DMF Ligands Research Articles

Syntheses, characterization and antibacterial activity of mononuclear and dinuclear copper(II) complexes containing a hydrazone ligand

An aroylhydrazone compound (HL) was prepared and explored as a ligand (HL = N’-(2-hydroxy-4-methoxybenzylidene)-3-hydroxy-4-methoxybenzohydrazide). Reaction of the aroylhydrazone ligand with copper bromide and copper chloride afforded two new copper(II) complexes, [Cu2Br2L2] (1) and [CuL(DMF)]Cl (2), respectively. The aroylhydrazone ligand and copper complexes were characterized by CHN elemental analyses and infrared spectroscopy. Structures were further confirmed by single crystal X-ray diffraction experiments. The aroylhydrazone compound coordinates to Cu atoms through its phenolate oxygen, imino nitrogen and carbonyl oxygen. The Cu atom in 1 adopts a square pyramidal coordination, with three donor atoms of one L and one phenolate oxygen of a second L in the basal plane, and with one Br ligand at the apical position. The Cu atom in 2 is square pyramidal, with three donor atoms of one L and one oxygen of a DMF ligand in the basal plane, and with one Cl ligand at the apical position. Crystal structures of the aroylhydrazone and the copper complexes are stabilized by hydrogen bonds. The complexes possess antibacterial activities against B. subtilis, S. aureus and E. coli.

Palladium-Catalyzed Esterification of Aryl Fluorosulfates with Aryl Formates.

An efficient palladium-catalyzed carbonylation of aryl fluorosulfates with aryl formates for the facile synthesis of esters was developed. The cross-coupling reactions proceeded effectively in the presence of a palladium catalyst, phosphine ligand, and triethylamine in DMF to produce the corresponding esters in moderate to good yields. Of note, functionalities or substituents, such as nitro, cyano, methoxycarbonyl, trifluoromethyl, methylsulfonyl, trifluoromethoxy, fluoro, chloro, bromo, methyl, methoxy, N,N-dimethyl, and [1,3]dioxolyl, were well-tolerated in the reactions, which could be kept for late-stage modification. The reactions employing readily available and relatively robust aryl fluorosulfates as coupling electrophiles could potentially serve as an attractive alternative to traditional cross-couplings with the use of aryl halides and pseudohalides as substrates.

6-Bromo-2-hydroxypyridinate-bridged Paddlewheel-Type Dirhodium Complex Isomers: Synthesis, Crystal Structures, Electrochemical Properties, and Structure-Dependent Absorption Properties

Two new paddlewheel-type dirhodium (Rh2) complex isomers, formulated as trans-2,2- and 3,1-forms of [Rh2(bhp)4] (bhp = 6-bromo-2-hydroxypyridinate), were obtained by the reaction of 6-bromo-2-hydroxypyridine with [Rh2(O2CCH3)4(H2O)2] and characterized by NMR, ESI-MS, and elemental analyses. Single crystal X-ray diffraction analyses clarified that the crystal structure of trans-2,2-form takes a conventional paddlewheel-type dimer structure with no axial coordination ligands, i.e., trans-2,2-[Rh2(bhp)4], whereas that of the 3,1-form changed significantly depending on the kinds of solvent used for crystallization processes; dimer-of-dimers-type tetrarhodium complex, i.e., 3,1-[Rh2(bhp)4]2, and a conventional paddlewheel-type dimer complex with an axial DMF ligand, i.e., 3,1-[Rh2(bhp)4(DMF)], were observed. The 3,1-form showed unique absorption changes that were not observed in the trans-2,2-form; the trans-2,2-form showed an absorption band at approximately 780 nm both in the solid state and in solution (CH2Cl2 and DMF), whereas the 3,1-form showed a similar absorption band at 783 nm in CH2Cl2 solution, but their corresponding bands were blue-shifted in solid state (655 nm) and in DMF solution (608 nm). The molecular structures and the origin of their unique absorption properties of these Rh2 complexes were investigated using density functional theory (DFT) and time-dependent DFT (TDDFT).

Halogen-Dependent Diversity and Weak Interactions in the Heterometallic Ni/Cd Complex Solids: Structural and Theoretical Investigation.

