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Efficient solar charging of a battery has been demonstrated in the past by sizing batteries many times that of a solar cell to reduce the effective current density experienced by the battery. Altho...

We demonstrate open circuit voltages exceeding 1.26 V for inverted planar CH3NH3PbI3 solar cells fabricated using a combination of lead acetate and PbCl2 precursors leading to smooth films and large grain sizes. Surface recombination is suppressed by careful optimization of the PTAA hole transport and PCBM electron transport layers. Suppression of bulk and surface recombination is verified by absolute photoluminescence measurements with external quantum efficiencies of amp; 8764;5 in complete cells. In addition, we find exceptionally long photoluminescence lifetimes in full cells and in layer stacks involving one or two contact layers. Numerical simulations reveal that these long photoluminescence lifetimes are only possible with extremely low recombination velocities at the interfaces between absorber and contact materials

Advanced energy materials 11(19), 2003489 (2021). doi:10.1002/aenm.202003489, Published by Wiley-VCH, Weinheim

Advanced energy materials 10, 2102290 (2021). doi:10.1002/aenm.202102290, Published by Wiley-VCH, Weinheim

Materials advances (2021). doi:10.1039/D0MA00902D, Published by Royal Society of Chemistry, Cambridge

The interfaces between absorber and transport layers are shown to be critical for perovskite device performance. However, quantitative characterization of interface recombination has so far proven to be highly challenging in working perovskite solar cells. Here, methylammonium lead halide (CH3NH3PbI3) perovskite solar cells are studied based on a range of different hole-transport layers, namely, an inorganic hole-transport layer CuOx, an organic hole-transport layer poly(triarylamine) (PTAA), and a bilayer of CuOx/PTAA. The cells are completed by a [6,6]-phenyl-C-61-butyric acid methyl ester (PCBM)/bathocuproine/Ag electron contact. Energy levels are characterized using photoelectron spectroscopy and recombination dynamics by combining steady-state photoluminescence and transient photoluminescence with numerical simulations. While the PTAA-based devices hardly show any interface recombination losses and open-circuit voltages >1.2 V, substantial losses are observed for the samples with a direct CuOx/perovskite interface. These losses are assigned to a combination of energetic misalignment at the CuOx/perovskite interface coupled with increased interface recombination velocities at the perovskite/PCBM interface.

An absorber layer that does not fully cover the substrate is a common issue for thin-film solar cells such as perovskites. However, models that describe the impact of pinholes on solar cell performance are scarce. Here, we demonstrate that certain combinations of contact layers suppress the negative impact of pinholes better than others. The absence of the absorber at a pinhole gives way to a direct electrical contact between the two semiconducting electron and hole transport layers. The key to understand how pinholes impact the solar cell performance is the resulting nonlinear diodelike behavior of the current across the interface between these two layers (commonly referred to as a shunt current). Based on experimentally obtained data that mimic the current–voltage characteristics across these interfaces, we develop a simple model to predict pinhole-induced solar cell performance deterioration. We investigate typical contact layer combinations such as TiO2/spiro-OMeTAD, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)/phenyl-C61-butyric acid methyl ester, and TiO2/poly(3-hexylthiophene). Our results directly apply to perovskite and other emerging inorganic thin-film solar cells, and the methodology is transferable to CIGS and CdTe. We find substantial differences between five commonly applied contact layer combinations and conclude that it is not sufficient to optimize the contact layers of any real-world thin-film solar cell only with regard to the applied absorber. Instead, in the context of laboratory and industrial fabrication, the tolerance against pinholes (i.e., the mitigation of shunt losses via existing pinholes) needs to be considered as an additional, important objective.

