Oxime Ligands Research Articles

Manuscript number: ejic.202400523Isomerism in Phenyl 2‐Pyridyl Ketoxime Metal Complexes

The octahedral complex [RhCl2(ppkoH)(ppko)] (1) was obtained from the reaction between RhCl3 and phenyl 2‐pyridyl ketoxime (ppkoH). Attempts to prepare the corresponding octahedral platinum compound from K2PtCl6 gave instead the square planar [Pt2+(ppko)2] (2), but when the halogen was changed to bromine, the octahedral [Pt4+Br2(ppko)2] (3) was formed. The crystal structures were determined by X‐Ray crystallography. All the compounds have two N,N‐chelating oxime ligands. In 1, one of them is deprotonated, while in 2 and 3 both ligands are deprotonated. Compounds 1 and 3 have two halogen ligands in trans position. In 1 the oxime groups are situated mutually in cis position with an intramolecular hydrogen bond between the two N‐O(H) groups. The formation of 2 involves reduction of the platinum metal and the complex has oximes in trans position to each other. Compound 3 has an all‐trans geometry. Since octahedral and square planar compounds have a possibility to isomerism, we studied the relative stability of different geometries by DFT calculations. A mixture of isomers is likely to be formed in the reactions, but the most stable form was found to crystallize. The properties of the electron density in the preferred isomers were also investigated via QTAIM methods.

Synthesis and Characterization of New Oxime Ligand and Its Cu(II) Complex: DFT Calculations, in Vitro Antibacterial Activity, Drug-Likeness Properties, and Molecular Docking Studies

Synthesis and Characterization of New Oxime Ligand and Its Cu(II) Complex: DFT Calculations, in Vitro Antibacterial Activity, Drug-Likeness Properties, and Molecular Docking Studies

An Adsorptive Membrane Platform for Precision Ion Separation: Membrane Design and First‐Principles Studies

One of the key challenges in separation science is the lack of precise ion separation methods and mechanistic understanding crucial for efficiently recovering critical materials from complex aqueous matrices. Herein, first‐principles electronic structure calculations and in situ Raman spectroscopy are studied to elucidate the factors governing ion discrimination in an adsorptive membrane specifically designed for transition metal ion separation. Density functional theory calculations and in situ Raman data jointly reveal the thermodynamically favorable binding preferences and detailed adsorption mechanisms for competing ions. How membrane binding preferences correlate with the electronic properties of ligands is explored, such as orbital hybridization and electron localization. The findings underscore the importance of the phenolate group in oxime ligands for achieving high selectivity among competing transition metal ions. In‐depth understanding on which specific atomistic site within the microenvironment of metal‐ligand binding pockets governs the ion discrimination behaviors of the host will build a solid foundation to guide the rational design of next‐generation materials for precision separation essential for energy technologies and environment remediation. In tandem, synthetic controllability is demonstrated to transform 3D micrometer‐scale crystals to a 2D crystalline selective layer in membranes, paving the way for more precise and sustainable advances in separation science.

Bis[μ-bis-(pyridin-2-yl)methanone oxime-κ3N:,N',N'']bis-[di-acetato-κ2O,O';κO-zinc(II)

The structure of the title complex, [Zn2(C2H3O2)4(C11H9N3O)2], is triclinic containing half of the mol-ecule in the asymmetric unit. Each zinc atom is coordinated to a pyridyl and oxime nitro-gen from one di-2-pyridyl ketone oxime (dpko) ligand and a third nitro-gen from the other dpko pyridyl ring. Additionally, each zinc is coordinated to two acetato anions, one of which is bidentate and the other monodentate. The uncoordinated oxygen of the monodentate acetato group is involved in a hydrogen bond with the oxime hydrogen. The packing in the crystal is assisted by weak C-H⋯O inter-actions between acetato groups and neighboring pyridyl rings.

Effect of ligand substituents on the reactivity pathways of copper(II) complexes towards electrocatalytic water oxidation.

The electrocatalytic water oxidation activity of three copper(II) complexes [Cu(L1H)(L1)](ClO4) (1), [Cu(L2H)(L2)(H2O)](ClO4) (2) and [Cu(L3H)(L2)](ClO4) (3) with aryl oxime ligands L1H, L2H and L3H [L1H = 1-(pyridin-2-yl)methanone oxime, L2H = 1-(pyridin-2-yl)ethanone oxime and L3H = 1-(pyridin-2-yl)propanone oxime] was investigated. All the three ligands have in common a pyridyl group attached to the carbon centre of the oxime moiety and differ in the second substituent attached to the carbon centre. Electrochemical investigation of the catalytic activity of complexes 1, 2 and 3 shows that the nature of the substituent attached to the carbon centre has an influence on the catalytic pathway and overall catalytic activity of these complexes.