Three novel heterometallic Ni/Cd coordination compounds [Ni(en)3][CdCl4]∙3dmso (1), [Ni(en)2(dmf)2][CdBr4] (2), and [Ni(en)3]2[CdI4](I)2 (3) have been synthesized through the self-assembly process in a one-pot reaction of cadmium oxide, nickel salt (or nickel powder), NH4X (X = Cl, Br, I), and ethylenediamine in non-aqueous solvents dmso (for 1) or dmf (for 2 and 3). Formation of the one- (1) or three-dimensional (2 and 3) hydrogen-bonded frameworks has been observed depending on the nature of the [CdX4]2- counter-anion, as well as on the nature of the solvent. The electronic structures of [Ni(en)3]2+ and [Ni(en)2(dmf)2]2+ cations were studied at the DFT and CASSCF levels, including the ab initio ligand field theory (AILFT) calculations. The non-covalent intermolecular contacts between the cationic nickel and anionic cadmium blocks in the solid state were investigated by the QTAIM analysis. The mechanism of ligand substitution at the nickel center in [Ni(en)2(dmf)2]2+ was theoretically investigated at the ωB97X-D4/ma-def2-TZVP//DLPNO-CCSD(T)/ma-def2-TZVPP level. The results demonstrate that thermodynamic factors are structure-determining ones due to low energy barriers of the rotation of dmf ligands in [Ni(en)2(dmf)2]2+ (below 3 kcal mol-1) and the reversible transformation of [Ni(en)2(dmf)2]2+ into [Ni(en)3]2+ (below 20 kcal mol-1).

Construction of Cu(DMF)2Cl Active Sites for Gas–Solid Acetylene Dimerization: Effects of DMF Ligand and Catalytic Mechanism

Construction of Cu(DMF)₂Cl Active Sites for Gas–Solid Acetylene Dimerization: Effects of DMF Ligand and Catalytic Mechanism

Rare earth inorganic-organic hybrid compounds based on Keggin-type polyoxometalate {SiW12} with fast-responsive photochromism and switchable luminescence properties

Four rare earth inorganic-organic hybrid compounds based on Keggin-type polyoxometalate {SiW12} with general formula [{RE(DMF)4(H2O)4RE(DMF)6}2{SiW12O40}3] (RE = La(1), Pr(2), Sm(3), Eu(4), DMF = N,N-dimethylformamide) were synthesized by the conventional solution method. Structure analyses indicate that four compounds are isostructural and are all built from three [SiW12O40]4– polyoxoanions and DMF ligands linked by RE3+. Compounds 1–4 are extremely sensitive to UV light and present excellent photochromic properties, in which the coloring and fading time of samples are both no more than 2 min, and the reversible coloring-fading process can be repeated for at least 10 cycles with little fatigue, suggesting that compounds 1–4 can be a series of fast-responsive and durable photochromic materials. Moreover, the solid-state photoluminescence spectra of compounds 3(Sm) and 4(Eu) display strong characteristic emissions of rare earth ions based on f–f transitions. Meanwhile, compound 4(Eu) has a longer fluorescence lifetime up to 566.74 μs. Notably, compounds 3(Sm) and 4(Eu) exhibit the switchable luminescence behavior induced by photochromism, which allows them to be used as potential molecular switches.

Desolvation-Degree-Induced Structural Dynamics in a Rigid Cerium-Organic Framework Exhibiting Tandem Purification of Ethylene from Acetylene and Ethane.

Due to the industrial requirements for high production and high quality of ethylene, efficient purification of ethylene from acetylene and ethane is of prime importance but challenging. Dynamic metal-organic frameworks (MOFs) have demonstrated intriguing structural dynamics and diverse applications recently. Among them, although a few flexible ones have exhibited interesting ethylene purification capability, rigid ones were yet barely investigated for such purpose. In this regard, a cerium(III)-based MOF was solvothermally synthesized, which is rigid and assembled from rod molecular building blocks associated with coordinative N,N-dimethylformamide (DMF) molecules. After liberating different degrees of DMF ligands via heating under vacuum or acetone exchange, both partially desolvated compounds of Ce-MOF-1 and Ce-MOF-2 were concertedly isolated in a fashion of single-crystal to single-crystal transformation. Although both newly generated materials crystallize in the same space group, they exhibit dissimilar unit cell parameters and slightly distinct ultramicropore sizes and pore microenvironments, thanks to the discrepancy in the desolvation degree. Consequently, Ce-MOF-1 and Ce-MOF-2 individually demonstrate C2H2- and C2H6-selective adsorption behavior, resulting in the potential tandem separation of C2H4 from C2H2 and C2H6 mixtures. The above results were successfully supported by not only single gas adsorption isotherms but also grand canonical Monte Carlo (GCMC) calculation studies and dynamic breakthrough experiments. The present work may pave the way for rigid MOFs aiming at advancing applications via solid-state structural dynamics.

