Hydrogen-bonded Supramolecular Network Research Articles

Hydrogen-bonded Supramolecular Network Enabled Gentle Reprogramming of Liquid Crystal Elastomer toward Evolutionary Robot.

In nature, many organisms augment chances of survival by reprogramming their structures to evolving environment, among which sea squirts being a prime example. Such reprogramming has been demonstrated in liquid crystal elastomer (LCE) actuator assembled with heat assistance. However, the required temperature being higher than the actuation temperature limits its application. Here, we reported a hydrogen-bonded supramolecular network LCE to construct soft modular and reprogrammable actuator by assembling with a gentle heat treatment. Leveraging the Michael addition reaction, we introduced hydrogen bonding to the LCE matrix with functionalized pyridine monomers. Experimental and molecular dynamics modeling proved the efficient dynamic hydrogen bond exchange at 60°C, significantly lower than the actuating temperature of the LCE. This gave rise to the reversible and robust adhesion of the same collection of LCE modules capable of being built into different bilayers and performing various morphing upon a short thermal stimulation. Therefore, we demonstrated that these comparatively weak cross-links enabled reconfiguration of the LCE actuator. With the developed hydrogen-bonding LCEs, we built proof-of-concept modular reprogrammable robot, performing crawling, sailing, and microcircuit repair tasks. This bioinspired and efficient method for evolutionary LCE robot offers a viable path for further development of intelligent actuators sustainable in complex environments.

Supramolecular hydrogen-bonded networks formed from copper(II) carboxylate dimers.

The well-known copper carboxylate dimer, with four carboxylate ligands extending outwards towards the corners of a square, has been employed to generate a series of crystalline compounds. In particular, this work centres on the use of the 4-hydroxybenzoate anion (Hhba-) and its deprotonated phenolate form 4-oxidobenzoate (hba2-) to obtain complexes with the general formula [Cu2(Hhba)4-x(hba)xL2-y]x-, where L is an axial coligand (including solvent molecules), x = 0, 1 or 2, and y = 0 or 1. In some cases, short hydrogen bonds result in complexes which may be represented as [Cu2(Hhba)2(H0.5hba)2L2]-. The main focus of the investigation is on the formation of a variety of extended networks through hydrogen bonding and, in some crystals, coordinate bonds when bridging coligands (L) are employed. Crystals of [Cu2(Hhba)4(dioxane)2]·4(dioxane) consist of the expected Cu dimer with the Hhba- anions forming hydrogen bonds to 1,4-dioxane molecules which block network formation. In the case of crystals of composition [Et4N][Cu2(Hhba)2(H0.5hba)2(CH3OH)(H2O)]·2(dioxane), Li[Cu2(Hhba)2(H0.5hba)2(H2O)2]·3(dioxane)·4H2O and [Cu2(Hhba)2(H0.5hba)2(H0.5DABCO)2]·3CH3OH (DABCO is 1,4-diazabicyclo[2.2.2]octane), square-grid hydrogen-bonded networks are generated in which the complex serves as one type of 4-connecting node, whilst a second 4-connecting node is a hydrogen-bonding motif assembled from four phenol/phenolate groups. Another two-dimensional (2D) network based upon a related square-grid structure is formed in the case of [Et4N]2[Cu2(Hhba)2(hba)2(dioxane)2][Cu2(Hhba)4(dioxane)(H2O)]·CH3OH. In [Cu2(Hhba)4(H2O)2]·2(Et4NNO3), a square-grid structure is again apparent, but, in this case, a pair of nitrate anions, along with four phenolic groups and a pair of water molecules, combine to form a second type of 4-connecting node. When 1,8-bis(dimethylamino)naphthalene (bdn, `proton sponge') is used as a base, another square-grid network is generated, i.e. [Hbdn]2[Cu2(Hhba)2(hba)2(H2O)2]·3(dioxane)·H2O, but with only the copper dimer complex serving as a 4-connecting node. Complex three-dimensional networks are formed in [Cu2(Hhba)4(O-bipy)]·H2O and [Cu2(Hhba)4(O-bipy)2]·2(dioxane), where the potentially bridging 4,4'-bipyridine N,N'-dioxide (O-bipy) ligand is employed. Rare cases of mixed carboxylate copper dimer complexes were obtained in the cases of [Cu2(Hhba)3(OAc)(dioxane)]·3.5(dioxane) and [Cu2(Hhba)2(OAc)2(DABCO)2]·10(dioxane), with each structure possessing a 2D network structure. The final compound reported is a simple hydrogen-bonded chain of composition (H0.5DABCO)(H1.5hba), formed from the reaction of H2hba and DABCO.

