1D Polymeric Structure Research Articles

Investigations of Nanoparticle Suspensions of Prussian Blue and Its Copper Analogue: Amine Functionalization and Electrochemical Studies

Prussian blue (PB) and its analogues are promising materials for electrochemical energy storage, yet their use in flow-type devices is limited by their lack of redox responsiveness as colloidal suspensions. We have investigated the redox chemistry amine functionalization of PB along with its Cu analogue (CuPBA). No redox response of colloidal PB was observed and suspensions of CuPBA formed films on electrode surfaces with and without applied potentials; the films were redox-active but the material that remained suspended in solution did not participate in redox chemistry. Propylamine (pa), ethylenediamine (en), or tetramethylethylenediamine (TMEDA) were added in an attempt to maintain well dispersed suspensions through nanoparticle surface functionalization. Propylamine modifications resulted in a loss of the CuPBA network and subsequent precipitation of insoluble materials. Coordination of ethylenediamine prompted the formation of Cu and Fe monomers ([Cu(en)2]m+/[Fe(CN)6]n-]) that remained soluble in aqueous electrolytes. In the absence of supporting electrolytes, these monomers formed a one-dimensional (1D) polymeric structure (Cu2Fe-1D). TMEDA modification preserved the CuPBA extended structure with only modest precipitate formation over 30 min. The redox responsiveness of these suspensions depended on conditions; in 1 M KCl, no redox chemistry was observed for the CuPBA. In pH 4 potassium hydrogen phthalate buffer, a signal was observed that was attributed to the Fe centers of CuPBA. Under these conditions, the material precipitated in ∼15 min and the signal was lost. Although the Fe centers in these networks are redox-active, additional work is needed to realize longer-term redox activity and stability. Ligand modifications can alter the properties of these networks but within a given ligand class, e.g., amines, the effects can vary greatly from the deconstruction of the framework to preventing film formation.

142Development of an alginate-gelatin bioink enhancing osteogenic differentiation by gelatin release.

Hydrogels are natural bioink options for cellular printing due to their high-water content and permeable three-dimensional (3D) polymeric structure, which are favorable for cellular anchoring and metabolic activities. To increase the functionality of hydrogels as bioinks, biomimetic components are often incorporated, such as proteins, peptides, and growth factors. In this study, we aimed to enhance the osteogenic activity of a hydrogel formulation by integrating both the release and retention of gelatin so that gelatin serves as both an indirect support for released ink component on cells nearby and a direct support for encapsulated cells inside a printed hydrogel, thereby fulfills two functions. Methacrylate-modified alginate (MA-alginate) was chosen as the matrix because it has a low cell adhesion effect due to the absence of ligands. The gelatin-containing MA-alginate hydrogel was fabricated, and gelatin was found to remain in the hydrogel for up to 21 days. The gelatin remaining in the hydrogel had positive effects on encapsulated cells, especially on cell proliferation and osteogenic differentiation. The gelatin released from the hydrogel affected the external cells, showing more favorable osteogenic behavior than the control sample. It was also found that the MA-alginate/gelatin hydrogel could be used as a bioink for printing with high cell viability. Therefore, we anticipate that the alginate-based bioink developed in this study could potentially be used to induce osteogenesis in bone tissue regeneration.

Induction and rationalization of supramolecular chirality in a Zn(II)porphyrin dimer using chiral substrates: Role of substrates in the architectural selectivity