Designing new two-dimensional (2D) semiconductors with high carrier mobilities is highly desirable for material innovation, especially when the configuration has novel topological properties. Here, we proposed a first-principles-based design of a 2D crystal, namely a Be2N6 monolayer. In which, each N atom is shared by two neighboring N atoms and one Be atom, forming a novel moiety of benzene-like N6 rings. Rather than the instability of hexazine, the Be2N6 monolayer has a moderate cohesive energy, good kinetic and thermodynamic stability, due to the stabilization effect of the Be element by forming twelve classical two-centre–two-electron (2c–2e) σ-bonds and five multicenter 6c–2e π-bonds. There are ten π electrons in a unit cell, which satisfies the Huckel rule [4n + 2] (n = 2), indicating the Be2N6 monolayer aromaticity. As a result, the Be2N6 monolayer has an ultra-high mechanical strength of up to 200 J m−2. Particle-swarm optimization (PSO) computations reveal that a cyclo-N6-containing Be2N6 monolayer is the lowest-energy configuration in 2D forms with a stoichiometry of 1 : 3, and therefore could be synthesized experimentally. Furthermore, the Be2N6 monolayer is an indirect semiconductor with a band gap of 1.71 eV at the hybrid functional level, close to that of the bulk amorphous silicon ∼1.6 eV widely used in solar cells. At this point, the high electron mobility of up to ∼104 cm2 V−1 s−1 and visible-light absorption of ∼105 cm−1 are observed for the Be2N6 monolayer. If realized, it will not only enrich the knowledge of the bonding nature of nitrogen but could also have potential applications in electronics and optoelectronics.

Non-radiative recombination processes are the biggest hindrance to approaching the radiative limit of the open-circuit voltage for wide-band gap perovskite solar cells. In addition, to high bulk quality, good interfaces and good energy level alignment for majority carriers at charge transport layer-absorber interfaces are crucial to minimize non-radiative recombination pathways. By tuning the lowest-unoccupied molecular-orbital of electron transport layers via the use of different fullerenes and fullerene blends, we demonstrate open-circuit voltages exceeding 1.35 V in CH3NH3Pb(I0.8Br0.2)3 device. Further optimization of mobility in binary fullerenes electron transport layer can boost the power conversion efficiency as high as 18.6%. We note in particular that the Voc-fill factor product is > 1.085 V, which is the highest value reported for halide perovskites with this band gap.

An azole-based metal–organic framework [Cd(tzphtpy)2]n·6.5nH2O, hydrothermally synthesized from the reaction mixture of a π-electron rich azole ligand 4-(tetrazol-5-yl)phenyl-2,2′:6′,2″-terpyridine (Htzphtpy) and CdBr2·4H2O, displays direct white-light emissions at a wide range of excitation wavelengths (286–386 nm) through modulating the relative intensity of complementary yellow and blue colors. Photoluminescence experiments and density of states and the calculations of time-dependent density functional theory demonstrate that the higher-energy blue emission is attributed to intraligand charge transfer, and the lower-energy yellow emission is related to interligand π–π interactions. The synergism of ligand-centered charge transfer and interligand π–π interactions is first found in white-light emitting azole-based metal–organic frameworks. Our work provides a new synthetic strategy for azole-based or other system white-light emitting materials.

An alternative approach to fabricate color-tunable and white-light-emitting lanthanide(III) coordination polymers (LnCPs) is demonstrated by employing a selective light-emitting tetrazolate–dicarboxylate ligand, which displays different color emissions when coordinated to different lanthanide(III) ions. The emission colour of the obtained LnCPs can be modulated from orange to white by simply adjusting the excitation wavelengths. White-light emissions, with high color rendering index and favorable correlated color temperature, have been successfully realized in new 2D single-component Sm(III) and two-component Eu(III)-doped Gd(III) coordination polymers excited at specific excitation wavelengths.

Herein, we report a novel high-dimensional I3O3 organic–inorganic hybrid framework, namely [Cd3(OH)2(tza)2]n (1) (H2tza = 1H-tetrazolate-5-acetic acid), where a rare pure ths inorganic connectivity of Cd–Ohydroxyl is observed. Meanwhile, 1 displays blue emission and high thermal stability up to 370 °C.

