Ligand Structure Research Articles

X-ray absorption and emission spectroscopy of N2S2 Cu(II)/(III) complexes.

This study investigates the influence of ligand charge on transition energies in a series of CuN2S2 complexes based on dithiocarbazate Schiff base ligands using Cu K-edge X-ray absorption spectroscopy (XAS) and Kβ valence-to-core (VtC) X-ray emission spectroscopy (XES). By comparing the formally Cu(II) complexes [CuII(HL1)] (HL12- = dimethyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and [CuII(HL2)] (HL22- = dibenzyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and the formally Cu(III) complex [CuIII(L2)], distinct changes in transition energies are observed, primarily attributed to the metal oxidation state. Density functional theory (DFT) calculations demonstrate how an increased negative charge on the deprotonated L23- ligand stabilizes the Cu(III) center through enhanced charge donation, modulating the core transition energies. Overall, significant shifts to higher energies are noted upon metal oxidation, emphasizing the importance of scrutinizing ligand structure in XAS/VtC XES analysis. The data further support the redox-innocent role of the Schiff base ligands and underscore the criticality of ligand protonation levels in future spectroscopic studies, particularly for catalytic intermediates. The combined XAS-VtC XES methodology validates the Cu(III) oxidation state assignment while offering insights into ligand protonation effects on core-level spectroscopic transitions.

Influence of Ylide Functionalization on the Catalytic Performance of Ferrocenyldiphosphines in Au(I)‐Catalyzed Hydroaminations and Hydrohydrazinations

Ylide‐functionalized phosphines (YPhos) have been shown to yield highly active gold catalysts owing to their high donor capacity. To examine the impact of ylide functionalization on a given ligand structure, a series of ferrocenyl diphosphines functionalized with no, one or two ylide moieties and their corresponding bimetallic gold complexes were prepared. The complexes feature an anti‐conformation of the two phosphine moieties, guaranteeing the presence of two independent metal centers. Comparative studies of the complexes in the hydroamination and hydrohydrazination of alkynes revealed a significant increase in catalytic activity for each newly introduced ylide group. The di‐YPhos ligands were revealed to be the most active precatalysts, functioning effectively even at 0.1 or 0.2 mol% catalyst loading. This catalytic efficiency was demonstrated for a series of alkynes, amines and hydrazines.

Linear, Planar, Orbicular, and Macrocyclic Multinuclear Zinc (Meth)acrylate Complexes.

Zinc carboxylate complexes are widely utilized as artificial models of metalloenzymes and as secondary building units of PCPs/MOFs. However, the relationship between the structure of the monodentate carboxylato ligand and the molecular arrangement of multinuclear zinc carboxylate complexes is not fully understood because of the coordination flexibility of the Zn ion and carboxylato ligands. Herein, we report the structural analysis of a series of complexes derived from zinc (meth)acrylate which has a linear infinite chain structure. The molecular structure of μ4-oxido-bridged tetranuclear complexes [Zn4(μ4-O)(OCOR)6] revealed a distorted Zn4O core. Crystallization of zinc acrylate under aqueous conditions afforded a μ3-hydroxido-containing pentanuclear complex [Zn5(μ3-OH)2(OCOR)8] as the repeating unit of an infinite sheet-like structure in the solid state. It was also obtained by the hydrolysis of the μ4-oxido-bridged tetranuclear complex. In sharp contrast, the methacrylate analog retained the methacrylato ligands under aqueous crystallization conditions to form a macrocyclic dodecanuclear complex with methacrylato as the sole ligand.

Highly Specific Sulfadiazine Detection Using a Two-Dimensional Europium-Organic Coordination Polymer.

