Application of 4,4'-(2-Carboxypropane-1,3-diyl)dibenzoic Acid in Coordination Metal Complexes:Synthesis,Characterization,and Theoretical Studies

[Pb（HL）（phen）]n （1） and [Cd3L2（phen）]n （2）, where phen = 1,10-phenanthroline and L = 4,4＇-（2-carboxylatopropane-1,3-diyl）dibenzoate, were hydrothermally prepared and fully characterized by X-ray single-crystal diffraction, infrared spectroscopy and thermogravimetric analyses. The decomposition temperature of 1 and 2 was measured to be ca. 304 and 416 ℃, respectively. The charge transfer transition based absorption of 1 and 2 was also verified by the powder scattering spectra and theoretical analyses.

Highly stable perovskite solar cells with a novel Ni-based metal organic complex as dopant-free hole-transporting material

Hole-transporting material(HTM)plays a paramount role in enhancing the photovltaic performance of perovskite solar cells(PSCs).Currently,the vast majority of these HTMs employed in PSCs are organic small molecules and polymers,yet the use of organic metal complexes in PSCs applications remains less explored.To date,most of reported HTMs require additional chemical additives(e.g.Li-TFSI,t-TBP)towards high performance,however,the introduction of additives decrease the PSCs device stability.Herein,an organic metal complex(Ni-TPA)is first developed as a dopant-free HTM applied in PSCs for its facile synthesis and efficient hole extract/transfer ability.Consequently,the dopant-free Ni-TPAbased device achieves a champion efficiency of 17.89%,which is superior to that of pristine Spiro-OMeTAD(14.25%).Furthermore,we introduce a double HTM layer with a graded energy bandgap containing a Ni-TPA layer and a CuSCN layer into PSCs,the non-encapsulated PSCs based on the Ni-TPA/CuSCN layers affords impressive efficiency up to 20.39%and maintains 96%of the initial PCE after 1000 h at a relative humidity around 40%.The results have demonstrated that metal organic complexes represent a great promise for designing new dopant-free HTMs towards highly stable PSCs.

Prominent removal of trace lead(Ⅱ)ions from polluted water by terephthalic acid reformed Al/Zn metal organic nanoflakes

Terephthalic acid reformed Al/Zn metal organic nanoflake was prepared and functionalized with trie-thylamine(T-AlZn).Without adding terephthalic acid,there was no product of metal organic nanoflake.T-AlZn has a remarkable performance in removing trace lead(Ⅱ)ions(Pb^(2+)).The adsorption equipoise with the removal rate≥97%was reached within 35 min.The removal rates of T-AlZn for Pb^(2+)declined by only 16.73%after four regenerations.The adsorption of T-AlZn for Pb^(2+)follows the Langmuir isotherms model and pseudo-second-order dynamics model.The utmost adsorption competence was calculated as 215.27 mg g^(-1).The T-AlZn adsorbent exhibits a bright prospect in the adsorption for Pb^(2+)and is a considerable candidate in the disposal of industrial sewage.

Polyoxometalate-based metal-organic complexes constructed from a new bis-pyrimidine-amide ligand with high capacitance performance and selectivity for the detection of Cr(Ⅵ)

In this paper,three new polyoxometalates(POM)-based metal–organic complexes constructed from a new semi-rigid organic ligand N,N'-bis(4-pyrimidinecarboxamido)-1,2-cyclohexane(4-bpmah)H_(2)[Cu(4-bpmah)_(2)(SiMo_(12)O_(40))(H_(2)O)_(2)]·2H_(2)O(1),H[Cu(4-bpmah)_(2)(PMo_(12)O_(4)0)(H_(2)O)_(2)]·2H_(2)O(2)and[Cu(4-bpmah)(H_(2)O)_(2)]·[Cu_(2)(TeMo_(6)O_(24))(H_(2)O)_(10)]·4H_(2)O(3)were synthesized by hydrothermal method.Single crystal X-ray analyses showed that complexes 1 and 2 were isostructural,in which the isolated Keggin-type[SiMo1_(2)O_(40)]^(4–)/[PMo_(12)O_(40)]^(3–)anions and[Cu(4-bpmah)_(2)(H_(2)O)2]^(2n+)units were expanded into 3D supramolecular structures through hydrogen bond interactions.In complex 3,the 1D[Cu(4-bpmah)(H_(2)O)_(2)]^(2n+)metal–organic chains and isolated[Cu_(2)(TeMo_(6)O_(24))(H_(2)O)_(10)]^(2n–)units were expanded into a 3D supramolecular framework by the hydrogen bond interactions.In this paper,carbon cloth working electrodes composited by the title complexes(1/CC,2/CC and 3/CC)were prepared and used as electrodes for supercapacitors.The performance of supercapacitors as well as the influence of electrolyte solution and title complexes quality load on the performance of supercapacitors were studied.Furthermore,the electrochemistry and electrocatalytic behaviors of complexes 1–3 bulk-modified carbon paste electrodes(1-CPE,2-CPE and 3-CPE)toward the reduction of KBrO_(3),KNO_(2),Cr(Ⅵ),as well as their sensing behaviors on Cr(Ⅵ)were investigated.