Three air-stable tetrahedral manganese(ii) dihalide complexes [MnX2(DPEPO)] (DPEPO = bis[2-(diphenylphosphino)phenyl]ether oxide; X = Cl, Br and I) were prepared. All of the obtained compounds were structurally characterized by single-crystal X-ray diffraction analyses, which reveal that they crystallize in centrosymmetric space groups and feature an isolated mononuclear structure with Mn(2+) in a tetrahedral environment. Interestingly, these complexes show excellent photoluminescent performance in neat solid form, with the highest total quantum yield (Φtotal) of up to 70% recorded for the dibromide complex. Intense green flashes of light could be observed by the naked eye when rubbing the manganese(ii) complexes.

Ionothermal reaction of NiCl2·6H2O and tetrazole-1-acetic acid (1-Htza) in ionic liquid [BMIM]Br (BMIM = 1-butyl-3-methylimidazolium) afforded a new 3D Ni(II) coordination polymer [Ni(1-tza)2]n 1. When 2,2′-bipy was introduced, another 1D chained polymer, [Ni(1-tza)(2,2′-bipy)(H2O)2]nXn·2nH2O (2, X = 0.78Br + 0.22Cl) was acquired. Both compounds have been structurally characterized by single-crystal X-ray diffraction analyses. In the obtained compounds, 1-Htza ligands adopt two different coordination modes: μ3-κN4:κO1:κO2 for 1, and μ2-κN4:κO1 for 2. The temperature-dependent magnetic susceptibilities of 1 and 2 have been measured and theoretically fitted by means of a 1-D chain model. A ferromagnetic interaction between Ni(II) ions exists in 1 with J = 3.24 cm− 1, while an antiferromagnetic interaction in 2 with J = − 5.72 cm− 1.

Reaction of tetrazole-1-acetic acid (1-Htza) with a Cu(II) salt in ionic liquids with different anions, [BMIM]X (BMIM = 1-butyl-3-methylimidazolium; X = Br−, BF4−, NTf2− (NTf2− = bis((trifluoromethyl)sulfonyl)amide)), afforded five Cu(II) coordination compounds, [Cu2(1-tza)4]Br·H3O·1/3H2O (1), [Cu2(1-tza)4]BF4·H3O·H2O (2), [Cu(μ2-Cl)(1-tza)(1-Htza)(H2O)]·0.5H2O (3), [CuCl(μ2-Cl)(1-Htza)2(H2O)]·H2O (4), and [CuCl2(1-Htza)2]·H2O (5). Single-crystal X-ray diffraction analyses reveal that 1–5 display various structures, and the 1-tza− ligand exhibits diverse coordination modes. Compounds 1 and 2 possess higher dimensional structures (a 2-D neutral Kagome topology network for 1 and a 3-D lvt-type topology framework for 2) with fully deprotonated 1-tza− ligands. Compounds 3–5 display lower dimensional structures (1-D, 1-D and 0-D for 3, 4 and 5, respectively) with partly or fully protonated 1-Htza. The anions of ionic liquids have significant influences on the final molecular architectures, which arise from different water miscibility of ionic liquids.

We employed two pairs of new in-situ-generated chiral amino acid-tetrazole ligands in constructing homochiral Zn(II) coordination compounds: [Zn(tzet)]n (1a for (S)-tzet and 1b for (R)-tzet, H2tzet = N-[2-(1H-tetrazol-5-yl)ethyl]tryptophan) and [Zn(tzep)(H2O)2]·H2O (2a for (S)-tzep and 2b for (R)-tzep, H2tzep = N-[2-(1H-tetrazol-5-yl)ethyl]proline), which were hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Structural analysis reveals that 1 features a 2D homochiral framework generated by both tetrazolate and carboxylate bridges in tzet(2-) ligands. The isolated structure of 2 is stabilized by extensive hydrogen bonds, which leads to formation of a supramolecular 2D architecture. The absolute configuration induced at the nitrogen atoms of 1 and 2 is strictly related to the neighboring chiral carbon atoms by hydrogen-bond interactions. To further investigate their chirality, the combined experimental and theoretical analyses of circular dichroism spectra reveal the absolute configurations and nature of the Cotton effects. Solid-state excitation and emission spectra for 1 and 2 at room temperature were investigated with relevant density of states calculation, and tunable photoluminescence emission of 1 under different excitation wavelengths was discussed. As nitrogen-rich tetrazolate compounds, 1 and 2 possess higher enthalpies of combustion and may serve as a new family of promising energetic materials.