Hydrogen-bonded supramolecular structures in copper(II) nitrobenzoates with N-methylnicotinamide: synthesis, supramolecular structure, Hirshfeld surface analysis, spectral and DFT study

The synthesis of six new copper(II) nitrobenzoate complexes with N-methylnicotinamide, used as an auxiliary ligand for a supramolecular interaction study, is reported. Crystal structures of six novel compounds [Cu(2-NO2bz)2(mna)2(H2O)2] (1), [Cu(2-NO2bz)2(mna)2(H2O)2]∙2H2O (2), [Cu(3-NO2bz)2(mna)2(H2O)2] (3), [Cu(3,5-(NO2)2bz)2(mna)2(H2O)2]∙2H2O (4), [Cu(4-NO2bz)2(mna)2(H2O)2]∙2(4-NO2bzH) (5) and [Cu(3,5-(NO2)2bz)2(mna)(H2O)3] (6) (mna = N-methylnicotinamide, 2-NO2bz = 2-nitrobenzoate, 3-NO2bz = 3-nitrobenzoate, 4-NO2bz = 4-nitrobenzoate, 3,5-(NO2)2bz = 3,5-dinitrobenzoate) were determined by X-ray analysis. Compounds 1–6 are mononuclear with a tetragonal-bipyramidal geometry around the Cu2+ ion. The molecules of the studied complexes are mostly linked by a combination of N–H…O and O–H…O hydrogen bonds between N-methylnicotinamide and water molecules into supramolecular hydrogen-bonded coordination chains and networks. Intermolecular interactions in the supramolecular structures were also studied using Hirshfeld surface analysis. In addition, the complexes 1–6 have been characterised by elemental analysis, IR, UV–Vis and EPR spectroscopy. Density functional theory calculations were performed in order to reproduce the EPR magnetic parameters. DFT calculations of the EPR parameters show a good agreement with the experimental results.

Supramolecular hydrogen-bonded organic networks grown on cellulose fibers for efficient proton conduction

Supramolecular hydrogen-bonded organic networks grown on cellulose fibers for efficient proton conduction

Piperazine-1,4-diol (PipzDiol): synthesis, stereodynamics and assembly of supramolecular hydrogen-bonded 2D networks

The manuscript describes a novel small building block, 1,4-piperazinediol (PipzDiol), which has an extended H-bond donor structure compared to piperazine.

Engineered design of a new HOF by simultaneous monitoring of reaction environment conductivity

The self-assembled Hydrogen−bonded organic frameworks (HOFs) formed by H-bonding between organic linkers were introduced as an exciting type of polymeric porous materials. Here, for the first time, we used sequential conductometry for online monitoring of the self-assembly process as a simple and effective way to find the optimal synthesis ratio of a new HOF. The pentagonal 1,2,4-triazole and the square molecule squaric acid were selected as synthons with different shapes. The obtained structure, [H4C2N3+][HC4O4-] (HOF-1), was revealed by single-crystal X-ray diffraction and further characterized by IR, solid-state UV, and thermogravimetric analysis (TGA). Crystal structure determination shows that HOF-1 crystallizes in monoclinic Cc space group with three-dimensional supramolecular hydrogen-bonded networks via intermolecular O－H⋯O, N－H⋯O, and C－H⋯O interactions. Based on the Electrochemical Impedance Spectroscopy (EIS) results, resistance characteristics of the material after crystallization are significantly reduced, and the dispersion effect is small, indicating that the compound has better uniformity and conductivity after crystallization. By calculation, the electrical conductivity of HOF-1 is excellent at about 10-6 ​S/cm and can be used as a potential proton conductive material.