Synthesis and spectroscopic characterization of Fe3+-BDC metal organic framework as material for lithium ion batteries

This work presents synthesis and spectroscopic characterization of a new metal-organic framework (MOF). The compound Fe-BDC-DMF was synthetized by the solvothermal method and prepared via a reaction between FeCl3.6H2O and benzene-1,4-dicarboxylic acid (H2BDC) or terephthalic acid using N,N-dimethylformamide (DMF) as solvent. The powder was characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) and infrared spectroscopy (IR) analysis. The electrochemical properties were investigated in a typical lithium-ion battery electrolyte by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charging and discharging. The synthetized Fe-BDC-DMF metal-organic framework (MOF) contains a mixture of three phases, identified by PXRD as: MOF-235, and MIL-53(Fe) monoclinic with C2/c and P21/c space groups. The structure of the Fe-BDC is built up from Fe3+ ions, terephalates (BDC) bridges and in-situ-generated DMF ligands. The electrochemical measurements conducted in the potential range of 0.5–3.5 V vs. Li+/Li0 show the voltage profiles of Fe-BDC and a plateau capacity of around 175 mAh/g.

Stable Nickel-Based Metal–Organic Framework Containing Thiophene/Diimidazole Units for Effective Near-Infrared Photothermal Conversion

Herein, a new Ni-based metal–organic framework (MOF, 1) bearing highly structural stability is synthesized by the reaction of utilizing a rigid and functionalized linker, 2,6-bis(pyridin-4-yl)-1,7-dihydrobenzo[1,2-d:4,5-d′]diimidazole (BBI4PY), in combination with Ni(NO3)2·6H2O and dibenzo[b,d]thiophene-3,7-dicarboxylic acid 5,5-dioxide (L1) under solvothermal conditions. The crystal structure of complex 1 is determined by single-crystal X-ray diffraction and is demonstrated to be a two-dimensional layered structure. In addition, PXRD, IR, TGA and UV/Vis-NIR spectra are also tested carefully to explore the solid structure of this complex. Remarkably, although no significant accumulation effect could be observed between the two-dimensional layers, a stacking interaction between DMF solvent molecules and ligand L1 could be found, which might promote non-radiative transitions and trigger obvious near-infrared photothermal conversion. Under 660 nm laser (0.6 W cm−2) illumination, the temperature of complex 1 increased rapidly from room temperature to 45.2 °C, with good thermal stability and cycle durability. Its photothermal conversion efficiency could reach 10.75%. This work provides an efficient way for assessing the promise of materials in the field of photothermal therapy.

Synthesis and spectroscopic characterization of NiII coordination network: Poly-[tris(µ4-Benzene-1,4-dicarboxylato)-tetrakis(µ1-dimethylformamide-κ1O)-trinickel(II)] as material for lithium ion batteries

The compound Ni3(C8H4O4)3(C3H7NO)3, poly-[tris(µ4-Benzene-1,4-dicarboxylato)-tetrakis(µ1-dimethylformamide-κ1O)-trinickel(II)], was synthesized by the solvothermal method prepared via reaction between NiCl2•6H2O and terephthalic acid using N,N-dimethylformamide (DMF) as solvent. The structure was characterized by powder X-ray diffraction and infrared spectroscopy analyses. The electrochemical properties as a potential active material in lithium-ion batteries were characterized by electrochemical impedance spectroscopy and galvanostatic charge-discharge curves in a battery half-cell.The characterization results show that the coordination network contains one independent structure in the asymmetric unit. It is constructed from Ni2+ ions, terephthalate bridges and in-situ-generated DMF ligands, forming two similar two-dimensional (2D) layer structures. These similar 2D layers are in an alternating arrangement and are linked with each other by dense H—H interactions (45%) to generate a three-dimensional (3D) supramolecular framework with ordered and disordered DMF molecules.The electrochemical measurements, conducted in the potential range of 0.5–3.5 V vs Li/Li+, show that Ni3(C8H4O4)3(C3H7NO)4 has good electrochemical properties and can work as anode in lithium-ion batteries. The material presents an initial specific capacity of ∼420 mAh g−1, which drops during consecutive scans but stabilizes at ∼50 mAh g−1. However, due to the wide potential range there are indications of a gradual collapse of the structure. The electrochemical impedance spectroscopy shows an increase of charge transfer resistance from 24 to 1190 Ohms after cycling likely due to this collapse.