A flexible Zn(II)porphyrin dimer has been utilized as an efficient host for the selective binding of several diols and diamines as substrates. Stepwise formation of a 1:1 host-guest polymer and 1:2 host-guest monomer via intermolecular self-assembling and disassembling processes, has been demonstrated with a series of diamine/diols. Transfer of chirality from the molecular to the supramolecular level has been rationalized with structural elucidation. The formation of the 1:1 host-guest polymer displays a bisignate CD couplet. X-ray structure demonstrates the presence of both clockwise and anticlockwise conformers, however, the conformer formed as per pre-organization in the substrate chirality contributes more towards the overall CD couplet in solution. The addition of the substrate in excess leads to the inversion of the CD couplet due to the formation of the monomeric complex. Architectural selectivity has been illustrated for the 1:1 host-guest complexation by simply tuning the length of the substrates. Crystallographic characterizations revealed linear 1D polymeric structures for the 1:1 host-guest complexes with longer diamines while shorter substrates stabilize cyclic dimer via intermolecular H-bonding between the urea bridge (cis-NH-CO-) of the two porphyrin dimers. Interestingly, the molecular structure of 1:1 host-guest complexes with diols displays a linear polymer despite the shorter length of the substrates. Along with weaker coordination of the alcoholic oxygen towards the Zn(II) ion, the presence of bulky substituents at the coordinating sites of the diols renders the formation of intermolecular H-bonding interactions. Thus, the nature of metal ion and their binding affinity towards the substrate, host-guest size complementarity, and the bulk of the substituents contribute cumulatively towards the architectural selectivity. The cyclic dimers display larger upfield shifts of the substrate protons in the 1H NMR spectra as compared to the linear polymers. Moreover, the computational calculations further substantiate the experimental observations.

Efficient emission of Zn(II) and Cd(II) complexes with nopinane-annelated 4,5-diazafluorene and 4,5-diazafluoren-9-one ligands: how slight structural modification alters fluorescence mechanism.

Zinc(II) and cadmium(II) chlorido complexes with an N,N-chelating nopinane-annelated 4,5-diazafluoren-9-one ligand (LO) were synthesized. While the zinc(II) complex is mononuclear and adopts a tetrahedral ZnN2Cl2 coordination geometry, its cadmium(II) analogue features a 1D polymeric structure due to the bridging coordination of chlorido ligands with Cd2+ ions having an octahedral CdN2Cl4 coordination geometry. The photophysical properties of the oxygen-containing LO ligand and its zinc(II) and cadmium(II) complexes were studied in solution and in the solid state and matched against the properties of its oxygen-free 4,5-diazafluorene congener L and its complexes of the same metal ions. Comprehensive experimental and theoretical studies revealed the impact of the oxygen atom in the ligand core on the luminescence of the ligands and the complexes. For the oxygen-free L ligand and L-based complexes, the structural differences between the S0 and S1 geometries are small, which leads to fluorescence with extraordinarily small Stokes shifts. The emission of these compounds is of locally excited character for L and of mixed locally excited + ligand-to-halide charge transfer character for the L-based complexes. The introduction of the oxygen atom in the ligand core results in a drastic red-shift of the emission band due to short-range charge transfer. The differences between the S0 and S1 geometries are much more pronounced for LO and LO-based compounds than those of their oxygen-free analogues, leading to an order of magnitude larger Stokes shifts. On going from solution to the solid state, LO and its complexes exhibit aggregation-induced emission (AIE) behaviour with photoluminescence quantum yields (PLQYs) reaching tens of percent.

Pre-selection of fibroblast subsets prompts prevascularization of tissue engineered skin analogues.