Exploration of new spin systems with low-dimensional subunits have been of great interest in the past decades due to their interesting physical properties and potential applications in molecular spintronics. Two inorganic supramolecular complexes, (Hg3S2)(FeCl4) and (Hg3S2)(CoCl4), with trigonally aligned 1-D infinite magnetic ∞1(FeCl4)2− or ∞1(CoCl4)2− chains have been prepared by solid-state reactions. They exhibit 3-D long-range spin order with strong field dependence and field induced metamagnetic behavior. The intrachain and interchain magnetic coupling constants were estimated by DFT+U and DFT+U+SOC calculations and the both complexes can be regarded as partially frustrated spin systems. The spin Hamiltonian was constructed, the ground state is proposed to be incommensurate spiral spin order, which differs from the commensurate 120° spin structure ground state of fully frustrated trigonal case by a little canted angle. This study shows that cooperative magnetic ordering induced by geometric frustration can be realized in inorganic supramolecular systems assembled by weak van der Waals’ interactions.

Two inorganic–organic hybrids, (MPDA)2n(Pb3I10)n (MPDA = p-Me3NC6H4NMe3) (1) and (H2EPDA)n(Pb2I6)n·2nH2O (H2EPDA = p-Et2NHC6H4NHEt2) (2), have been solvothermally synthesized using p-phenylenediamine (PDA) as a precursor. Their iodoplumbate ions all show 1-D chain structures, but differ in interlinkage modes of [PbI6] octahedra: the former is both face- and edge-sharing, while the latter is face-sharing. The chain-like structure in 1 was reported only once in the literature. The results of optical absorption spectra and theoretical calculations for compounds PbI2 and 1–2 reveal a quantum confinement effect. Photoluminescent analyses show that they all exhibit blue emissions upon UV irradiation, which mainly originate from charge transfer from iodine atoms to ammoniums.

The first homochiral binuclear metal complex cation-containing inorganic–organic hybrid chalcogenidometalates [Ni2(teta)3](Ge4S10)·H2O (1 and 1′; teta = triethylenetetramine) were prepared, which spontaneously separate in enantiomers upon crystallization; a unique water-mediated hybrid supramolecular helix, and the correlation between molecular chirality and absolute helicity are observed in the entantiomers.

Hydrothermal reaction of NaN3, Na(4-cba) (4-Hcba = 4-cyanobenzoic acid) and ZnBr2 afforded a novel 3D Zn(II) coordination polymer [Zn2(4-tzba)2(H2O)]n 1 (4-H2tzba = 4-(5H-tetrazol)benzoic acid). In situ [2 + 3] cycloaddition reaction of nitrile and azide in the presence of ZnBr2 yielded tetrazolate-5-carboxylate 4-tzba2− ligand. Compound 1 displays an unprecedented four-connected topological network with 1D hexagonal channels constructed from trigonal rings [Zn3(4-tzba)6]. The solid-state photoluminescent studies revealed that 1 exhibits a strong blue emission mainly originating from 4-tzba2− ligand-centered charge transition.

