbO nanoparticles, and DFT study

A new 1D extended lead (II) coordination polymer [Pb(2-apinh) (NO3)2]n (1), (2-apinh = 2-acetylpyridine isonicotinoylhydrazone) has been synthesized by a thermal gradient method in a branched tube and characterized by elemental analysis, FT-IR, thermal analysis and single crystal X-ray diffraction. The single-crystal X-ray data show that the coordination number of Pb(II) in [Pb(2-apinh)(NO3)2] moieties is five (PbN2O3) with a stereo-chemically active lone pair on lead(II), and thus its coordination sphere is hemidirected. Moreover, each [Pb(2-apinh) (NO3)2] unit is linked by the secondary Pb⋯O7i interactions to form 1D extended coordination polymer, which approximately completes the Pb(II) coordination sphere with a Pb⋯O5 interaction (PbN2O5) in a holodirected geometry. In the solid state, the 1D chains are connected through non-covalent interactions, such as π⋯π stacking, C–H⋯π and C–H⋯O interactions to form 3D supramolecular network. Moreover, compound 1 exhibits 1D left-handed helical infinite chains along the c axis by non-covalent interactions. The structure of 1 has been optimized by density functional theory. The calculated structural parameters and IR spectra for the complex are in accordance with its crystal structure. PbO nanoparticles were obtained by thermolysis of 1 at 180 °C with oleic acid as a surfactant and characterized via FT-IR, XRD, and SEM.

Some mixed ligand halo complexes of mercury(II). Experimental support for Basolo’s principle of crystallisation

Neutral Hg2Cl4L (1), Hg2Br4L·dimethylformamide (2) and Hg2I4L (3) are synthesized where L is the 1:2 condensate of 1,2-diaminoethane and 1-methyl-2-imidazolecarboxaldehyde. X-ray crystal structures show that 1 and 3 are dinuclear with a distorted tetrahedral N2X2 (X=Cl or I) coordination sphere for Hg. Complex 2 is a one-dimensional polymer with bromide bridges. The metal has a square pyramidal (N2Br3) environment in all three complexes. Complexes 1–3 are reacted with R4NX (R=Me, Et or n-Butyl; X=Cl−, Br− or I−). While 1 and 3 show no reactions, 2 gives a crystalline complex (4) only when R=n-Bu and X=Br−. Complex 4 is ionic containing two independent n-Bu4N+ cations and two independent halves of centrosymmetric Hg2Br6L2− anions. The observed crystallisation of the anion Hg2Br6L2− only with the cation n-Bu4N+ and not with Me4N+ or Et4N+ is a consequence of Basolo’s principle of crystallisation of ionic salts which insists on the matching of the sizes of the counter ions. Though the size of the cation n-Bu4N+ matches with the hypothetical chloride and iodide analogues of 4, they are not formed. This is because while 2 has a tendency to increase the coordination number of Hg (as it polymerises), 1 and 3 do not show any such tendency.

Polymer Photonic Crystal Nanocavity for Precision Strain Sensing

We propose and experimentally demonstrate flexible one-dimensional polymer photonic crystal nanocavities with quality factors exceeding 104 for precision sensing of strain at experimentally measured values of 10–4. Relying on the cavity’s compact structure and polymer’s low Young’s modulus, the cavity’s displacement and the applied force are estimated as 0.94 nm and 55 nN, respectively. This flexible-nanocavity microsensor shows high linearity and repeatability. The microsensor concept is also compatible with liquid environments. The ease of fabrication, flexibility, and biocompatibility of the polymer microsensor promise applications in strain and force measurements at the microscale in the physical, material, and life sciences.

Thermally bisignate supramolecular polymerization.