Sulfadiazine (SFZ) is an inexpensive large-consumption antibiotic used for treat bacterial infections but an excess of residues in food can be harmful. Fast and specific luminescence detection of SFZ is highly challenging because of the interference of structurally similar antibiotics. In this work, we develop a two-dimensional europium-organic coordination polymer with excellent luminescence and water stability for highly specific detection of SFZ in the range of 0-0.2 mM. Structural analysis shows that the high stability of coordination polymer is due to the high coordination number of europium ion and the special chelating coordination structure of ligand. The experiment results revealed that the high selectivity and effectively luminescence quenched behaviour of coordination polymer toward SFZ is caused by highly efficient inner filter effect.

[Gd(HB-DO3A)]: Equilibrium, Dissociation Kinetic and Structural Differences in a Simple Homolog of [Gd(HP-DO3A)] (Prohance®).

[Gd(HP-DO3A)] (gadoteridol) as an active compound of ProHance® is a widely employed contrast agent in clinical MRI scans in the last 30 years. Recent concerns about the long-term retention of gadolinium-based contrast agents (GBCAs) led to a deeper investigation of the structural features underlying the integrity of the paramagnetic metal complex. Several human and nonclinical studies have noted marked differences among the macrocyclic GBCAs, with the least retention of Gd traces and most rapid elimination consistently being reported for [Gd(HP-DO3A)]. It was deemed of interest to assess how minor structural/electronic changes associated to the ligand structure may affect basic properties of the metal complex with several [Gd(HP-DO3A)] analogues synthesized and characterized in the last years. We recently reported that the closest homolog of [Gd(HP-DO3A)], i. e.: [Gd(HB-DO3A)], in which a (±)-2-hydroxy-1-propyl pendant arm is replaced by a (±)-2-hydroxy-1-butyl moiety, showed a significantly different retention behaviour in the model interaction with collagen, despite the apparently very minor structural difference. In this paper we report a comprehensive study of the structural, thermodynamic, kinetic and relaxation properties of [Gd(HB-DO3A)], compared to the parent [Gd(HP-DO3A)] and to other closely related macrocyclic GBCAs to assess whether very minor structural changes can modulate the physico-chemical properties of Gd3+ complexes.

Synthesis, structure and effects of an azoimine functionalized iridium complex on cancer cells

A novel ligand L having azoimine bond with quinoline moiety reacts with [(2-ppy)2Ir(μ-Cl)]2 in dichloromethane medium to produce an iridium(III) complex of composition [Ir(2-ppy)2(L)]. Here, the iridium centre is bound to neutral bidentate N, N donating sites of the ligand (L), where the azo part of L is not involved in chelation. The ligand and complex are characterized by elemental analysis, NMR spectroscopy, ESI-MS mass spectrometry, FTIR, UV–Vis and luminescence spectroscopic techniques. The ligand structure and the geometry around iridium centre of complex [Ir(2-ppy)2(L)] is confirmed by the single-crystal X-ray diffraction (XRD) method. DFT studies were also performed to support the experimental aspects of the complex as well as electronic distribution in molecular orbitals of various energy states. The complex exhibits blue emission band at 428 nm with quantum yield (Φ) 0.136. Further, in vitro analysis of the anticancer activity of the complex was studied mainly with the MCF - 7 cell line. The results showed that the complex have good IC50 values when compared to the standard drug cisplatin.

Ligand-dictated planar versus bent nickel(II) chelates of the Schiff bases: Synthesis, crystal structures, optical properties, DFT and molecular docking studies