The papillary and reticular dermis harbors phenotypically distinct fibroblasts, whose functions such as maintenance of skin's microvasculature are also distinct. Thus, we hypothesized that pre-selection of the subpopulations of fibroblasts would benefit the generation of skin tissue engineered (TE) constructs, promoting their prevascularization in vitro. We first isolated papillary and reticular fibroblasts using fluorescence-activated cell sorting and studied the effect of their secretome and extracellular matrix (ECM) on human dermal microvascular endothelial cell (hDMEC) organization. Subsequently, we developed a bilayered 3D polymeric structure with distinct layer-associated features to house the subpopulations of fibroblasts, to generate a skin analogue. Both papillary and reticular fibroblasts were able to stimulate capillary-like network formation in a Matrigel assay. However, the secretome of the two subpopulations was substantially different, being enriched in VEGF, IGF-1, and Angio-1 in the case of papillary fibroblasts and in HGF and FGF-2 for the reticular subset. In addition, the fibroblast subpopulations deposited varied levels of ECM proteins, more collagen I and laminin was produced by the reticular subset, but these differences did not impact hDMEC organization. Vessel-like structures with lumens were observed earlier in the 3D skin analogue prepared with the sorted fibroblasts, although ECM deposition was not affected by the cell's pre-selection. Moreover, a more differentiated epidermal layer was obtained in the skin analogue formed by the sorted fibroblasts, confirming that its whole structure was not affected. Overall, we provide evidence that pre-selection of papillary and reticular fibroblasts is relevant for promoting the in vitro prevascularization of skin TE constructs.

Designing 3D Polymeric Structures through Capillary Wetting on Colloidal Monolayer (Adv. Funct. Mater. 1/2023)

Designing 3D Polymeric Structures through Capillary Wetting on Colloidal Monolayer (Adv. Funct. Mater. 1/2023)

Square-pyramidal mononuclear, dinuclear and polymeric copper(II) complexes with (2-pyridinylmethyl)amino derivatives

The coordination behavior of three ligand precursors 2-[(2-pyridinylmethyl) amino]acetic acid hydrochloride, 4-[(2-pyridinylmethyl)amino]benzoic acid hydrochloride and 4-{[2-(pyridin-2-ylmethylamino)ethylamino]methyl}- benzoic acid hydrochloride, HL1?HCl?HL3?HCl, respectively, in copper(II) complexes is described. The complexes were characterized by elemental analysis, ESI mass spectrometry and IR spectroscopy, as well as X-ray structural analysis. The reaction of copper(II) with HL1?HCl in methanol afforded the polymeric complex [{Cu(?-Cl)2(MeL1-?2N,N?)}n] (1) featuring the methyl ester of L1 (MeL1). With HL2?HCl or HL3?HCl, the dimeric complex [{CuCl(?-Cl)(HL2-?2N,N?)}2] (2) or the mononuclear complex [CuCl2(HL3- ?3N,N?,N??)] (3) were obtained. All complexes exhibited square-pyramidal geometries. In 1, polymeric chains are formed through bridging chlorido ligands without typical hydrogen bonding interaction. Contrarily, the COOH group in 2 is participating in the formation of intermolecular hydrogen bonding forming a supramolecular structure. In 3, intermolecular hydrogen bonding (Cl???H(O)) leads to a 1-D polymeric structure. The copper(II) complex 2 diminished viability of human 8505C, MCF-7, 518A2 and SW-480 cell lines. The tumoricidal effect of 2 was realized mainly through caspase-mediated apoptosis.

Designing 3D Polymeric Structures through Capillary Wetting on Colloidal Monolayer

AbstractColloidal lithography has provided a facile means to create regular micro‐ and nano‐patterns by employing colloidal crystals as masks. However, the patterns are usually restricted to 2D as most techniques do not exploit the spherical shape of colloidal masks. Here, 3D structures are designed by utilizing capillary wetting of liquified photoresists on colloidal monolayers of silica particles. The silica particles are anchored at planar air‐photoresist interfaces to have an equilibrium contact angle without interfacial deformation for thick polymer layers. By contrast, when the polymer layers are thin enough, they wet the colloidal monolayer by forming periodic wavy interfaces to provide a constant Laplace pressure. The photo‐crosslinking of the photoresist and subsequent removal of silica particles leave behind periodic nanostructures with 3D‐undulated surfaces. Importantly, the structure and waviness are further controllable by adjusting the polymer thickness relative to the particle radius. As the shape of the interface is determined by capillarity, the 3D structures are reproducible as long as the dimension is smaller than the capillary length. The use of photoresists enables the production of micropatterns of the periodic wavy structures by photolithography. As one of the potential applications, structurally‐colored patterns are demonstrated with enhanced plasmonic and diffraction colors.