One of the enticing characteristics of supramolecular polymers is their thermodynamic reversibility, which is attractive, in particular, for stimuli-responsive applications. These polymers usually disassemble upon heating, but here we report a supramolecular polymerization that occurs upon heating as well as cooling. This behaviour arises from the use of a metalloporphyrin-based tailored monomer bearing eight amide-containing side chains, which assembles into a highly thermostable one-dimensional polymer through π-stacking and multivalent hydrogen-bonding interactions, and a scavenger, 1-hexanol, in a dodecane-based solvent. At around 50 °C, the scavenger locks the monomer into a non-polymerizable form through competing hydrogen bonding. On cooling, the scavenger preferentially self-aggregates, unlocking the monomer for polymerization. Heating also results in unlocking the monomer for polymerization, by disrupting the dipole and hydrogen-bonding interactions with the scavenger. Analogous to 'upper and lower critical solution temperature phenomena' for covalently bonded polymers, such a thermally bisignate feature may lead to supramolecular polymers with tailored complex thermoresponsive properties.

Research of spin-orbit interaction in organic conjugated polymers

The effect of spin-orbit interaction on the one-dimensional organic polymer was investigated theoretically. Spin-orbital interaction led to the spatial separation of energy band but did not eliminate spin degeneration, which was different from energy level splitting in the Zeeman Effect. Spin-orbit interaction had little effect on the energy band structure, charge density, and lattice position, etc.; Spin precession was obtained when a polaron was transported along the polymer chain, which theoretically proved that it was feasible to control the spin precession of polaron in organic polymers by the use of external electric field.

Organic free decavanadate based materials: Inorganic linkers to obtain extended structures

Decavanadate based extended structures containing compounds [{Na3(H2O)8(μ2-H2O)6Ag2}HV10O28]n·6nH2O (1), [Co(H2O)6]n[{Na2(H2O)6(μ2-H2O)4Co(H2O)2}V10O28]n·4nH2O (2) and [Zn(H2O)6]n[{Na2(H2O)6(μ2-H2O)4Zn(H2O)2}V10O28]n·4nH2O (3) have been synthesized from respective aqueous solutions of sodium metavanadate. Compounds 1, 2 and 3 crystallize in a triclinic space group P-1. Compound 1 is a three-dimensional inorganic solid, whereas compounds 2 and 3 are isomorphous one-dimensional inorganic polymers. In the crystal structure of compound 1, the silver (I) cation is coordinated to the terminal oxygen as well as bridging oxygen atoms of decavanadate anion and it is also connected to bridging oxygen atom of trimeric sodium aqua cluster cation. In the crystals of compound 2, one hexa-hydrated cobalt cation is present as a counter cation and one “di-sodium cobalt aqua-complex” cation is supported on the [V10O28]6– cluster anion by coordinate covalent bond. Compound 3 is isomorphous with compound 2, with Zn2+ present (in compound 3) in the place of Co2+ (in compound 2). Compounds 1, 2 and 3 are characterized by routine elemental analyses, FT-IR spectroscopy and unambiguously by single crystal X-ray crystallography. In the crystal structure of compound 1, an unusual silver dimer is observed.

A new example of intra-molecular C-H⋯Ni anagostic inter-actions: synthesis, crystal structure and Hirshfeld analysis of cis-bis-[4-methyl-2-(1,2,3,4-tetra-hydro-naphthalen-1-yl-idene)hydrazinecarbo-thio-amidato-κ2N1,S]nickel(II) di-methyl-formamide monosolvate.

The reaction of NiII acetate tetra-hydrate with 4-methyl-2-(1,2,3,4-tetra-hydro-naphthalen-1-yl-idene)hydrazinecarbo-thio-amide in a 2:1 molar ratio and recrystallization from di-methyl-formamide yielded the title compound, [Ni(C12H14N3S)2]·C3H7NO. The ligands act as monoanionic κ2N1,S-donors, forming five-membered metallarings. The NiII ion is fourfold coordinated in a distorted square-planar cis-configuration, which is rather uncommon for mono-thio-semicarbazone complexes. Intra-molecular H⋯Ni trans-inter-actions are observed [H⋯Ni distances are 2.50 and 2.57 Å] and thus anagostic inter-actions can be suggested. The Hirshfeld surface analysis indicates that the major contributions for the crystal packing are H⋯H (66.6%), H⋯S (12.3%) and H⋯C (10.9%) inter-actions. In the crystal, the complex mol-ecules are linked by di-methyl-formamide solvent mol-ecules through N-H⋯O inter-actions into one-dimensional hydrogen-bonded polymers along [010].