Two nickel(II) coordination compounds [Ni(LI)2] (1) and [Ni(LII)2] (2) (HLI = N-cyclohexyl-3-methoxysalicylideneimine, HLII = N-cyclohexyl-3-ethoxysalicylideneimine) were synthesized with the aim to reveal and compare the influence of the electronically and structurally similar methyl (Me) and ethyl (Et) funcionalities in a close proximity to the chelate backbone of the corresponding parent ligand. It was established that a minor difference in the structure of the parent ligand (Me in LI vs. Et in LII) leads to a crucial difference in the geometry of a complex molecule: a planar structure of 1 with two cycloalkane functionalities directed on the opposite sides of a molecule, and a bent structure of 2 with two cycloalkane functionalities directed on the convex side of a molecule. The coordination core of both complexes is a NiN2O2 planar square, formed due to two trans-coordinated ligands LI and LII, respectively. Solutions of the title compounds in CH2Cl2, MeOH and EtOH absorb up to about 475 nm due to intraligand transitions and LMCT. The DFT-based calculations were also applied to shed light on the structural and optical features of 1 and 2. In silico prediction using a molecular docking approach showed that both complexes can potentially inhibit a number of the SARS-CoV-2 proteins. The so-called ligand efficiency scores for complex Nsp14_N7-MTase–1 are within the recommended ranges for a drug, while the same scores for complexes Nsp14_N7-MTase–2, PLpro–1 and Mpro–1 fall in the ranges for a Hit.

Structural, Theoretical and Biological Studies on Cu2+ and Co2+ Complexes of New Thiosemicarbazone Ligands

Two sets of Cu2+, and Co2+ complexes of two 4 – Pyridyl thiosemicarbazone derivatives ligands symbolized by (H3L1), and (H3L2), were synthesized and examined utilizing different analytical, and spectroscopic techniques such as (FT-IR, Elemental Analysis, Magnetic studies, PXRD, UV-Vis, and GC-MS). Thermal stability along with kinetic parameters of both Co2+ complexes were studied. 1H NMR technique was used to confirm the structures of both ligands. The proposed geometries of complexes were recognized by density function theory (DFT) calculations using Material software. Additionally, Quantum theory of atoms in molecules (QTAIM) topological analyses for both ligands were obtained using Multiwfn software. The cyclic voltammogram revealed that copper ions are electroactive and exhibited two reduction waves. Fluorescence studies for both ligands showed a direct increase in the intensity of emissions because of increasing Co2+ concentration in solution. Moreover, several biological evaluations were carried out for all six compounds to evaluate their potential use as biological agents, including antioxidant activity using 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid (ABTS) radical scavenging approach, anti-microbial activity against Staphylococcus aureus, Escherichia coli, and Candida albicans, DNA degradation activity, in addition to anticancer activity, along with molecular docking theoretical study against MCF-7 breast cancer cell line to determine the compounds ability to act as antitumor. It was found that the investigated compounds (especially the free ligands) have beneficial effects such as antimicrobial, antitumor, and DNA degradation agents. Furthermore, Co2+ complex (2) has the highest ABTS scavenging activity.

A Multifaceted Approach Towards Organometallic Anticancer Agent Development

The approaches taken to develop novel metal-based anticancer agents have considerably changed over the last 50 years since the discovery of the platinum drugs and focus now on compounds that interact with proteins overexpressed in tumor cells, show novel modes of DNA interactions or accumulate with higher selectivity in tumors, to name a few. The structural diversity of anticancer agents has steadily increased and organometallic compounds are widely investigated. Over the years, bioorganometallic chemistry has developed into the thriving field of research it is today and in particular the development of anticancer agents with bioactive co-ligands coordinated to the metal center has received a lot of attention.In this personal perspective, I discuss concepts we use in anticancer metallodrug design and metallomics strategies to interrogate their modes of action. I focus on the impact of ligand structures on the biological activity of their organometallic complexes, complemented by observations of unexpected reactions and surprising behavior in the presence of biomolecules.

Synthesis of Quinoline-based New Organic Chemosensors and its Application in Fluorophoric Detection of Metal-ions in Environmental Samples and Confirmation of Results using Molecular Modelling: A Complete Study

Quinoline-based two new ligands have been synthesized (QL1 and QL2) by reacting 8-quinoline carboxylic acid with derivatives of L-valine under a condensation reaction. The synthesized ligands were characterized by spectroscopic techniques such as 1H NMR, UV, IR, HRMS and CHNS. The 3D structures of both ligands were optimized for the lowest energy and the HOMO-LUMO orbitals were developed. The photoluminescence analysis of both ligands showed the fluorescence emission wavelengths on 492 and 508 nm, respectively for QL1 and QL2. The substituents on the quinoline ring influence the change in fluorescence emission wavelengths. Synthesized ligands acted as selective fluorescence turn-off chemosensors for Cu2+ ions and demonstrated the sensitive detection of Cu2+ ions in different water samples at the nanomolar scale. The interaction between metal ion and ligands were also studied by developing DFT structures.