Hydrothermal reaction of Na(3-cba) (3-cba = 3-cyanobenz-oate), NaN 3 and a metal salt with either 2,2'-bipyridine (2,2'-bipy) or 1,10-phenanthroline (phen) afforded four novel Zn II / Cd II polymers, which have been structurally characterized by single-crystal X-ray diffraction analysis. In situ [2 + 3] cycloaddition reaction of nitrile and azide in the presence of a Zn II or Cd II salt yielded the ligand 3-(5H-tetrazolyl)benzoate (3-tzba 2- ) [3-H 2 tzba = 3-(5H-tetrazolyl)benzoic acid]. The obtained polymers are formulated as [Zn 2 (3-tzba)(N3 ) (OH)(2,2'-bipy)](1),[Zn(3-tzba)(2,2'-bipy)(H 2 O)]·3H 2 O(2), [Zn 2 (3-tzba) 2 -(phen) 2 ]·H 2 O (3) and [Cd 4 (3-tzba) 2 (N 3 ) 4 (2,2'-bipy) 3 ]·H 2 O (4). A crystalline mixture of Zn II polymers 1 and 2 with infinite ladder-like chain and zigzag chain structures, respectively, was obtained from the reaction in the presence of 2,2'-bipy. The replacement of 2,2'-bipy with phen as an auxiliary ligand yielded 3, which shows a pearl-necklace-like chain structure. Further, the introduction of Cd II instead of Zn II resulted in the formation of 4, which has a 2D corrugated layer structure. The 3-tzba 2- ligands display four different coordination modes in 1-4, and modes μ 2 -κN2:κO1,O2 (in 2) and μ 3 -κN3:κO1:κO2 (in 3) are observed in tetrazolate-5-carboxylate polymers for the first time. Photoluminescent studies in the solid state at room and low temperature revealed that 1-4 exhibit interesting luminescent behaviors, and the relevant density of states (DOS) calculation results showed that their photoluminescence mainly originates from ligand-centered emission and is dependent on the organic ligand incorporated into the polymer.

Hydrothermal reaction of Cd(NO3)2, Co(NO3)2, Na(3-cba) and NaN3 yielded a 3D heterometallic coordination polymer, [Cd(μ5-3-tzba)(μ2-3-cba)(μ3-OH)Co(H2O)]n·2nH2O 1 (3-H2tzba = 3-(5H-tetrazol)benzoic acid and 3-Hcba = 3-cyanobenzoic acid), which was characterized by single-crystal X-ray diffraction. The in situ [2 + 3] cycloaddition reaction of nitrile and azide in presence of Cd(II) salt afforded tetrazolate-based 3-tzba2− ligand. In 1, metal-oxo chains [Cd(μ3-OH)Co]n are linked by 3-tzba2− in an unprecedented μ5-κN1:κN2:κN3:κN4:κO1,O2 coordination mode to form 2D layers, which are further pillared by 3-cba− to generate a 3D open framework encapsulating 1D chiral channels. Variable-temperature magnetic studies show that 1 exhibits antiferromagnetic interactions between Co(II) ions bridged by μ3-OH group.

Hydrothermal reaction of 1H-tetrazolate-5-ethyl acetate (Htzea), MCl2 (M = Zn, Cd) and NaOH at different reaction temperatures produced three new coordination polymers: 2-D layered polymer [Zn(tza)(H2O)2]n 1, and 1-D chained supramolecular isomers 2 and 3 formulated as [Cd(tza)(H2O)2]n (H2tza = 1H-tetrazolate-5-acetic acid), respectively. In these obtained polymers, tza2− ligand adopts variable coordination modes: μ3-κN3:κO1:κO2,N1 and μ3-κN1:κN3:κO2 for 1, and μ3-κN2:κN1,O2:κO1,O2 for 2 and 3. The effects of reaction temperature and metal centers on the final polymeric frameworks have been discussed. Polymers 1–3 exhibit blue photoluminescence mainly arising from intraligand transitions of tetrazolate rings in tza2− ligand.

Two new lead(II) coordination polymers, [Pb(NO3)(tzib)]n (1) and [Pb(tzib)2]n (2), were successfully synthesized from the reaction of a rigid ligand 1-tetrazole-4-imidazole-benzene (Htzib) and lead(II) nitrate in different solvents. The obtained polymers have been characterized by single-crystal X-ray diffraction analyses, which show that both polymers feature 2D layer structures. The inorganic anion nitrate in 1 shows a μ2-κO3:κO3 bridging mode to connect adjacent lead ions into a zigzag chain, and then the organic ligands tzib(-) join the neighboring chains into a 2D layer by a μ3-κN1:κN2:κN6 connection mode. In 2, there are two different bridging modes of the tzib(-) ligand: μ3-κN1:κN2:κN6 and μ3-κN1:κN6 to coordinate the lead ions into a 2D layer structure. Interestingly, both polymers displayed broadband emissions covering the entire visible spectra, which could be tunable to near white-light emission by varying excitation wavelengths.