Alkali-excited gel structure and compositions evolution in geopolymers synthesized from the spent FCC catalyst and steel slag

The effect of the alkaline activation process, especially the SiO2/Na2O molar ratio (Ms) in the prepared alkaline activator, on the geopolymer materials prepared using the spent fluid catalytic cracking (FCC) catalyst and steel slag as raw materials is investigated in this study. The results indicate that the compressive strength of prepared geopolymers has been greatly affected by the alkaline environment. The compressive strength of obtained samples is improved obviously in the strong alkaline environment. Meanwhile, the number of amorphous gels in the prepared geopolymers increased with Ms decreasing. It is conducive for the silicon-oxo-aluminate species in the oligomers to polymerize into polymers with 3D polymeric structures, which would lead to the surface of as-prepared samples becoming smoother and the structure becoming denser. Moreover, the strong alkaline environment is beneficial for Ca2+ to involve in the geopolymerization reaction and form the N(C)ASH gel, which can further enhance the compressive strength of the prepared geopolymer.

XCT and DLW: Synergies of Two Techniques at Sub-Micrometer Resolution

Direct Laser Writing (DLW) and X-ray computed tomography (XCT) both offer unique possibilities in their respective fields. DLW produces full three-dimensional (3D) polymer structures on the microscale with resolutions below 100 nm. The fabricated structures can be analysed by XCT or X-ray microscopy (XRM), which incorporates additional X-ray lenses, in three dimensions down to a minimal basic spatial resolution of about 500 nm or 50 nm, respectively. In this work, two different DLW structures are analysed via XCT. Internal defects are detected and analysed for the purpose of quality control. Defects and structures with sizes down to 1.5 µm are successfully analysed. A 3D reconstruction and internal, hidden features of the fabricated structures are shown and discussed. In a first-of-its-kind study, we demonstrate the detectability of a single-voxel line inside a fabricated structure that would not be detectable with SEM or light microscopy. Furthermore, the direct fabrication on a PET substrate is shown to overcome the high X-ray absorbance of commonly used glass substrates. Attenuation spectra of SZ2080 and glass substrates are compared to a fabrication route direct on a 170 µm PET foil. The practical aspects of XCT measurements for DLW structures on different substrates will be discussed.

Field-Induced Slow Magnetic Relaxation in CoII Cyclopropane-1,1-dicarboxylates.

New CoII substituted malonate field-induced molecular magnets {[Rb6Co3(cpdc)6(H2O)12]∙6H2O}n (1) and [Cs2Co(cpdc)2(H2O)6]n (2) (where cpdc2− stands for cyclopropane-1,1-dicarboxylic acid dianions) were synthesized. Both compounds contain mononuclear bischelate fragments {CoII(cpdc)2(H2O)2}2− where the quasi-octahedral cobalt environment (CoO6) is complemented by water molecules in apical positions. The alkali metal atoms play the role of connectors between the bischelate fragments to form 3D and 2D polymeric structures for 1 and 2, respectively. Analysis of dc magnetic data using the parametric Griffith Hamiltonian for high-spin CoII supported by ab initio calculations revealed that both compounds have an easy axis of magnetic anisotropy. Compounds 1 and 2 exhibit slow magnetic relaxation under an external magnetic field (HDC = 1000 and 1500 Oe, respectively).

Partially Ordered Lanthanide Carboxylates with a Highly Adaptable 1D Polymeric Structure.