Black Phosphorus Nanosheet/Melamine Cyanurate Assemblies as Functional Active Layers for Artificial Synapse Memristors

The aqueous solution for the liquid-phase exfoliation (LPE) of 2D black phosphorus (BP) is rarely used due to the environmental instability of BP caused by oxygen and water molecules. In this study, we demonstrate a melamine-assisted LPE in aqueous conditions to achieve high-quality BP nanosheets with effective exfoliation, where the assembled melamine molecule on BP enhances the peeling force together with the in situ protection against BP oxidation, leading to the well-dispersion of highly crystalline BP in water that enables the eco-friendly and biocompatible process. Moreover, we develop an approach to extract BP together with a supramolecular assembly of melamine-cyanurate (MCA) by adding the cyanuric acid in melamine solution, formatting the hydrogen-bonded supramolecular network together with the incorporated BP nanosheets. Such one-step self-assembly of BP and the supramolecular complex are readily integrated into two-terminal devices, namely memristor and threshold switch (TS) selector, where BP nanosheets bridge the proton transfer of the hydrogen bond network in individual supramolecules, modulating analog resistive switching as synaptic behaviors of the neuromorphic system. TS selector is achieved through stacking pure MCA layer to block proton hopping under the threshold voltage, exhibiting high nonlinearity of 30 mV/dec with on/off resistance ratio up to 104 and retention time over 4000 s. This study provides an effective LPE of BP in aqueous solution and explores an extraction route of as-exfoliated BP with a supramolecular complex ready for integration of a memristor, which paves the way for versatile applications of BP on emerging nanoelectronics and optoelectronics.

Coordination Polymers in Dicyanamido-Cadmium(II) with Diverse Network Dimensionalities

The synthesis and structural characterization of six dicyanamido-cadmium(II) complexes are reported: catena-[Cd(μ1,3-dca)(μ1,5-dca)(3-ampy)] (1), catena-[Cd3(μ1,3,5-dca)2(μ1,5-dca)4(pyNO)2(H2O)2] (2), catena-{Cd(H2O)2(μ1,5-dca)2](2,6-lut-NO)} (3), catena-[Cd(Me2en)(μ1,5-dca)2] (4), catena-[Cd(Me4en)(μ1,5-dca)2] (5), and [Cd(1,8-damnp)2(dca)2] (6), where dca = dicyanamide anion, 3-ampy = 3-aminopyridine, pyNO = pyridine-N-oxide, 2,6-lut-NO = 2,6-lutidine-N-oxide, Me2en = N,N-dimethyl-ethylenediamine, Me4en = N,N,N′,N′-tetramethyl-ethylenediamine, and 1,8-damnp = 1,8-diaminonaphthaline. The coordination polymers have different dimensionalities: 1 and 5 form 3D networks structures; 3 and 4 form polymeric 1D chains and 1DD double chains, respectively. Ribbons of three fused polymeric chains are observed in 2. In 6, the mononuclear complex units form a hydrogen-bonded supramolecular 3D network. In the coordination polymer compounds, the dca linkers display three bonding modes: the most common μ1,5-dca and the least popular μ1,3- and μ1,3,5-dca bonding. The luminescence emission and thermal properties of the complexes were investigated.

Strong, tough and healable elastomer nanocomposites enabled by a hydrogen-bonded supramolecular network

Epoxidized natural rubber (ENR)/organic-modified layered double hydroxide (O-LDH) nanocomposites were prepared in this work. The O-LDH can participate in the formation of a hydrogen-bonded supramolecular network in the ENR matrix. The network can effectively improve mechanical properties. With 20 phr O-LDH, the stress, strain and Young's modulus of the final ENR/O-LDH nanocomposite increase to 2.80 MPa, 542% and 4.70 MPa, which is 366%, 113% and 427% of the neat ENR, respectively. Meanwhile, the ENR/O-LDH nanocomposites show self-healing behavior due to the dynamic hydrogen-bonded supramolecular network and chain diffusion. The ENR/O-LDH-10 exhibited the highest self-healing efficiency of about 78% (120 °C, 12 h). When the O-LDH content exceeds 10 phr, the restricting effect of fillers weakens the ability to reconstruct hydrogen-bonding, and thus reduces the healing efficiency of the ENR nanocomposites, despite continuous increased mechanical properties. This work opens up many opportunities for creating advanced elastomers that are strong, tough and self-healable through the design of a dynamic supramolecular network.