Nickel‐ and Palladium‐Catalyzed Copolymerizations of Norbornene with Polar α‐Olefins.

Recent progress regarding the copolymerization of norbornene with various polar α‐olefins catalyzed by nickel and palladium catalysts is reviewed here with special attention paid to the diverse catalyst frameworks, polar monomer scopes as well as polymer microstructures. Both the influences of steric effect and electron property of ligand substituents and the type of polar monomers on the catalytic behaviors (activity, stability, polarity tolerance, etc.) and the polymer microstructures (molecular weight and distribution, comonomer contents, etc.) have been summarized. The introduction of noncyclic‐olefins, such as polar vinyl monomers, polar higher α‐olefins, and polar styrenes, into rigid cyclic‐based polynorbornene chain resulted in significant modifications on the polarity, compatibility, thermostability, processibility, transparency, and many other properties of the material, which has also been discussed in the review. The contents of this review have been classified according to the type of polar monomers involved in the norbornene copolymerization, and each section included nickel and palladium catalysts bearing different ligand structures, which will be meaningful for the development of new types of catalysts and new families of norbornene‐based cyclic olefin copolymer materials in the future.

Organosilicon-Based Ligand Design for High-Performance Perovskite Nanocrystal Films for Color Conversion and X-ray Imaging.

Perovskite nanocrystals (PNCs) bear a huge potential for widespread applications, such as color conversion, X-ray scintillators, and active laser media. However, the poor intrinsic stability and high susceptibility to environmental stimuli including moisture and oxygen have become bottlenecks of PNC materials for commercialization. Appropriate barrier material design can efficiently improve the stability of the PNCs. Particularly, the strategy for packaging PNCs in organosilicon matrixes can integrate the advantages of inorganic-oxide-based and polymer-based encapsulation routes. However, the inert long-carbon-chain ligands (e.g., oleic acid, oleylamine) used in the current ligand systems for silicon-based encapsulation are detrimental to the cross-linking of the organosilicon matrix, resulting in performance deficiencies in the nanocrystal films, such as low transparency and large surface roughness. Herein, we propose a dual-organosilicon ligand system consisting of (3-aminopropyl)triethoxysilane (APTES) and (3-aminopropyl)triethoxysilane with pentanedioic anhydride (APTES-PA), to replace the inert long-carbon-chain ligands for improving the performance of organosilicon-coated PNC films. As a result, strongly fluorescent PNC films prepared by a facile solution-casting method demonstrate high transparency and reduced surface roughness while maintaining high stability in various harsh environments. The optimized PNC films were eventually applied in an X-ray imaging system as scintillators, showing a high spatial resolution above 20 lp/mm. By designing this promising dual organosilicon ligand system for PNC films, our work highlights the crucial influence of the molecular structure of the capping ligands on the optical performance of the PNC film.

Prediction of viral protease inhibitors using proteochemometrics approach

Being widely accepted tools in computational drug search, the (Q)SAR methods have limitations related to data incompleteness. The proteochemometrics (PCM) approach expands the applicability area by using description for both protein and ligand structures. The PCM algorithms are urgently required for the development of new antiviral agents. We suggest the PCM method using the TLMNA descriptors, combining the MNA descriptors of ligands and protein sequence N-grams. Our method was validated on the viral chymotrypsin-like proteases and their ligands. We have developed an original protocol allowing us to collect a comprehensive set of 15 protein sequences and more than 9000 ligands from the ChEMBL database. The N-grams were derived from the 3D-based alignment, accurately superposing ligand-binding regions. In testing the ligand set in SAR mode with MNA descriptors, an accuracy above 0.95 was determined that shows the perspective of the antiviral drug search in virtual chemical libraries. The effective PCM models were built with the TLMNA descriptor. The strong validation procedure with pair exclusion simulated the prediction of interactions between the new ligands and new targets, resulting in accuracy estimation up to 0.89. The PCM approach shows slightly lower accuracy caused by more uncertainty compared with SAR, but it overcomes the problem of data incompleteness.