Synthesis and DFT calculations of metal(II) oxime complexes bearing cysteine as coligand and investigation of their biological evolutions in vitro and in silico

New complexes with the formula of [ML(Cys)(H2O)2] were obtained as a result of the reaction between the oxime ligand [HL: 4-(4-bromophenylaminoisonitrosoacetyl)biphenyl], cysteine (Cys), and the metal(II) salts (Mn, Ni, Co, Zn, Cu). The newly synthesized compounds were characterized using conventional techniques such as molar conductance, magnetic measurements, elemental analysis, infrared spectroscopy, and thermal analysis (TGA/DTA). Based on the conductivity measurements in DMF, it was determined that the complexes were non-electrolytes. The TGA/DTA analysis was performed to examine the thermal stability and degradation behavior of all samples, and results demonstrated that metal oxides or sulfides formed as a result of the decompositions. In conjunction with other data obtained, the elemental analysis confirmed the octahedral coordination of the complexes with deprotonated oxime (O, O-donor) and amino acid (N, S-donor) ligands and two coordinated waters. The compounds’ optimized geometries, molecular electrostatic potential diagrams, and frontier molecular orbitals were computed at the DFT/B3LYP level using the 6-311 G(d,p) and LANL2DZ basis sets. The antibacterial and DNA cleavage activities of all synthesized compounds were also screened, and molecular docking simulations were performed. According to the results of molecular docking studies conducted with three different proteins, the best interaction was found to be between HL-1HNJ with a binding energy of −9.5 kcal/mol. The stability of the HL-1HNJ complex was also verified by a molecular dynamics simulation performed for 50 ns. Communicated by Ramaswamy H. Sarma

Synthesis, Characterization, and Anticancer Activity of Phosphanegold(i) Complexes of 3-Thiosemicarbano-butan-2-one Oxime.

Four novel phosphanegold(I) complexes of the type [Au(PR3)(DMT)].PF6 (1-4) were synthesized from 3-Thiosemicarbano-butan-2-one oxime ligand (TBO) and precursors [Au(PR3)Cl], (where R = methyl (1), ethyl (2), tert-butyl (3), and phenyl (4)). The resulting complexes were characterized by elemental analyses and melting point as well as various spectroscopic techniques, including FTIR and (1H, 13C, and 31P) NMR spectroscopy. The spectroscopic data confirmed the coordination of TBO ligands to phosphanegold(I) moiety. The solution chemistry of complexes 1-4 indicated their stability in both dimethyl sulfoxide (DMSO) and a mixture of EtOH:H2O (1:1). In vitro cytotoxicity of the complexes was evaluated relative to cisplatin using an MTT assay against three different cancer cell lines: HCT116 (human colon cancer), MDA-MB-231 (human breast cancer), and B16 (murine skin cancer). Complexes 2, 3, and 4 exhibited significant cytotoxic effects against all tested cancer cell lines and showed significantly higher activity than cisplatin. To elucidate the mechanism underlying the cytotoxic effects of the phosphanegold(I) TBO complexes, various assays were employed, including mitochondrial membrane potential, ROS production, and gene expression analyses. The data obtained suggest that complex 2 exerts potent anticancer activity against breast cancer cells (MDA-MB-231) through the induction of oxidative stress, mitochondrial dysfunction, and apoptosis. Gene expression analyses showed an increase in the activity of the proapoptotic gene caspase-3 and a reduction in the activity of the antiapoptotic gene BCL-xL, which supported the findings that apoptosis had occurred.