A new family of 14 isostructural [Ln(piv)3(en)]∞ lanthanide pivalate (piv−, 2,2-dimethylpropanoate) complexes with ethylenediamine (en) was synthesized by a topology-preserving transformation from 1D coordination polymers [Ln(piv)3]∞. The crystal structures of the compounds were determined by single-crystal and powder X-ray diffraction, which demonstrated that despite the regular ligand arrangement within the chains, the latter are intricately packed within the partially ordered crystal, as only two of four ligands are strictly bound by the translational symmetry. The peculiarities of the lanthanide coordination environment were explored by total X-ray scattering with pair distribution function analysis. Periodic DFT calculations revealed the chain stabilization by intrachain H-bonds and weak interchain interactions. Noticeably, the energy difference was infinitesimally small even between the two considered extreme variants of ordered packing, which is in line with the disturbed packing order of the chains. The luminescent properties of Eu and Tb complexes were investigated in order to prove the energy transfer between lanthanide ions within the heterometallic complex. This opens up the prospect of creating new materials for optical applications. The heterometallic compound Eu0.05Tb0.95(piv)3(en) was synthesized, and was found to demonstrate temperature-dependent luminescence with a linear dependence of the thermometric parameter I(Eu)/I(Tb) within the temperature range from −80 °C to 80 °C, and had a maximum relative sensitivity value of 0.2%/K.

Synthesis, Characterization and Biomimetic Activity of Heterogenized Dioxidomolybdenum(VI) and Analogous Homogeneous Complexes

AbstractTwo mononuclear cis‐[MoVIO2] complexes with Schiff base ligands, H4L1 (I) and H4L2 (II) (derived from the condensation of 3,5‐diformyl‐4‐hydroxybenzoic acid with isonicotinoylhydrazide and nicotinoylhydrazide) were synthesized using [MoVIO2(acac)2] (Hacac=acetylacetone) and ligand in 1 : 1 molar ratio in methanol. The obtained homogeneous complexes [MoVIO2(H2L1)]n (1) and [MoVIO2(H2L2)(MeOH)] (2) were supported on titania functionalized with amine group (APTMS‐TiO2) to obtain heterogeneous complexes [MoVIO2(HL1)(MeOH)]@APTMS‐TiO2 (3) and [MoVIO2(HL2)(MeOH)]@APTMS‐TiO2 (4), respectively. All the isolated complexes were characterized by various spectral techniques (FT‐IR, UV‐visible, 1H and 13C NMR), elemental (CHN) and thermogravimetric analyses; heterogeneous complexes were additionally characterized by transmission electron microscopy, diffuse reflectance, X‐ray photoelectron spectroscopy and Powder‐X‐ray diffraction studies. The single‐crystal X‐ray diffraction analysis of complexes 1 and 2 confirms the distorted octahedral geometry for both complexes, where ligands coordinate to the metal centre through Ophenolate, Nazomethine, and Oenolate. Complex 1 has a 3D polymeric structure, where the sixth site of one molecule of Mo is coordinated to the pyridinic nitrogen of the other molecule while 2 is monomeric. These complexes are explored as bio‐mimicking model catalysts for the type II copper site in phenoxazinone synthase. These complexes catalyze the oxidative condensation of o‐aminophenol (OAP) into 2‐aminophenoxazine‐3‐one (APX) utilizing aq. H2O2 in the MeCN‐MeOH mixture. For complexes 1 and 2, the value of turnover number (kcat) obtained for phenoxazinone synthase‐like activity is 2.14 and 1.76 h−1, respectively. Under the optimized reaction parameters, the yield of 2‐aminophenoxazine‐3‐one (APX) obtained is 97 and 92 % for complexes 3 and 4, respectively.

Characterization of a 30 µm pixel size CLIP-based 3D printer and its enhancement through dynamic printing optimization.