Palladium(II) NCS‐Pincer Complexes Mediated Regioselective Cross Dehydrogenative Alkenation of 2‐Arylthiophenes

In this report, we have synthesized two NCS pincer ligands by the Schiff base reaction of 3‐((phenylthio)methoxy)benzaldehyde (P) with alkyl amines (tbutylamine (L1) and 1‐adamantylamine (L2)). The palladium pincer complexes (tbutylamine = C1 and 1‐adamantylamine = C2) of these ligands were synthesized by their reaction with PdCl2(CH3CN)2. The newly synthesized ligands and complexes were characterized using various techniques such as 1H, 13C{1H} Nuclear Magnetic Resonance (NMR), Ultraviolet–visible (UV‐Visible), Fourier Transform Infrared (FTIR) Spectroscopy, and High‐Resolution Mass Spectrometry (HRMS). The structure of ligand and its coordination mode with palladium precursor were studied with the help of single‐crystal X‐ray diffraction. The complexes showed distorted square planar geometry around the palladium center. The palladium pincer complexes were used as catalysts for the regioselective cross‐dehydrogenative alkenation of 2‐arylthiophene derivatives. The complex C2, where sterically bulky adamantyl ligand is part of the side arm showed a higher yield of alkenation reaction. Only 2.5 mol% catalyst loading was sufficient to achieve 74‐95% yields of desired products with excellent functional group tolerance under mild reaction conditions. The poisoning experiments (PPh3 and Hg) showed the homogeneous nature of the catalytic process. The plausible mechanism of the reaction was proposed based on the control experiments and time‐dependent HRMS studies.

Covalent and Visible‐Light Photoswitchable Derivatives of the Potent Synthetic Opioid Isotonitazene and Other Nitazenes

Isotonitazene belongs to a potent class of m‐opioid receptor (µOR) ligands, known as nitazenes. The lack of knowledge surrounding this agonist and others in its class has sparked thorough re‐investigations. To aid in these investigations, the purportedly covalent yet underexplored nitazene BIT was biochemically re‐evaluated in this work, along with a newly synthesized analogue, Iso‐BIT. Moreover, in the pursuit of understanding the mechanism, function, and interactions of µOR, this study involved developing photoswitchable derivatives of nitazene as potential probe molecules. Converting known ligands into azo‐containing photoswitchable derivatives offers the opportunity to modulate ligand structure with light, allowing for photocontrol of compound activity. While photocontrol of µOR activity could not be entirely achieved, photophysical evaluation of these arylazobenzimidazole derivatives revealed a novel photoswitch scaffold that responds to visible light. Furthermore, azo‐containing 2e and 3e emerged as promising nitazene derivatives that were able to form an exceptionally high fraction of covalent‐ligand receptor complexes with wild‐type µOR at physiological pH.

Ab initio modeling of human IRS1 protein to find novel target to dock with drug MH to mitigateT2DM diabetes by insulin signaling.