A comparative structural and property investigation of four new bivalent transition metal complexes based on 4-nitrophenylacetic acid with rigid 4-nitrobenzoate analogues

The synthesis, spectral, thermal, magnetic properties, and structural features of four new one-dimensional (1-D) polymers having formula [M(4-npa)2(μ2-H2O)(H2O)2]·2H2O where (M=Mn 1; M=Co 2; M=Zn 3; M=Ni 4; 4-npa=4-nitrophenylacetate) are investigated and compared with corresponding 4-nitrobenzoate (4-nba) analogues. The single crystal studies reveal that compounds 1–3 are isostructural and crystallize in the centrosymmetric monoclinic space group P21/c. Their structure consists of distorted octahedra of a unique central metal ion, two crystallographically unique monodentate 4-npa ligands, two terminal water molecules, a μ2-bridging bidentate water and two lattice water molecules. The central metal exhibits a distorted {MO6} octahedron with two O atoms from terminal water molecules disposed cis to each other, two O atoms from the monodentate carboxylates also disposed in a cis geometry and the remaining two O atom from the μ2-bridging bidentate water disposed trans. The μ2-brindging mode of water leads to the formation of an extended 1-D chain structure. The lattice water links parallel 1-D chains with the aid of H-bonding interactions. The IR, XRD powder pattern, thermal characterization and elemental analysis reveal that the structure of polycrystalline compound 4 is nearly identical with that of other 4-npa analogues.

Temperature-Induced, Selective Assembly of Supramolecular Colloids in Water.

In this article, we report the synthesis and physical characterization of colloidal polystyrene particles that carry water-soluble supramolecular N,N′,N″,-trialkyl-benzene-1,3,5-tricarboxamides (BTAs) on their surface. These molecules are known to assemble into one-dimensional supramolecular polymers via noncovalent interactions. By tethering the BTAs to charge-stabilized particles, the clustering behavior of the resulting colloids was dictated by a balance between interparticle electrostatic repulsion and the BTA-mediated attractions. Through careful tuning of the dispersing medium’s ionic strength, a regime was found in which particle aggregation could be reversibly induced upon heating the dispersion. These findings clearly indicate that hydrophobic interactions, which become stronger upon heating, play an important role during the clustering process. Besides the thermoreversible nature of the generated hydrophobic interparticle attractions, we found the clustering to be selective, that is, the BTA-functionalized colloids do not interact with nonfunctionalized hydrophobic polystyrene particles. This selectivity in the association process can be rationalized by the preferred stacking of the surface-tethered BTAs. These selective intermolecular/particle bonds are likely stabilized by the formation of hydrogen bonds, as previously observed for analogous molecular BTA assemblies. The resulting driving force responsible for particle clustering is therefore dual in nature and depends on both hydrophobic attractions and hydrogen bonding.

Orbitals, Occupation Numbers, and Band Structure of Short One-Dimensional Cadmium Telluride Polymers.

Recent work found that soldering CdTe quantum dots together with a molecular CdTe polymer yielded field-effect transistors with much greater electron mobility than quantum dots alone. We present a computational study of the CdTe polymer using the active-space variational two-electron reduced density matrix (2-RDM) method. While analogous complete active-space self-consistent field (CASSCF) methods scale exponentially with the number of active orbitals, the active-space variational 2-RDM method exhibits polynomial scaling. A CASSCF calculation using the (48o,64e) active space studied in this paper requires 1024 determinants and is therefore intractable, while the variational 2-RDM method in the same active space requires only 2.1 × 107 variables. Natural orbitals, natural-orbital occupations, charge gaps, and Mulliken charges are reported as a function of polymer length. The polymer, we find, is strongly correlated, despite possessing a simple sp3-hybridized bonding scheme. Calculations reveal the formation of a nearly saturated valence band as the polymer grows and a charge gap that decreases sharply with polymer length.