Synthesis, characterization and structural study of two imidazole oxime ligand and their ZnII mononuclear coordination compounds

This paper presents a combined experimental and computational study of two new mononuclear Zinc(II) coordination compounds. The {Zn(MICO)2Cl2} (I) and{Zn(MIPMO)2Cl2} (II) complexes have been synthesized and characterized by NMR, UV, FTIR and single crystal X-ray diffraction techniques. The single crystal X-ray analyses reveal that the centrosymmetric ZnII cation in both complexes {Zn(MICO)2Cl2} (I) and {Zn(MIPMO)2Cl2} (II) is tetrahedrally coordinated by two chelating imidazole oxime ligands and by two chlorine atoms in a distorted tetrahedral geometry. The intremolecular interactions were found to play an important role in determining the most favorable structure of the free ligands, therefore controlling the final coordination mode. The cohesion of the structure and stability are ensured by intermolecular OH···O, OH···N, OH···Cl and CH···O hydrogen bonds. Hirshfeld surface analysis was performed to study the nature of intermolecular interactions within the crystal structure via 3D and 2D fingerprint surfaces and to demonstrate H-bonding with close contacts in crystal via dnorm surface. The stability of the prepared ZnII complexes has been evaluated through the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), and energy gap. The molecular geometries and electronic transitions of the two complexes and their ligands in the ground state have been calculated using the mPW1PW91 basis at the TZVP level of theory.

Synthesis, characterization and structural study of new nickel(II) and mercury (II) complexes with imidazole oxime ligand

In this work, we reported the experimental study of two new complexes named bis[chloro(1-methyl-1H-imidazole-2-carbaldehyde oxime) Nickel(II) {Ni(L)2Cl2} (I) and Di-μ-chloro-bis[chloro(1-methyl-1H-imidazole-2-carbaldehyde oxime) mercury(II) {Hg2(L)2Cl4}, DMF (II) based on (1-methylimidazole-2-aldoxime, L). The synthesis, crystallization, and characterization were detailed. Complex I display a hexa-coordinated compound with a distorted octahedral geometry. The NiII ion is coordinated to two ligands in bidentate mode through nitrogen atoms. Complex II has one unique HgII atom and forms a dimeric complex that contains two HgII atoms related by a crystallographic inversion center. In this complex, the oxime ligand is ligated to the metal ion in a monodentate fashion through the nitrogen atoms. On the basis of bond distances, this complex exhibits a distorted tetrahedral geometry around each mercury center metal. The complexes are analyzed using single-crystal diffraction, FT-IR, NMR, and UV–visible. Cyclic voltammetry was also used to understand the electrochemical behavior of the ligand and both complexes. Furthermore, we have performed DFT calculations to get more about the spectral electronic transitions' nature, reactivity, and electronic structure of the ligand and complexes.

Iridium(III) and Rhodium(III) Half-Sandwich Coordination Compounds with 11H-Indeno[1,2-b]quinoxalin-11-one Oxime: A Case of Spontaneous Resolution of Rh(III) Complex

Two half-sandwich iridium(III) and rhodium(III) complexes with 11H-indeno[1,2-b]quinoxalin-11-one oxime (IQ-1) ligand were prepared by the reaction of the proligand with [M(Cp*)Cl2]2 (M = Ir, Rh) dimers. The reaction between IQ-1 and [Ir(Cp*)Cl2]2 in methanol gave the complex [Ir(Cp*)(IQ-1)Cl] (1), which crystallized in a centrosymmetric space group as a true racemate. Whereas complex [Rh(Cp*)(IQ-1)Cl] (2) in the form of a racemic conglomerate was obtained by the reaction of [Rh(Cp*)Cl2]2 and IQ-1 in methanol. The crystal structures of complexes 1 and 2 (R and S enantiomers) were determined by X-ray diffraction analysis, and the structural features were compared in order to understand the structural factors leading to the spontaneous enantiomer resolution of the rhodium(III) complex. In the crystal packing of 1, intermolecular C–H···C contacts between a pair of enantiomers link the molecules into centrosymmetric dimers and lead to the formation of heterochiral crystals of 1. In contrast, the intramolecular contacts CH···Cl and CH···C in complex 2 bind all three ligands around the chiral Rh(III) metal center. In addition, a combination of intermolecular CH···O and CH···C contacts leads to the formation of a homochiral supramolecular structure. These interactions altogether reinforce the spontaneous resolution in complex 2.

Ring-Opening Polymerization of L-Lactide Catalyzed by Potassium-Based Complexes: Mechanistic Studies.