Highly efficient removal of trace lead(Ⅱ)from wastewater by 1,4-dicarboxybenzene modified Fe/Co metal organic nanosheets

A novel Fe/Co metal organic complex nanosheet modified by 1,4-dicarboxybenzene(BDC),i.e.,FeCo@BDC,was prepared,and highly efficient removal performance for trace lead(Ⅱ)(Pb^(2+))was demonstrated in the neutral aqueous solutions.The removal rates were higher than 95%and the adsorption was equilibrated in 15 min.The isotherms and kinetics for the adsorption Pb^(2+)by the FeCo@BDC adsorbents followed Langmuir model and pseudo-second-order model,respectively.The maximum adsorption capacity was 220.48 mg g^(-1).The FeCo@BDC adsorbents also own a prominent regeneration performance.The prominent performance of in the removal of trace Pb^(2+)makes FeCo@BDC an ideal candidate as commercial adsorbent materials.

Hollow click-based porous organic polymers for heterogenization of [Ru（bpy）3]2＋ through electrostatic interactions

A facile approach for the heterogenization of transition metal catalysts using non-covalent interactions in hollow click-based porous organic polymers （H-CPPs） is presented. A catalytically active cationic species, [Ru（bpy）3]〉 （bpy = 2,2＇-bipyridyl）, was immobilized in H-CPPs via electrostatic interactions. The intrinsic properties of [Ru（bpy）3]〉 were well retained. The resulting Ru- containing hollow polymers exhibited excellent catalytic activity, enhanced stability, and good recyclability when used for the oxidative hydroxylation of 4-methoxyphenylboronic acid to 4-methoxyphenol under visible-light irradiation. The attractive catalytic performance mainly resulted from efficient mass transfer and the maintenance of the chemical properties of the cationic Ru complex in the H-CPPs.

Efficient perovskite solar cells employing a solution-processable copper phthalocyanine as a hole-transporting material

The development of alternative low-cost and high-performing hole-transporting materials(HTMs) is of great significance for the potential large-scale application of perovskite solar cells(PSCs) in the future.Here,a facilely synthesized solution-processable copper tetra-(2,4-dimethyl-3-pentoxy) phthalocyanine(CuPc-DMP) via only two simple steps,has been incorporated as a hole-transporting material(HTM) in mesoscopic perovskite solar cells(PSCs).The optimized devices based on such a HTM afford a very competitive power conversion efficiency(PCE) of up to 17.1%measured at 100 mW cm^(-2) AM 1.5G irradiation,which is on par with that of the well-known 2,2',7,7'-tetrakis(N'N'-di-p-methoxyphenylamine)-9,9'-spirobifluorene(spiro-OMeTAD)(16.7%) under equivalent conditions.This is,to the best of our knowledge,the highest value reported so far for metal organic complex-based HTMs in PSCs.The advantages of this HTM observed,such as facile synthetic procedure,superior hole transport characteristic,high photovoltaic performance together with the feasibility of tailoring the molecular structure would make solution-processable copper phthalocyanines as a class of promising HTM that can be further explored in PSCs.The present finding highlights the potential application of solution processed metal organic complexes as HTMs for cost-effective and high-performing PSCs.