A heterometallic polymer based on bis-salicylidene Schiff base ligand, synthesis, electronic chemistry, and antibacterial property

ABSTRACTA new heterometallic complex containing bis-Schiff base, namely, [(Salbn)NiNa(DMF)(H2O)]·N(CN)2 (1) (Salbn = bis(3-methoxysalicylidene) benzene-1, 2-diamine, DMF = N, N-dimethyl formamide) has been prepared through one-pot refluxing and condensation approach. Complex 1 was characterized by elemental analysis, IR spectroscopy, X-ray single-crystal diffraction, and powder X-ray diffraction analysis. The intermolecular hydrogen bonding interaction connects the Schiff base complex units through the [N(CN)2]− anion into dimer aggregate. These aggregates are further linked by weak hydrogen bondings and strong π–π interactions to give rise to one-dimensional chelating double-chain supramolecular polymer. Cyclic voltammetry measurement reveals the oxidation and reduction process of the compound is irreversible in nature. Polymer 1 exhibits emission spectrum maximum at 548 nm under ultraviolet excitation. Antibacterial property measurement indicates that 1 has strong inhibition toward Staphylococcus aureus.

AgI and PbII as Additional Assembling Cations in Uranyl Coordination Polymers and Frameworks

Five mono- or polycarboxylic acids have been used to generate a series of eight heterometallic uranyl complexes involving silver(I) or lead(II) cations, all synthesized under (solvo)-hydrothermal conditions. Pimelic acid (H2pim) gave complexes [Ag(bipy)2]2[UO2(pim)(NO3)]2 (1) and [UO2Pb(pim)2(bipy)(H2O)]·0.5bipy·H2O (2) (bipy = 2,2′-bipyridine), which both crystallize as one-dimensional (1D) polymers, but differ in that the silver(I) cations are separate counterions, while carboxylate-bound lead(II) cations are an essential component of the polymer. Only silver(I)-containing species were obtained with all-cis-1,3,5-cyclohexanetricarboxylic acid (H3chtc), [UO2Ag(chtc)(H2O)2] (3) and [Ag(bipy) (CH3CN)]2[UO2(chtc)]2 (4); both contain two-dimensional (2D) uranyl carboxylate subunits with honeycomb {63} topology, these being united into a three-dimensional (3D) framework with the lonsdaleite {66} topology by bridging, oxo-bound silver(I) cations in 3. Both silver- and lead-containing complexes were obtained with 3,3′,4,4′-biphenyltetracarboxylic acid (H4bptc), [UO2Ag(bptc)(4,4′-bipyH)] (5) and [UO2Pb(bptc)(bipy)2] (6) (4,4′-bipy = 4,4′-bipyridine), and they both display a 2D uranyl carboxylate network with the {44.62} topology, the additional cations and N-donors being decorating species. In this case, a higher dimensionality was obtained not with an additional cation, but with a coordinated N-methyl-2-pyrrolidone (NMP) molecule, since [(UO2)2(bptc)(NMP)1.5(H2O)1.5]·1.5H2O (7) crystallizes as a three-dimensional (3D) framework. In the presence of silver(I), 3-pyrimidin-2-yl-benzoic acid (Hpyb) gave the complex [UO2Ag(pyb)3(H2O)2]·4H2O (8), in which the two coordination sites are occupied in accord with Hard/Soft Acid/Base (HSAB) principles, uranyl being chelated by three carboxylate groups and silver(I) being bound to nitrogen atoms; the 1D polymer formed bridges to another through silver–uranyl oxo bonding. In contrast, the homometallic, molecular complex [UO2(pyb)2(bipy)] (9) was obtained in the presence of lead(II) cations. The lead-containing complex with 2,6-pyridinedicarboxylic acid (H2pydc), [UO2Pb2(pydc)2(phen)2(HCOO)1.5(NO3)0.5]·0.5H2O (10) (phen = 1,10-phenanthroline), crystallizes as a 1D polymer in which uranyl is bound to two O,N,O-donors, as usual with this ligand, polymerization being due to lateral double lead(II) bridges. Variations in uranyl emission maxima positions appear to be essentially related to the uranium coordination number within the present series.