Two non-toxic potassium compounds, 1 and 2, with a commercial oximate ligand have been prepared and fully spectroscopically characterized. Their activity as catalysts for the ring-opening polymerization (ROP) process of LLA has been studied, showing that they are extremely active and able to polymerize the monomer in a few minutes. For derivative 2, the presence of a crown ether in the potassium coordination sphere affects the nuclearity of the compound and consequently its solubility, with both aspects having an influence in the polymerization process. Detailed studies of the polymerization mechanism have been performed, and an unusual anionic mechanism was observed in absence of a co-initiator. Indeed, the monomer deprotonation generates a lactide enolate, which initiates the polymerization propagation. On the contrary, when a 1:1 ratio of cat:BnOH is used, a mixture of mechanisms is observed, the anionic mechanism and the activated monomer one, while from a cat:BnOH ratio of 1:2 and over, only the activated monomer mechanism is observed.

A new Pd(II) complex containing acetophenone oxime and 1,3-Bis(diphenylphosphino)propane ligands; crystal structure, catalytic activity, molecular docking and in vitro cytotoxic evaluation

A new palladium (II) complex of the type [Pd{C,N-C6H4{C(Me) = NOH}-2}(dppp)]ClO4 (2) has been prepared by the reaction of the cyclopalladated oxime complex [Pd{C,N-C6H4{C(Me) = NOH}-2}(μ-Cl)]2 (1) with 1,3-Bis(diphenylphosphino)propane (dppp). The new complex has been synthesized via a bridge-splitting reaction in the presence of NaClO4 under mild conditions. Complex 2 was fully characterized by elemental analysis (CHN), spectroscopic methods (IR, 1H-, 31P-, 13C NMR) and single-crystal X-ray diffraction analysis. The structure shows the palladium atom to be in a slightly distorted square-planar geometry surrounded by one C,N-chelating oxime ligand and one P,P-chelating dppp ligand forming five- and a six-membered metallocyclic rings, respectively. The catalytic activity of complex 2 has been evaluated using Suzuki cross coupling reactions. The coupled products of these reactions were obtained in good to excellent yields and purity, low catalyst loading and short reaction times. The cytotoxic activity of complexes 1 and 2 were comparatively studied against HeLa, A549, and 1321 N1 cell lines, which showed a greater efficiency of the mononuclear complex 2 over the binuclear complex 1. Finally, molecular docking simulation was employed as a computational method to investigate the interactions of complexes 1 and 2 with the protein involved in apoptosis.

Synthesis, structural elucidation, in vitro antibacterial activity, DFT calculations, and molecular docking aspects of mixed-ligand complexes of a novel oxime and phenylalanine

An oxime ligand (HL) was synthesized by the condensation of 4-biphenylhydroxymoyl chloride with 2-amino-5-bromopyridine. The oxime ligand was reacted with l-phenylalanine and metal(II) acetate salts (Co(II), Ni(II), and Cu(II)) to synthesize mixed-ligand complexes. Structural elucidation of the newly synthesized ligand and complexes was performed by elemental analysis, 13C NMR, 1H NMR, FT-IR, ICP-OES, the measurements of molar conductivity and magnetic susceptibility. The thermal properties of the compounds were characterized by TG/DTA analyses. The antibacterial activities of the compounds were evaluated in vitro by the resazurin-aided broth microdilution method. Optimized molecular geometries of the HL and its metal complexes were calculated using the density functional theory (DFT) of the B3LYP method with 6-311G (d, p) and LANL2DZ basis sets. The NMR chemical shift values, vibrational frequencies, and HOMO-(LUMO or SOMO) energies were also computed using the mentioned level. A molecular docking study was performed to demonstrate the interactions of the synthesized compound with beta-ketoacyl-ACP synthase III (KAS III), an enzyme that has a key role in bacterial survival. Based on the MIC values and binding energy scores, both in vitro and in silico studies showed that the antibacterial activity of the Cu(II) complex was better than the other studied molecules.

Arene-ruthenium(II) complexes with tetracyclic oxime derivatives: synthesis, structure and antiproliferative activity against human breast cancer cells