(Hg6P4Cl3)(PbCl3) (I) and (Hg23P12)(ZnCl4)6 (II) are synthesized by solid state reactions of Hg2Cl2, Hg(CN)2, PbCl2, and red phosphorus for compound (I) (Pyrex tube, 340 °C, 5 d, 90% yield), and from mixtures of HgCl2, Hg2Cl2, Zn, and red phosphorus for compound (II) (Pyrex tube, 400 °C, 5 d, 80% yield).

Two new different-bond-type hybrid compounds, (Hg6P4Cl3)(PbCl3) (1) and (Hg23P12)(ZnCl4)6 (2), with supramolecular interactions between host and guest moieties, which based on metal–pnicogen, pnicogen–pnicogen, and metal–halogen bonds were obtained by solid-state reactions. Compounds 1 and 2 show large second-harmonic-generation (SHG) activity and are transparent in the wide mid-IR region, providing an effective route for searching new IR nonlinear-optical material systems by combining two or more different bond types with no IR absorption within a single compound through supramolecular assembly. Theory predications based on first-principles calculations are also performed on the SHG properties of 1 and 2.

(II) crystallizes in the triclinic space group P with Z = 1 and (III) in the monoclinic space group P21/c with Z = 2 (single crystal XRD).

To observe the efficacy and safety of Fushile, a compound preparation of several Chinese herbal drugs, in the treatment of benign prostatic hyperplasia (BPH).A multi-centered, open and self-controlled clinical trial was performed in 60 BPH patients, who were treated with Fushile for 12 weeks. The efficacy of the compound was evaluated by the International Prostate Syndrome Score (IPSS), maximum flow rate (Qmax), post void residual (PVR) and prostate volume as the primary indexes and by the quality of life (QOL) score and average urinary flow rate (Qave) as the secondary indexes.After 12 weeks of Fushile treatment, IPSS, Qmax, PVR, QOL and Qave of the BPH patients were significantly improved (P0.01), but there was no significant difference in the volume of the prostate before and after the treatment (P0.05). No adverse events were observed in any of the patients.Fushile can significantly improve voiding symptoms, increase urinary flow and reduce PVR in BPH patients. It is effective and safe in the treatment of BPH.

To observe changes of plasma polypeptide hormone levels in rats with gastric ulcer after exposure to intense noise, and to discuss their mechanism.80 Wistar rats were used in the study. Plasma levels of rat gastrin (GAS), motilin (MTL), osteocalcin (BGP), substance P (SP), neurotensin (NT) and somatostatin (SS) in rats were measured by radioimmunoassay.(1) In non-noise-exposure but with gastric ulcer group, the plasma MTL [(160.70 +/- 40.34) pg/ml] and BGP [(27.63 +/- 13.13) pg/ml] levels on 10 d after gastric ulcer model operation were remarkably higher than those in control group [(89.21 +/- 49.94) pg/ml, (9.10 +/- 1.38) pg/ml respectively] (P0.05 and P0.01), while the GAS level was remarkably descended [(107.00 +/- 21.75) vs (158.48 +/- 20.92) pg/ml] (P0.01). (2) In noise-exposure but without gastric ulcer group, the plasma MTL [(312.80 +/- 207.42) pg/ml] and BGP [(17.76 +/- 12.33) pg/ml] levels on 10 d were also significantly increased as compared with the control group (P0.01 and P0.05 respectively), while the GAS levels didn't change. (3) In noise-exposure + gastric ulcer group, the areas of gastric ulcer on 10 d and 40 d after noise and operation [(15.33 +/- 7.26) and (15.11 +/- 12.45) mm(2) respectively] were significantly larger than those of the control [(8.22 +/- 6.66), (3.67 +/- 9.90) mm(2)] (P0.05). The plasma MTL levels on 10 d and 40 d [(244.44 +/- 68.11) and (191.20 +/- 60.50) pg/ml respectively] were higher than those in control group [(160.70 +/- 40.34) and (93.10 +/- 52.90) pg/ml respectively] (P0.01).Intense noise exposure may make the rat gastric ulcer worsened and induce negative effect on healing of it. The gastrointestinal endocrine would be disturbed by combined effect of intense noise exposure with gastric ulcer in rats.