Addition to “Dominance of Chain Entanglement over Transient Sticking on Chain Dynamics in Hydrogen-Bonded Supramolecular Polymer Networks in the Melt”

Addition to “Dominance of Chain Entanglement over Transient Sticking on Chain Dynamics in Hydrogen-Bonded Supramolecular Polymer Networks in the Melt”

Formation of supramolecular hydrogen-bonding chains and networks from copper (II) halogenobenzoates with N-methylnicotinamide: Supramolecular isomerism

The self-assembly of supramolecular structures from copper (II) halogenobenzoate complexes containing N-methylnicotinamide ligand have been explored. The following compound and polymorph structures were determined by single-crystal X-ray structural analysis-the compounds [Cu(4-Fbz)2(mna)2(H2O)], [Cu(4-Clbz)2(mna)2(H2O)], [Cu(4-Brbz)2(mna)2(H2O)], two polymorphs of [Cu(2,6-Cl2bz)2(mna)2(H2O)2]·2H2O, [Cu(3,5-Cl2bz)2(mna)2(H2O)2]·2H2O, [Cu(3-Fbz)2(mna)2(H2O)2]·2H2O, and [Cu(3-Clbz)2(mna)2(H2O)2]·2H2O, two polymorphs of [Cu(3-Brbz)2(mna)2(H2O)2]·2H2O, [Cu(3-Ibz)2(mna)2(H2O)2]·2H2O, [Cu(2,5-Cl2bz)2(mna)2(H2O)2]·2H2O, [Cu(2,3-Cl2bz)2(mna)2(H2O)2]·H2O, [Cu(2,6-Cl2bz)2(mna)2(H2O)]·2H2O, [Cu(3,4-Cl2bz)2(mna)2(H2O)]·2H2O, [Cu(3-Brbz)2(mna)2(H2O)] and [Cu(2-Fbz)2(mna)2(μ-H2O)]n, (mna = N-methylnicotinamide, 4-Fbz = 4-fluorobenzoate, 4-Clbz = 4-chlorobenzoate, 4-Brbz = 4-bromobenzoate, 3-Fbz = 3-fluorobenzoate, 3-Clbz = 3-chlorobenzoate, 3-Brbz = 3-bromobenzoate, 3-Ibz = 3-iodobenzoate, 2-Ibz = 2-iodobenzoate, 2,3-Cl2bz = 2,3-dichlorobenzoate, 2,5-Cl2bz = 2,5-dichlorobenzoate, 2,6-Cl2bz = 2,6-dichlorobenzoate, 3,4-Cl2bz = 3,4-dichlorobenzoate and 3,5-Cl2bz = 3,5-dichlorobenzoate). The compounds are monomeric complexes with a distorted octahedral or square-pyramidal coordination sphere around Cu2+ ion. The two polymorph sets of [Cu(2,6-Cl2bz)2(mna)2(H2O)2]·2H2O and [Cu(3-Brbz)2(mna)2(H2O)2]·2H2O are two examples of coordination compounds which are conformation and supramolecular isomers. The crystal structure of complex [Cu(4-Fbz)2(mna)2(H2O)] shows the phase transition in two temperatures. The compound [Cu(2-Fbz)2(mna)2(μ-H2O)]n is a coordination polymer with bridging aqua ligand. The molecules of all compounds are connected by N–H…O and O–H…O hydrogen bonds from NHCH3 groups of N-methylnicotinamide and water molecules which create supramolecular hydrogen-bonding-coordination chains and networks. The intermolecular interactions were studied by Hirshfeld surface analysis.

Hydrogen Bonding as a Supramolecular Tool for Robust OFET Devices.

In the present study, we demonstrated the effect of hydrogen bonding in the semiconducting behaviour of a small molecule used in organic field-effect transistors (OFETs). For this study, the highly soluble dumbbell-shaped molecule, Boc-TATDPP based on a Boc-protected thiophene-diketopyrrolopyrrole (DPP) and triazatruxene (TAT) moieties was used. The two Boc groups of the molecule were removed by annealing at 200 °C, which created a strong hydrogen-bonded network of NH-TATDPP supported by additional π-π stacking. These were characterised by thermogravimetric analysis (TGA), UV/Vis and IR spectroscopy, XRD and high-resolution (HR)-TEM measurements. FETs were fabricated with the semiconducting channel made of Boc-TATDPP and NH-TATDPP separately. It is worth mentioning that the Boc-TATDPP film can be cast from solution and then annealed to get the other systems with NH-TATDPP. More importantly, NH-TATDPP showed significantly higher hole mobilities compared to Boc-TATDPP. Interestingly, the high hole mobility in the case of NH-TATDPP was unaffected upon blending with [6,6]-phenyl-C71-butyric acid methyl ester (PC71 BM). Thus, this robust hydrogen-bonded supramolecular network is likely to be useful in designing efficient and stable organic optoelectronic devices.