Six new arene-ruthenium(II) complexes containing two different η6-arene ligands – benzene and hexamethylbenzene, with indenoquinoxalinone oxime analogues (11H-indeno[1,2-b]quinoxalin-11-one oxime, 6H-indeno[1,2-b]pyrido[3,2-e]pyrazin-6-one oxime and 6–(hydroxyimino)indolo[2,1-b]quinazolin-12(6H)-one oxime (tryptanthrin-6-oxime)) as N,N’- chelating ligands are reported. The complexes were characterized by elemental analysis, IR, UV–VIS, 1H and 13C NMR spectroscopy and by single-crystal X-ray structure analysis. Complexes adopt a half-sandwich «piano-stool» geometry with oxime ligands in anionic form, the ruthenium(II) center coordinates one arene, one N,N-bidentate oximate and one chloride ligand. The computational analysis of non-covalent intermolecular interactions revealed weak attraction between the oxime oxygen atoms and the nearest hydrogen atoms of the oxime and the arene ligands. The cytotoxic activity of the complexes was evaluated against human breast cancer cell line MCF-7 and cisplatin-resistant human breast cancer cell line MCF-7CR as well as non-cancerous human breast epithelial cell line MCF10A. The cytotoxicity tests show micromolar IC50 values and tryptanthrin-6-oxime hexamethylbenzene-ruthenium(II) complex was found to exhibit the best antiproliferative activity among the studied compounds against the MCF-7 and MCF-7CR cell lines (IC50 9.0 ± 4.4 and 8.9 ± 1.5 µM, respectively).

Synthesis and crystal structure of a new chiral α-amino-oxime nickel(II) complex.

A dinuclear nickel complex with (S)-limonene based amino-oxime ligand has been isolated and its crystal structure determined. The resolved structure of dichloridobis-{(2S,5R)-2-methyl-5-(prop-1-en-2-yl)-2-[(pyridin-2-yl)methyl-amino]-cyclo-hexan-1-one oxime}dinickel(II), [Ni2Cl2(C16H23ClN3O)2], at 100 K has monoclinic (P21) symmetry. The two NiII ions in the dinuclear complex are each coordinated in a distorted octa-hedral environment by three nitro-gen atoms, a terminal chloride and two μ bridging chlorides. Each oxime ligand is coordinated to nickel(II) by the three nitro-gen atoms, leading to two five-membered chelate rings, each displaying an envelope conformation. In the crystal, numerous inter-molecular and intra-molecular hydrogen bonds lead to the formation of a three-dimensional network structure.

Efficient Extraction of Metal Ions Using a Recirculating Two‐Stage Flow Reactor

AbstractWe report a simple flow reactor for the selective extraction of target metal ions from an aqueous solution, using passive mixers and liquid‐liquid separators. The extraction takes place in two stages. In the first stage, target metal ions are selectively transferred to an organic phase containing extractant molecules; and, in the second stage, an acid solution strips the metal ions from the organic phase and regenerates the (uncomplexed) extractant molecules, thereby allowing them to be recirculated through the reactor. Using aqueous mixtures of copper sulphate and nickel sulphate as test solutions, copper ion extraction rates of 98 % are achieved, using the copper‐selective phenolic oxime ligand 5‐(tert‐butyl)‐2‐hydroxybenzaldehyde oxime as a molecular extractant. The two‐stage, recirculating nature of the reactor minimises the use of both the extractant molecules and the supporting organic solvent, resulting in a greener, more economical process.

Synthesis, Crystal Structure and Magnetic Properties of 1D Chain Complexes Based on Azo Carboxylate Oxime Ligand

Two carboxylate-bridged one-dimensional chain complexes, {[MnII(MeOH)2][FeIII(L)2]2}n (1) and {[MnII(DMF)2][MnIII(L)2]2·DMF}n (2) [H2L = ((2-carboxyphenyl)azo)-benzaldoxime], containing a low-spin [FeIII(L)2]− or [MnIII(L)2]− unit were synthesized. Magnetic measurements show that the adjacent high-spin MnII and low-spin MIII ions display weak antiferromagnetic coupling via the syn–anti carboxyl bridges, with J = −0.066(2) cm−1 for complex 1 and J = −0.274(2) cm−1 for complex 2.

Synthesis, structural elucidation and electrochemical behavior of some oxime-phenylalanine mixed ligand complexes