IRS1 is a cytoplasmic adaptor protein that helps incellulargrowth, glucose metabolism, proliferation, anddifferentiation. Highly disordered (insulin receptor substrate 1) IRS1 protein sequence (mol.wt- 131,590.97da) has been used to develop model using ab initio modeling technique by I-Tassar tool and Discovery Studio/ DogSite Server to decipher a novel active site. The constructed protein model has been submitted with PMDB Id- PM0082210. GRAVY index of IRS1 model ( - 0.675) indicated surface protein-water interaction. Protparam tool instability index (75.22) demonstrated disorderedness combined with loops owing to prolines/glycines. After refinement,the Ramachandran plot showed that 88 percent of AAs were presentin the allowed region and only 0.5% in the disallowed region.Novel IRS1 model proteinhas 10 α-helices, 22 β-sheets, 20 β-hairpins, 5 β-bulges, 47 strands, 105 β-turns, and 8 γ-turns. Docking of IRS1 with drug MH demonstrated interaction of Ser-70, Thr-18, and Pro-69 with C-H bonds; Gln-71, and Glu-113 with hydrogen bonds; while both Glu-114 and Glu-113 with salt-bridge connection. Permissible 1.0-1.5Å range of RMSD fluctuation between 20 and 45ns was obtained in simulation of IRS1 and IRS1-met complex confirmed that both complexes were stable during whole simulation process. RMSF result showed that except positions 57AA and 114AA, the binding of drug had no severe effects on the flexibility of the IRS1 and IRS1-met complex. The RoG value of compactness and rigidity showed little change in IRS1 protein. SASA value of IRS1 indicated non-significant fluctuation between IRS1 and drug MH means ligand (drug) and IRS1 receptor form stable structure. Hydrogen bond strength of IRS1 and IRS1-met was 81.2 and 76.4, respectively, which suggested stable interaction.

Boron Complexes of Tridentate Acyl Pyridylhydrazones

AbstractSince the development of the chemistry and applications of boron dipyrromethene dyes (BODIPYs), numerous other platforms based on boron complexes of N‐donor ligands have emerged as molecular optoelectronic materials. By tailoring the structure of the ligand bound to boron, the optical and electronic properties of a compound can be precisely tuned for unique properties, such as aggregation‐induced emission (AIE) in the case of boron difluoride hydrazones (BODIHYs). We examine the impact of modifying the typical bidentate hydrazone ligand structure used to prepare BODIHYs to enable a tridentate coordination mode to produce boron complexes of tridentate acyl pyridylhydrazones. This change allows for the use of arylboronic acids as sources of boron and facilitates the inclusion of complex organic components at the boron centre, including the formation of dye‐dye conjugates. The synthesized compounds exhibit distinct optical and electronic properties when compared to BODIHYs, such as reversible electrochemical reduction and up to a >300 nm pseudo‐Stokes shift in the solid state, all of which were supported by density functional theory calculations.

Mono- and bi-nuclear phosphine-phenolate neutral nickel catalysts via simple Schiff-Base condensation for ethylene polymerization

In catalytic olefin polymerization, a significant amount of effort has been invested to modify either phosphine substituent or ligand backbone in recently advanced phosphine-phenolate [P,O] neutral nickel catalysts. Unlike other commonly used ligands like phenoxy-imines [N,O] and α-diimines [N,N], [P,O] ligands often require a laborious synthesis technique, which has hindered the rational design of ligand structures and the development of new catalysts. Here we present a novel and effective strategy for creating catalysts using [N,O,P] hybrid ligands. The substituent adjacent to the phenoxy group can be efficiently modified through straightforward Schiff-base condensation reactions with various amines that have established synthetic routes and diverse structures. This process results in the preparation of a series of highly active [P,O] nickel catalysts (up to 1.7 × 107 g mol-1h−1) that are capable of producing ultrahigh molecular weight polyethylene (UHMWPE) (Mw = 243.7 × 104 g/mol) in ethylene polymerization. The additional binding site greatly facilitates modulation of catalytic properties by additives, and parameters such as catalytic activity, polymer molecular weight, and polymer branching can be tuned in this way. Furthermore, binuclear [P,O] neutral nickel catalysts for olefin polymerization are synthesized for the first time using a sequence of diamines. The strategy presented in this work greatly improves the efficiency for the design and synthesis of [P,O] nickel and related catalysts. These findings will be advantageous for future catalyst design and screening.