Crystal structures of 1'-amino-cobaltocenium-1-carb-oxy-lic acid chloride monohydrate and of its azo dye 1'-[2-(1-amino-2,6-dimethylphenyl)diazen-1-yl]cobaltocenium-1-carb-oxy-lic acid hexa-fluorido-phosphate monohydrate.

1'-Amino-cobaltocenium-1-carb-oxy-lic acid chloride, [Co(C5H6N)(C6H5O2)]Cl·H2O, (3), and its azo derivative 1'-[2-(1-amino-2,6-dimethylphenyl)diazen-1-yl]cobaltocenium-1-carb-oxy-lic acid hexa-fluorido-phosphate, [Co(C13H14N3)(C6H5O2)]PF6·H2O (5) were obtained from cobaltocenium-1,1'-di-carb-oxy-lic acid hexa-fluorido-phosphate by converting one carboxyl group to its chloro-carboxyl derivative followed by chloride/azide exchange, Curtius rearrangement, diazo-tiation and azo coupling with 2,6-di-methyl-aniline. Both title compounds crystallize as their monohydrates. In the crystal structure of 3, both functional groups lie in the same direction, with the Cp rings being nearly eclipsed, and participate in an extended hydrogen-bonded supra-molecular network including the counter-ion and the water mol-ecule of crystallization. Although the functional groups in 5 are somewhat further apart, bearing a greater torsion angle with the Cp rings now staggered, a similar supra-molecular network is observed with not only the carb-oxy-lic acid and azo groups, but also with the more remote amino group participating in a hydrogen-bonded network, again including the counter-ion and the water mol-ecule. The hexa-fluorido-phosphate ion shows positional disorder. Compound 3 was refined as an inversion twin. In 5, each of the six F atoms is disordered over two sets of sites in a 1:1 ratio.

Supramolecular hydrogen-bonded organic networks through acid–base pairs as efficient proton-conducting electrolytes

The research of developing new proton-conducting materials via a simple and cost-effective method is vital in fuel cell technology.

MnIII-FeIII Heterometallic Compounds within Hydrogen-Bonded Supramolecular Networks Promoted by an [Fe(CN)5(CNH)]2- Building Block: Structural and Magnetic Properties.

The reaction of [Fe(CN)6]3- and [Mn(acacen)]+ (H2acacen = N, N'-bis(acetylacetone)ethylenediamine) building units in the presence of supramolecular cations, [(F-Anil)(18-crown-6)]+ (F-Anil+ = 3-fluoroanilinium) or [(Me-F-Anil)(18-crown-6)]+ (Me-F-Anil+ = 3-fluoro-4-methylanilinium), affords two new bimetallic compounds, [(F-Anil)(18-crown-6)][Mn(acacen)Fe(CN)5(CNH)]·MeOH (1) and [(Me-F-Anil)(18-crown-6)][Mn(acacen)(MeOH)Fe(CN)5(CNH)]·MeOH (2), respectively. Compound 1 exhibits a one-dimensional topology, while compound 2 is a dinuclear discrete system due to the coordination of a MeOH molecule at the axial position of the [Mn(acacen)]- unit. For both systems, the acidity of the corresponding supramolecular cation triggers the protonation of the FeIII moiety as [Fe(CN)5(CNH)]2-. Moreover, the resulting -CNH ligand induces hydrogen bonding interactions connecting the chains for 1 or the molecules for 2 into higher dimensional supramolecular networks. Magnetic properties of compounds incorporating these [Fe(CN)5(CNH)]2- building blocks were, for the first time, thoroughly investigated, indicating a three-dimensional antiferromagnetic order of single-chain magnets for 1 and an antiferromagnetically interacting S = 3/2 spin ground state for 2.

Associating Imidazoles: Elucidating the Correlation between the Static Dielectric Permittivity and Proton Conductivity.

Broadband dielectric spectroscopy is employed to investigate the impact of supramolecular structure on charge transport and dynamics in hydrogen-bonded 2-ethyl-4-methylimidazole and 4-methylimidazole. Detailed analyses reveal (i)an inverse relationship between the average supramolecular chain length and proton conductivity and (ii)no direct correlation between the static dielectric permittivity and proton conductivity in imidazoles. These findings raise fundamental questions regarding the widespread notion that extended supramolecular hydrogen-bonded networks facilitate proton conduction in hydrogen bonding materials.