Resolving microscopic and complex 3D polymeric structures while maintaining high print speeds in additive manufacturing has been challenging. To achieve print precision at micrometer length scales for polymeric materials, most 3D printing technologies utilize the serial voxel printing approach that has a relatively slow print speed. Here, a 30-µm-resolution continuous liquid interface production (CLIP)-based 3D printing system for printing polymeric microstructures is described. This technology combines the high-resolution from projection microstereolithography and the fast print speed from CLIP, thereby achieving micrometer print resolution at x103 times faster than other high-resolution 3D printing technologies. Print resolutions in both lateral and vertical directions were characterized, and the printability of minimum 30 µm features in 2D and 3D has been demonstrated. Through dynamic printing optimization, a method that varies the print parameters (e.g. exposure time, UV intensity, and dark time) for each print layer, overhanging struts at various thicknesses spanning 1 order of magnitude (25 µm - 200 µm) in a single print are resolvable. Taken together, this work illustrates that the micro-CLIP 3D printing technology, in combination with dynamic printing optimization, has the high resolution needed to enable manufacturing of exquisitely detailed and gradient 3D structures, such as terraced microneedle arrays and micro-lattice structures, while maintaining high print speeds.

Hybrid microfabrication of 3D pyrolytic carbon electrodes by photolithography and additive manufacturing

We report a novel hybrid method for fabricating high aspect ratio 3D pyrolytic carbon electrodes combining UV photolithography and additive manufacturing with commercially available SLA 3D printers and materials. By using a 3D printed chip holder, aligned 3D printing on a patterned silicon chip was possible. This allowed for the fabrication of cylindrical polymer micropillars with a height of 2173 ± 26 μm and a width of 316 ± 11 μm on SU-8 precursor structures defining the leads, contact pads and underlying 2D electrode prepared using UV lithography. Microfabrication of 3D structures with these dimensions is impossible to achieve with SU-8 photolithography alone. The hybrid polymer structures were converted into 3D carbon electrodes with high structural integrity using a 3-step pyrolysis process optimized for the specific 3D print resin. During this process, the micropillars shrunk to 30 ± 3% in height and 35 ± 1% in width of the polymer precursor structures, while maintaining the macroscopic shape and microscopic surface roughness. Electrochemical experiments confirmed that the pyrolytic carbon formed a monolithic conductive 3D electrode. The surface roughness contributed to a 17 ± 5% increase in electroactive surface area compared to the geometrical surface area of the micropillars. • · 3D polymer microstructures fabricated by a novel hybrid process combining SU-8 photolithography and additive manufacturing • Optimization of a pyrolysis process converting the 3D polymer structures into 3D pyrolytic carbon electrodes • Electrochemical characterization demonstrating monolithic integration and increased surface area of the 3D electrodes

Off-Stoichiometry Thiol-Enes Polymers Containing Silane Groups for Advanced Packaging Technologies.

New modified off-stoichiometry thiol–enes polymers, called OSTE-MS polymers, were developed by introducing mercaptosilane into the polymer mixture. This modification made it possible to introduce silane groups into the polymer frame, due to which the polymer gained the ability to bond with silicon wafers without modification of the wafer surface by any adhesive. The optimal composition for creating 3D polymer structures on a chip was selected, which consists of a volume ratio of 6:6:1 of allyl monomer, mercapto monomer, and mercaptosilane, respectively. The hardness, shift force, tensile strength, Young’s modulus, optical transparency, glass transition temperature, thermal stability, and chemical resistance of the OSTE-MS polymer, and the viscosity for the prepolymer mixture were studied. On the basis of the OSTE-MS polymer, 3D polymer structures of the well type and microfluidic system on the silicon chips were obtained.

Two independent and consecutive Michael addition of 1,3-dimethylbarbituric acid to (2,6-diarylidene)cyclohexanone: Flying-bird-shaped 2D-polymeric structure

Abstract Two independent and consecutive intermolecular Michael addition of 1,3-dimethylbarbituric acid to 2,6-diarylidenecyclohexanone as an α,β-unsaturated ketone leads to synthesis of a new type of meso form 5,5′-((2-oxocyclohexane-1,3-diyl)bis(arylmethylene))bis(1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione) in good yield. These compounds showed a 2D-polymeric structure via intermolecular H-bonds. Structure elucidation is carried out by 1H NMR, 13C NMR, FT-IR, and X-ray diffraction analyses. A plausible reaction mechanism is discussed.