Glycols in the Synthesis of Zinc-Anilato Coordination Polymers

We report the synthesis, structural investigation, and thermal behavior for three zinc-based 1D-coordination polymers with 3,6-di-tert-butyl-2,5-dihydroxy-p-benzoquinone, which were synthesized in the presence of different glycols. The interaction of zinc nitrate with glycols, followed by using the resulting solution in solvothermal synthesis with the anilate ligand in DMF, makes it possible to obtain linear polymer structures with 1,2-ethylene or 1,2-propylene glycols coordinated to the metal. The reaction involving 1,3-propylene glycol under similar conditions gives a crystal structure that does not contain a diol. The crystal and molecular structures of the synthesized compounds were determined using single crystal by X-ray structural analysis. The influence of glycol molecules coordinated to the metal on the thermal destruction of synthesized compounds is shown.

Ligated Solvent Influence on Interpenetration and Carbon Dioxide and Water Sorption Hysteresis in a System of 2D Isoreticular MOFs.

Four two-dimensional (2D), fluorinated metal-organic frameworks (MOFs), [Cu(hfipbb)(DMF)]n·0.5(DMF)n (1), [Cu(hfipbb)(DEF)]n (2), [Cu3(hfipbb)3(DMA)3]n·6(DMA)n·2(H2O)n (3), and [Cu2(hfipbb)2(DEA)2]n·2(DEA)n·2(H2O)n (4), have been synthesized where hfipbb = 4,4'-(hexafluoroisopropylidene)bis(benzoate), DMF = N,N'-dimethylformamide, DEF = N,N'-diethylformamide, DMA = N,N'-dimethylacetamide, and DEA = N,N'-diethylacetamide. The choice of either a formamide or acetamide solvent ligand leads to a 2D, doubly interpenetrated (1 and 2) or noninterpenetrated (3 and 4) MOF structure. Despite their lower potential void spaces, the doubly interpenetrated structures have superior carbon dioxide and hydrogen sorption properties. Their 195 K CO2 sorption isotherms display inflection points, followed by ∼3-fold increases in their sorption capacities and very large extents of hysteretic behavior. This shows that small changes in the identity of the ligated solvent ligand can affect whether the resulting MOF is interpenetrated or noninterpenetrated and so drastically affect the sorption properties. In addition, the activated phase of a fifth MOF, synthesized through DMF ligand exchange with water in 1 (1W), does not display an inflection point and subsequent increased CO2 sorption at 195 K, despite having the same degree of interpenetration, showing that even more subtle differences in the desolvated phases can lead to marked differences in their sorption behavior.

Design of a MOF based on octa-nuclear zinc clusters realizing both thermal stability and structural flexibility.

An octa-nuclear zinc (Zn8) cluster-based two-fold interpenetrated metal-organic framework (MOF) of [(CH3)2NH2]2[Zn8O3(FDC)6]·7DMF (denoted as Zn8-as; H2FDC = 9H-fluorene-2,7-dicarboxylic acid; DMF = N,N-dimethylformamide) was synthesized by the reaction of a hard base of a curved dicarboxylate ligand (H2FDC) with the borderline acid of Zn(II) under solvothermal conditions. Zn8-as shows significant crystal volume shrinkage upon heating, yielding a solvate-free framework of [(CH3)2NH2]2[Zn8O3(FDC)6] (Zn8-de). Zn8-de displays gated adsorption for C2H2 and type-I adsorption for CO2, attributed to the framework flexibility and the different interactions between the gas molecules and the host framework.

RETRACTED: New Cu(II) coordination polymer inhibits cervical cancer development by regulating BRCA1 protein via miR-9-5p

A novel Cu(II)-based coordination polymer [chemical composition, {[CuL(CH3CO2)](H2O)(DMF)}n (1, DMF=N,N-dimethylformamide) was successfully prepared via Cu(NO3)2·3H2O reaction with HL ligand in DMF and H2O mixture by using a hetero-donor ligand 4-(bis(4-(4H-1,2,4-triazol-4-yl)phenyl)amino)benzoic acid (HL) featuring carboxylic acid and triazole groups. Reverse transcription-polymerase chain reaction (RT-PCR) was adopted to determine miR-9-5p expression in cervical cancer cells after compound treatment. Bioinformatic analysis and luciferase reporter assay were utilized to confirm miR-9-5p and BRCA1 interaction to discover the potential goal of miR-9-5p in cervical cancer cells. Cell Counting Kit-8 (CCK-8) and reactive oxygen species (ROS) detection kits were adopted to examine cancer cell proliferation and ROS accumulation after compound treatment.