Hydrothermal reaction of cyano-substituted viologen derivatives and NaN3 with corresponding metal salts in the presence/absence of H2PTA (H2PTA = p-phthalic acid) yielded three azide-based polynuclear coordination polymers: [Co4(N3)4(PTA)3(4-CV)2]n·2nH2O 3D (1), [Co4(N3)4(PTA)3(3-CV)2]n·nH2O 3D (2), and [Cu6(N3)14(4-CV)2]n 2D (3) (3/4-CV+ = 4,4′-bipyridinium-N-methyl-3/4-benzonitrile). The azido bridges are employed to construct two types of polynuclear cluster units: tetranuclear [Co4(μ1,1-N3)4] and hexanuclear [Cu6(μ1,1-N3)6(μ1,1,1-N3)4]. Polymers 1 and 2 are isostructural, and exhibit similar 3D frameworks constructed by unprecedented linear tetranuclear CoII4 units with a four-connected 65·8 topology. Polymer 3 features a 2D (4,4) topological network built up by hexanuclear CuII6 segments. The azide anion exhibits diverse coordination modes: μ1,1-N3 in 1 and 2, and μ1,1-, μ1,3-, μ1,1,1- and μ1,1,3-N3 in 3. Variable-temperature magnetic susceptibility data denote that 1 and 2 display a weak antiferromagnetic interaction in CoII4 units and 3 shows a dominant ferromagnetic exchange in CuII6 units.

Hydrothermal reaction of N-(2-cyanoethyl)glycine and NaN3 with corresponding metal salts yielded three energetic coordination polymers: [Zn(tzeg)]n1 and [M(tzeg)(H2O)]n (M = Cd2+ for 2, Cu2+ for 3) (H2tzeg = N-[2-(1H-tetrazol-5-yl)ethyl]glycine), which were characterized by single-crystal X-ray diffraction. Nitrogen-rich tzeg2− ligand is a new in situ generated organic compound through [2 + 3] cycloaddition reaction of nitrile and azide, which adopts two different coordination modes in 1–3. Polymer 1 features an achiral 3D network built up by interweaving of left/right-handed helical channels. Isostructural 2 and 3 exhibit an achiral 2D network formed alternately by left/right-handed helical chains. As nitrogen-rich energetic materials, 1 and 3 possess higher enthalpies of combustion (ΔHc), which are −12.054 and −11.583 kJ g−1, respectively, than the classical energetic compounds 1,3,5-trinitro-1,3,5,-triazine (RDX, −9.6 kJ g−1) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX, −9.44 to −9.88 kJ g−1). The solid-state excitation and emission spectra for 1–3 were investigated at room temperature, which reveals ligand-centered luminescent emissions in the intensity order of 2 > 1 > 3. Variable-temperature magnetic susceptibility data show that 3 displays a weak antiferromagnetic interaction mainly resulting from magnetic exchange coupling between Cu2+ ions through double tetrazolato bridges.

Four Zn(II) tetrazolate coordination compounds have been hydrothermally synthesized and structurally determined by single-crystal X-ray diffraction. They are formulated as [Zn(3-tzbd)2]n·nH2O (1), [Zn2(3-tzbd)2(OH)2(4,4′-bipy)]n·nH2O (2), [Zn2(3-tzbd)3(N3)(4,4′-bipy)2]n·nH2O (3) and Zn2(3-tzbd)4(phen)2 (4), where 3-Htzbd = 3-(5H-tetrazol)benzaldehyde. The 3-tzbd− ligand, which was in situ generated through a [2 + 3] cycloaddition reaction of nitrile and azide, displays diverse coordination modes. Compound 1 exhibits a (4,4)-connected two-dimensional (2D) layer generated by the linkage of dinuclear units of [Zn2(μ2-3-tzbd)2] and μ2-3-tzbd− ligands. In 2, Zn(II) atoms are connected by μ2-3-tzbd− ligands and μ3-OH− anions to form unusual double-stranded stair-like chains, which are further linked by 4,4′-bipy to create a 2D sheet. Compound 3 features an unprecedented one-dimensional (1D) four-legged, triple-ladder chain composed of tetranuclear units [Zn4(μ2-3-tzbd)4(μ2-N3)2]. Two Zn(II) atoms in 4 are bridged by μ2-3-tzbd− ligands to result in an isolated dinuclear structure. In addition, the luminescent properties of 1–4 were investigated in the solid state at room temperature. The relevant density of states (DOS) calculation results show that their photoluminescence mainly originates from ligand-centered emission and is dependent on the organic ligand incorporated into the compounds.