Novel pyrazole-based carboxylate ligand as a building block for assembling lanthanides in luminescent 2D and 3D MOFs

New pyrazole-based carboxylic ligand 1-(carboxymethyl)-1H-pyrazole-3,5-dicarboxylic acid (H3L) as well as its lanthanide complexes [LnL(H2O)2]n, Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8) and [LnL(H2O)]n, Ln = Dy (9), Ho (10), Er (11), Tm (12), Yb (13), Lu (14) have been prepared and studied. Compounds 1–8 represent a 3D polymer structure while 9–14 are 2D-polymers. Lanthanide-centered luminescence of compounds 4–9 is studied in detail. It is shown that high energy triplet level of H3L ligand (27100 cm−1) is able to sensitize not only the yellow-green luminescence of Tb3+ and Dy3+ ions, but also the red-orange luminescence of Sm3+ and Eu3+. NIR-luminescence of the neodymium complex 4 is possible upon direct excitation through the f-f transition of the Nd3+ ion.

Stimuli-Responsive Liquid Crystal Printheads for Spatial and Temporal Control of Polymerization.

Polymerization reactions triggered by stimuli play a pivotal role in materials science, with applications ranging from lithography to biomedicine to adaptive materials. However, the development of chemically triggered, stimuli-responsive systems that can confer spatial and temporal control on polymerization remains a challenge. Herein, chemical-stimuli-induced polymerization based on a liquid crystal (LC) printhead is presented. The LC responds to a local chemical stimulus at its aqueous interface, resulting in the ejection of initiator into the solution to trigger polymerization. Various LC printhead geometries are designed, allowing programming of: i) bulk solution polymerization, ii) synthesis of a thin surface-confined polymeric coating, iii) polymerization-induced self-assembly of block copolymers to form various nanostructures (sphere, worm-like, and vesicles), and iv) 3D polymeric structures printed according to local solution conditions. The approach is demonstrated using amphiphiles, multivalent ions, and biomolecules as stimuli.

Structure and properties of two new heteroleptic bismuth(III) dithiocabamates of the general composition Bi(S2CNH2)2X (X = Cl, SCN)

Abstract The title compounds were prepared by precipitation from acidic solutions of the reactants in acetone/water. Bi(S2CNH2)2Cl (1) crystallizes in the non-centrosymmetric trigonal space group P32 with a = 8.6121(3) and c = 11.1554(4) Å, Z = 3; Bi(S2NH2)2SCN (2) in P21/c (monoclinic) with a = 5.5600(2), b = 14.3679(5), c = 12.8665(4) Å, and β = 90.37(3)°. In the crystal structure of 1 Bi3+ is in a sevenfold coordination of two bidentate and one monodentate S2CHNH2 − anions with an asymmetric coordination pattern of five Bi–S and two Bi–Cl− bonds. The linkage of these polyhedra via common Cl–S edges leads to a 1D polymeric structure with undulated chains propagating in the direction [001]. These chains are linked by strong and medium strong hydrogen bonds forming the 3D crystal structure. In the crystal structure of 2 the Bi3+ cation is in an eightfold coordination. The polyhedron can be described as a significantly distorted tetragonal anti-prism, capped by an additional S atom. Two of these prisms share a common quadrilateral face to form a “prism-double” (Bi2S10N2). These building units are linked by common edges, and the resulting 1D infinite angulated chains propagate along [100]. By contrast to organo-dithiocarbamate compounds, where C–H···X bridges are dominant, the interchain connections in the crystal structures of 1 and 2 are formed exclusively via N–H···S, N–H···Cl, and N–H···N interactions, generating the 3D networks. A significant eccentricity of the Bi3+ cation in the crystal structures of both complexes is observed. Both compounds emit light in the orange range of the electromagnetic spectrum.