Crystal structure of hexa-kis-(N,N-di-methyl-form-amide-κO)iron(III) μ-chlorido-bis-(tri-chlorido-cadmium).

The title compound, [Fe(C3H7NO)6][Cd2Cl7], crystallizes in the trigonal space group R and is assembled from discrete [Fe(DMF)6]3+ cations (DMF = N,N-di-methyl-formamide) and [Cd2Cl7]3- anions. In the cation, the iron(III) atom, located on a special position of site symmetry, is coordinated by six oxygen atoms from DMF ligands with all Fe-O distances being equal [2.0072 (16) Å]. A slight distortion of the octa-hedral environment of the metal comes from the cis O-Fe-O angles deviating from the ideal value of 90° [86.85 (7) and 93.16 (7)°] whilst all the trans angles are strictly 180°. The central Cl atom of the [Cd2Cl7]3- anion is also located on a special position of site symmetry and bridges two corner sharing, tetra-hedrally coordinated CdII atoms. The two Cd atoms and the central Cl atom are colinear. The two sets of terminal chloride ligands on either side of the dumbbell-like anion are rotated relative to each other by 30°. In the crystal, the cations and anions, stacked one above the other along the c-axis direction, are held in place principally by electrostatic inter-actions. There are also C-H⋯Cl and C-H⋯O inter-actions, but these are rather weak. Of the six crystal structures reported to date for ionic salts of [Fe(DMF)6] n+ cations (n = 2, 3), five contain FeII ions. The title compound is the second example of a stable compound containing the [Fe(DMF)6]3+ cation. The existence of both [Fe(DMF)6]2+ and [Fe(DMF)6]3+ cations shows that the DMF ligand coordination sphere can accommodate changes in the charge and spin states of the metal centre.

Direct Molecule Substitution Enabled Rapid Transformation of Wet PbBr2(DMF) Precursor Films to CsPbBr3 Perovskite

Owing to the solubility limitation of the bromide ion, a two-step dipping method was mostly used to prepare CsPbBr3 films. However, the commonly used well-crystallized PbBr2 precursor film is too compact for the diffusion of CsBr solution. Inconvenient conversion resulted in CsPbBr3 films with poor phase purity. Additionally, long immersion time in solution made films suffer from destructive decomposition. Herein, a wet PbBr2(DMF) precursor film was proposed to rapidly form the CsPbBr3 film. A direct molecule substitution between the DMF (N,N-dimethylformamide) ligand and CsBr promotes the conversion, which was experimentally proved by Fourier transform infrared spectroscopy. Phase purity, surface coverage, and crystallinity of final CsPbBr3 films were improved. The best-performance planar carbon-based CsPbBr3 perovskite solar cell (PSC) obtained with a wet PbBr2(DMF) film showed a power conversion efficiency (PCE) of 5.25%. Compared with the optimized PSC assembled using CsPbBr3 obtained with a well-crystallized PbBr2 film, which has a PCE of 2.64%, the PCE was boosted by ∼100%.

Enhanced Surface Ligands Reactivity of Metal Clusters by Bulky Ligands for Controlling Optical and Chiral Properties.

Surface ligands play critical roles in determining the surface properties of metal clusters. However, modulating the properties and controlling the surface structure of clusters through surface-capping-agent displacement is challenging. Herein, [Ag14 (SPh(CF3 )2 )12 (PPh3 )4 (DMF)4 ] (Ag14 -DMF; DMF=N,N-dimethylformamide), with weakly coordinated DMF ligands on surface silver sites, was synthesized by a mixed-ligands strategy. Owing to the high surface reactivity of Ag14 -DMF, the surface ligands are labile, easily dissociated or exchanged by other ligands. Based on the enhanced surface reactivity, easy modulation of the optical properties of Ag14 by reversible "on-off" DMF ligation was realized. When chiral amines were introduced to as-prepared products, all eight surface ligands were replaced by amines and the racemic Ag14 clusters were converted to optically pure homochiral Ag14 clusters as evidenced by circular dichroism (CD) activity and single-crystal X-ray diffraction (SCXRD). This work provides a new insight into modulation of the optical properties of metal clusters and atomically precise homochiral clusters for specific applications are obtained.