A new carboxylate-introduced 1,2,3-triazole, 1-(3,5-dicarboxyphenyl)-4-carboxy-1H-1,2,3-triazole (H3dcpct), was synthesized by 1,3-dipolar cycloaddition of a terminal alkyne to azide in the presence of a Cu(II) salt. Hydrothermal reaction of H3dcpct and Mn(NO3)2·6H2O or Co(NO3)2·6H2O in different NaOH/H3dcpct molar ratios afforded four new coordination polymers [Mn(dcpt)(H2O)2]·0.25H2O 1, [Mn(dcpt)(H2O)] 2, [Co(dcpt)(H2O)2]·H2O 3 and [Co(H2O)6][Co2(dcpct)2(H2O)6]·2H2O 4 (H2dcpt = 1-(3,5-dicarboxyphenyl)-1H-1,2,3-triazole). The in situ hydrothermal decarboxylation of H3dcpct into H2dcpt in 1–3 was found and its possible mechanism is proposed. In 1 and 3, dcpt2− ligands bridge Mn(II) and Co(II) ions, respectively, to give two similar 2D layered structures with a (6,3)-connected network topology. Polymer 2 displays a whole achiral 3D open framework with both chiral and achiral channels in the same direction and possesses an unprecedented (3,6)-connected (4·82)(42·812·10) network topology. The structure of 4 features a 1D chained net, in which no decarboxylation occurred. Variable-temperature magnetic susceptibility data show that 1 exhibits a weak ferromagnetic interaction and 2 manifests an overall antiferromagnetic interaction between their respective Mn(II) ions, while 3 and 4 display an antiferromagnetic interaction between Co(II) ions and/or spin-orbital coupling. The thermal stabilities of all obtained polymers have also been examined.

Hydrothermal reaction of ZnCl2, NCCH2CH2COONa and NaN3, in the absence/presence of auxiliary ligand 2,2′-bipy/4,4′-bipy, gave birth to three novel coordination polymers, namely, [Zn(tzp)]n (1), [Zn2(tzp)(N3)(OH)(2,2′-bipy)]n (2) and [Zn2(tzp)2(4,4′-bipy)]n (3) (H2tzp = 1H-tetrazolate-5-propionic acid). The tzp2− ligand was in situ generated through the [2 + 3] cycloaddition reaction of nitrile and azide, which was first untilized to synthesize coordination compounds. Polymer 1 behaves as a three-dimensional (3-D) network built up by the fusion of one-dimensional (1-D) pseudo-channels formed by the linkage of tzp2− ligands and tetrahedral Zn nodes. When the chelating 2,2′-bipy was introduced into the reaction system, a two-dimensional (2-D) puckered network 2 was constructed, where 1-D pseudo-channels, similar to those in 1, are bridged by azide ions in an end-on (EO) mode. Employment of the linear bridging 4,4′-bipy ligand as the auxiliary ligand resulted in the formation of an unusual 3-D polymer 3, where the connection of Zn and tzp2− produces a 2-D network, which are further joined by 4,4′-bipy. The tzp2− ligands in 1–3 show the flexible conformations and different coordination modes, with the tetrazolate group being the 1,4-N mode and the carboxylate group being the syn–anti, syn–syn and monodentate mode, respectively. The results suggest that the flexible nature of the tzp2− ligand as well as the introduction of auxiliary ligands is responsible for the formations of 1–3. Their photoluminescent properties and thermal stabilities have also been discussed.