Four new mixed ligand complexes Me(II)/phenylalanine (phe)/HL [HL =4-(4-bromophenyl- aminoisonitrosoacetyl)biphenyl and Me = Co, Ni, Cu, Zn] were synthesized. These complexes are formulated as: [CoL(phe)(H2O)2], [NiL(phe)(H2O)2], [CuL(phe)(H2O)2] and [ZnL(phe)(H2O)2]. All the compounds were characterized by elemental analyses, FT-IR, magnetic susceptibility measurements, TG/DTA and cyclic voltammetry (CV) experiments. IR spectral data confirmed the coordination of the oxime ligand to the metal ions through the oxime and carbonyl oxygen. The geometrical structures of the complexes have been found to be octahedral. The measured molar conductance values of the complexes in DMF are in agreement with the non-electrolytic nature ofthe complexes. The elemental analyses confirm a 1:1:1 [metal:HL:L(phenylalanine)] molar ratio. Thermal behavior of the compound was investigated by thermal gravimetric analysis (TG) and differential thermal analysis (DTA) techniques. All the complexes were transformed into metal oxides after thermal degradation. The electrochemical properties of both ligand and their complexes were analyzed by cyclic voltammetry (CV) using glassy carbon electrode in DMF solution containing 0.1 M TBAP as supporting electrolyte.
 
 KEY WORDS: Oxime, electrochemical characterization, mixed ligand complexes, amino acid, phenylalanine
 
 Bull. Chem. Soc. Ethiop. 2020, 34(3), 543-556.
 DOI: https://dx.doi.org/10.4314/bcse.v34i3.10

Synthesis, characterization, and density functional theory studies of hydrazone–oxime ligand derived from 2,4,6‐trichlorophenyl hydrazine and its metal complexes searching for new antimicrobial drugs

Novel 13 mononuclear complexes derived from 3‐(2‐(2,4,6‐trichlorophenyl) hydrazono) butan‐2‐one oxime with various molar ratio, geometry and different mode of interaction were prepared using transition metal Cd2+, Zn2+, Cu2+, Ni2+, Co2+, Fe3+, Mn2+, and VO2+. The structure of these compounds was investigated physically, analytically, and spectrophotometrically. The ligation sites of the free 3‐(2‐(2,4,6‐trichlorophenyl) hydrazono) butan‐2‐one oxime were designated via molecular modeling calculations. Furthermore, quantum chemical parameters for the ligand and its complexes were calculated. The analytical and spectral data revealed that the complexes (2–13) were formed with molar ratio of (1 M:1 L) or (1 M:2 L) in which hydrazone oxime adhered with the metal ion as a univalent or neutral bidentate chelator, via the imino nitrogen atom of hydrazone moiety and oximato nitrogen atom of deprotonated/protonated oxime moiety adopting different geometrical structures. The electron spin resonance (ESR) spectra of Cu2+complexes (7–8) and (10–11) were referred to axial symmetry with g||> g┴> ge, which indicated that unpaired electron is localized in a d(x2 − y2)orbital with notable bonding covalency nature. The thermo analysis (thermogravimetry [TG]) confirmed that the complexes were decayed in one, two, three, or four steps starting with dehydration process, elimination of coordination water molecules, or removal of anions and completed with the whole decomposition of the complexes with the formation of metal oxide. The ligand did not exhibit antimicrobial activities, but its complexes showed variable activities.

De novo synthesis of bifunctional conjugated microporous polymers for synergistic coordination mediated uranium entrapment

This work reports a de novo synthesis of novel bifunctional conjugated microporous polymers (CMPs) exhibiting a synergistic-effect involved coordination behavior to uranium. It is highlighted that the synthetic strategy enables the engineering of the coordination environment within amidoxime functionalized CMP frameworks by specifically introducing ortho-substituted amino functionalities, enhancing the affinity to uranyl ions via forming synergistic complexes. The CMPs exhibit high Brunauer-Emmett-Teller (BET) surface area, well-developed three-dimensional (3D) networks with hierarchical porosity, and favorable chemical and thermal stability because of the covalently cross-linked structure. Compared with the amino-free counterparts, the adsorption capacity of bifunctional CMPs was increased by almost 70%, from 105 to 174 mg/g, indicating evidently enhanced binding ability to uranium. Moreover, new insights into coordination mechanism were obtained by in-depth X-ray photoelectron spectroscopy (XPS) analysis and density functional theory (DFT) calculation, suggesting a dominant role of the oxime ligands forming a 1:1 metal ions/ligands (M/L) coordination model with uranyl ions while demonstrating the synergistic engagement of the amino functionalities via direct binding to uranium center and hydrogen-bonding involved secondary-sphere interaction. This work sheds light on the underlying principles of ortho-substituted functionalities directed synergistic effect to promote the coordination of amidoxime with uranyl ions. And the synthetic strategy established here would enable the task-specific development of more novel CMP-based functional materials for broadened applications.