Effect of ligand structure and metal center on ethylene oligomerization with N, N′ Schiff base late transition complexes: experiments and calculations

A series of N, N’ bis(pyridine-imine) Schiff base late transition metal (Fe, Co, and Ni) complexes with different ligand structures and catalytic active sites were synthesized. Ethylene oligomerization results showed that bis(pyridine-imine) iron complex had the highest catalytic activity (10.8 × 105 g/mol Fe h), and the catalytic activity of cobalt complex was the lowest (2.5 × 105 g/mol Co h); nickel complex had the highest selectivity toward high carbon olefins (28.6%), while the iron complex had the lowest (0.2%). The structure-activity relationship between the catalyst structure and catalytic properties for ethylene oligomerization was further studied by density functional theory (DFT) calculations. The bis(pyridine-imine) iron complex had the highest energy gap value and the most stable catalyst structure, which was more conducive to oligomerization; and the N–M–N bond of the nickel complex had the smallest bond angle, which was beneficial for chain growth. Based on the Cossee mechanism, a mechanism for ethylene oligomerization catalyzed by bis(pyridine-imine) metal complexes was proposed. To further study the micro reaction process of ethylene oligomerization, a molecular model of pyridine imine nickel complex and its catalytic ethylene oligomerization reaction path were proposed. The structure and energy of the reaction intermediate and transition state were calculated using DFT. The molecular model of the nickel complex had a lower ethylene insertion barrier and β-H elimination of energy barriers, indicating that the molecular model of the pyridine imine nickel complex had ethylene oligomerization active centers.

Zirconium-containing nanoscale coordination polymers for positron emission tomography and fluorescence-guided cargo delivery to triple-negative breast tumors

Nanoscale coordination polymer (NCP) is a class of hybrid materials formed by self-assembly of metal ions and organic ligands through coordination. The applications of NCP in biomedicine are quite extensive due to the diversity choice of metal ions and organic ligands. Here we designed Zr-P1 NCP based on Zr4+ selected as metal ion nodes and tetrakis(4-carboxyphenyl) ethylene as bridging ligands. Zr-P1 NCP was modified with functionalized pyrene derived polyethylene glycol (Py-PAA-PEG-Mal) on the surface and further conjugated with cRGD for active targeting of integrin αvβ3 overexpressed in triple-negative breast cancer. Doxorubicin was loaded on Zr-P1 NCP with encapsulation efficiency up to 22 % for the treatment of triple negative breast cancer. 89Zr-P1 NCP can be used for in vivo tumor imaging due to the fluorescence properties resulting from the enhanced aggregation-induced Emission (AIE) behavior of P1 ligands and its positron emission tomography (PET) capability. Cellular evaluation indicated that the functionalized Zr-P1@PEG-RGD presented a good function for tumor cell targeting imaging and doxorubicin could be targeted to triple negative breast cancer when it was loaded onto Zr-P1@PEG-RGD, which corroborated with the in vivo results. In summary, 89Zr-P1@PEG-RGD can serve as a biocompatible nanoplatform for fluorescence and PET image-guided cargo delivery. Statement of SignificanceNanoscale coordination polymer (NCP) is a class of hybrid materials formed by self-assembly of metal ions and organic ligands through coordination. The diversity of available metals and ligand structures upon NCP synthesis plays an advantage in establishing multimodal imaging platforms. Here we designed 89Zr-P1@PEG-RGD NCP based on Zr4+ selected as metal ion nodes and tetrakis(4-carboxyphenyl) ethylene as bridging ligands. 89Zr-P1@PEG-RGD nanomaterials have positron emission tomography (PET) capability due to the incorporation of zirconium-89, which can be used for in vivo tumor imaging with high sensitivity. The chemotherapeutic drug DOX was loaded on Zr-P1 NCP for the treatment of triple-negative breast cancer, and dual modality imaging can provide visual guidance for drug delivery.