Enhanced Surface Ligands Reactivity of Metal Clusters by Bulky Ligands for Controlling Optical and Chiral Properties

AbstractSurface ligands play critical roles in determining the surface properties of metal clusters. However, modulating the properties and controlling the surface structure of clusters through surface‐capping‐agent displacement is challenging. Herein, [Ag14(SPh(CF3)2)12(PPh3)4(DMF)4] (Ag14‐DMF; DMF=N,N‐dimethylformamide), with weakly coordinated DMF ligands on surface silver sites, was synthesized by a mixed‐ligands strategy. Owing to the high surface reactivity of Ag14‐DMF, the surface ligands are labile, easily dissociated or exchanged by other ligands. Based on the enhanced surface reactivity, easy modulation of the optical properties of Ag14 by reversible “on‐off” DMF ligation was realized. When chiral amines were introduced to as‐prepared products, all eight surface ligands were replaced by amines and the racemic Ag14 clusters were converted to optically pure homochiral Ag14 clusters as evidenced by circular dichroism (CD) activity and single‐crystal X‐ray diffraction (SCXRD). This work provides a new insight into modulation of the optical properties of metal clusters and atomically precise homochiral clusters for specific applications are obtained.

Probing the Mechanism for 2,4'-Dihydroxyacetophenone Dioxygenase Using Biomimetic Iron Complexes.

In this study, we report the synthesis and characterization of [Fe(T1Et4iPrIP)(2-OH-AP)(OTf)](OTf) (2), [Fe(T1Et4iPrIP)(2-O-AP)](OTf) (3), and [Fe(T1Et4iPrIP)(DMF)3](OTf)3 (4) (T1Et4iPrIP = tris(1-ethyl-4-isopropyl-imidazolyl)phosphine; 2-OH-AP = 2-hydroxyacetophenone, and 2-O-AP- = monodeprotonated 2-hydroxyacetophenone). Both 2 and 3 serve as model complexes for the enzyme-substrate adduct for the nonheme enzyme 2,4'-dihydroacetophenone (DHAP) dioxygenase or DAD, while 4 serves as a model for the ferric form of DAD. Complexes 2-4 have been characterized by X-ray crystallography which reveals T1Et4iPrIP to bind iron in a tridentate fashion. Complex 2 additionally contains a bidentate 2-OH-AP ligand and a monodentate triflate ligand yielding distorted octahedral geometry, while 3 possesses a bidentate 2-O-AP- ligand and exhibits distorted trigonal bipyramidal geometry (τ = 0.56). Complex 4 displays distorted octahedral geometry with 3 DMF ligands completing the ligand set. The UV-vis spectrum of 2 matches more closely to the DAD-substrate spectrum than 3, and therefore, it is believed that the substrate for DAD is bound in the protonated form. TD-DFT studies indicate that visible absorption bands for 2 and 3 are due to MLCT bands. Complexes 2 and 3 are capable of oxidizing the coordinated substrate mimics in a stoichiometric and catalytic fashion in the presence of O2. Complex 4 does not convert 2-OH-AP to products under the same catalytic conditions; however, it becomes anaerobically reduced in the presence of 2 equiv 2-OH-AP to 2.

A mixed‐valence copper(I/II) coordination polymer directed with a bifunctional soft‐hard pyrazolate−carboxylate ligand

AbstractA mixed‐valent, one‐dimensional Cu(I/II) coordination polymer with the formula [CuII{CuI3(Hmpba)(mpba)2}DMF] ⋅ ∼3DMF was obtained with the bifunctional ligand 4‐(3,5‐dimethyl‐1H‐pyrazol‐4‐yl)benzoic acid (H2mpba) in N,N‐dimethylformamide (DMF) via solvothermal reaction. The compound exhibits a trinuclear {CuI3(Hmpba)(mpba)2}2− metallo‐linker with the softer Cu(I) linearly‐coordinated by the softer pyrazolate nitrogen donor atom. This metallo‐linker connects the harder Cu(II) ions through its harder carboxylate groups into a chain structure. Two Cu(II) ions form a paddlewheel unit and are, thus, surrounded by four carboxylate groups. Cu(II) is five‐coordinated with a terminal DMF ligand. Parallel chains are connected into supramolecular layers through the common R22(8) hydrogen‐bond motif of the singly‐deprotonated carboxyl groups of the Hmpba ligand. These layers are further organized by Cu(I)−Cu(I) interactions into a 3D supramolecular array.