Enhancement of microphase ordering and mechanical properties of supramolecular hydrogen-bonded polyurethane networks

Enhanced thermoreversible and mechanical properties in supramolecular polyurethanes have been realised by the incorporation of flexible DBDI derived hard segments.

Hybrid Deep Eutectic Solvents with Flexible Hydrogen-Bonded Supramolecular Networks for Highly Efficient Uptake of NH3.

Serious environmental concerns have led to a great demand for efficient uptake of NH3 by solvents. However, traditional aqueous absorbents have many shortcomings and efforts to use ionic liquids have met with limited success. A hybrid deep eutectic solvents (DESs) designed with a flexible hydrogen-bonded supramolecular network exhibits both exceptional NH3 uptake capacity and superior desorption-regeneration performance, along with superb NH3 /CO2 selectivity and environmental merit. Elucidated by molecular dynamic simulations and spectroscopic analysis, the abundant hydrogen-bonding sites in the hybrid DESs bind every atom of the NH3 molecule and enable strong physical reversible solvation, whereas the multiple interactions among the hybrid components create a flexible hydrogen-bonded supramolecular network and allow for solvent-unbreaking absorption to ensure the full participation of the solvent and process stability. A mass solubility of NH3 up to 0.13 g g-1 was achieved at 313 K and 101 kPa by the hybrid DES choline chloride/resorcinol/glycerol (1:3:5), which is higher than all reported ionic liquids and ordinary DESs. Moreover, the performance remained the same after ten absorption-desorption cycles and the DESs could be easily regenerated.

Thermo-switchable pressure-sensitive adhesives with strong tunable adhesion towards substrate surfaces of different hydrophilicity

Short-chain oligomeric poly(ethylene glycols), PEGs, are capable of forming supramolecular hydrogen-bonded stoichiometric network complexes with stimuli-responsive polymer such as N-substituted high molecular weight polyamide, poly(N-isopropyl acrylamide), PNIPAM, demonstrating Lower Critical Solution Temperature (LCST) in aqueous solutions. H-bonding occurs through interaction of PEG terminal hydroxyl groups with complementary amide groups in the PNIPAM monomer units. The complexes combine high cohesive strength (due to H-bond crosslinking of long-chain macromolecules) with large free volume (resulting from telechelic structure and essential length of PEG chains). Combination of these factors is the necessary condition of pressure sensitive adhesion. “Smart” pressure-sensitive adhesives (PSAs) adhere towards the hydrophilic substrates at room temperature and detach reversibly at the temperatures above LCST, while their behavior towards hydrophobic substrates follows opposite pattern. As contact angle measurements have shown, at room temperatures the thermo-switchable PSAs have low contact angle with water, which becomes large at temperatures above LCST. Under temperature elevation, the complex turns hydrophobic inside out and loses hydrophilicity, similarly to the complexes of another «smart» polyamide, poly-N-vinyl caprolactam (PVCL), with PEG-400. Evident correlation has been observed between the strength of hydrogen bonding and molecular structures of both the PVCL – PEG and PNIPAM – PEG PSA complexes and their adhesion.

Influence of N-donor ancillary ligands on the structures of three cadmium(II) complexes with L-shaped carboxylate ligand

This work presents a systematic investigation on reactions of cadmium nitrate with L-shaped 1-carboxymethylpyridinium-4-carboxylate (L) ligand in the presence of three different N-donor ancillary ligands 2,2′-bipyridine (2,2′-bipy), 1,10-phenanthroline (1,10-phen), and 4,4′-bipyridine (4,4′-bipy). Three new cadmium(II) complexes, namely, [Cd(L)2(H2O)4] (1), [Cd(L)2(1,10-phen)]·7.54H2O (2), and [Cd(L)2(H2O)]·2H2O (3), were obtained and characterized by single-crystal X-ray diffraction, as well as IR spectroscopy. Structure analysis shows only 1,10-phen ligand takes part in coordination in complex 2. Complex 1 possesses a 3D hydrogen-bonded supramolecular network, which are constructed by the linkage of neutral mononuclear [Cd(L)2(H2O)4] molecules via abundant O–H⋯O hydrogen-bonds. Compared with 1, complex 2 features a 2D layer structure, which is made up of 1D tubes consisting of helical chains via π-π interactions. Complex 3 displays a 3D metal-organic framework with {65·8} topology. The results reveal that different N-donor auxiliary ligands have a subtle effect on the final structures of coordination supramolecules. Moreover, the solid photoluminescent property of 2 was also studied at room temperature.