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Comprehensive Summary: Carbonylation reactions are a valuable synthetic method to construct carbonyl compounds and carbonylation reactions of aryl halides stand out as a highly significant tool for generating carbonyl substituted arenes. However, the important reactions have never been realized in aromatic metallacycles. Herein, we present the first carbonylation reactions of metallaaromatics, specifically alkoxycarbonylation and aminocarbonylation reactions of an osmapentalyne. During the carbonylation process, the electronic and steric properties of nucleophiles are regarded as critical factors. The alcohols with bulky substituents (isopropanol) require more reaction time and tert‐butyl alcohol is inert in the reaction. Comparatively, amines, being stronger nucleophiles, exhibit divergent behaviors. Bulky amines undergo aminocarbonylation, whereas small amines prefer direct nucleophilic additions. Control experiments revealed that the intermediate derived from coupling of metal carbyne with CO plays a significant role in the carbonylation reaction. According to these observations, a divergent pathway for the reaction is proposed. Furthermore, the photophysical properties of these carbonyl‐functionalized osmapentalene complexes are studied, and the maximum absorption peak of compound with a carboxylic group exhibits a significant red‐shift due to the smaller HOMO‐LUMO gap. These findings contribute to expanding the reactivity of metallaaromatics and offer new opportunities for the synthesis of carbonyl‐functionalized metallacycles. [ABSTRACT FROM AUTHOR]

When reacted in dry, degassed toluene, [Ir(COD)Cl]2 (COD = cyclo­octa-1,5-diene) and 2 equivalents of 2-(di-tert-butyl­phosphinito)anthra­quinone (tBuPOAQH) were found to form a unique tri-iridium compound consisting of one monoanionic dinuclear tri-μ-chlorido complex bearing one bidentate tBuPOAQ ligand per iridium, which was charge-balanced by an outer sphere [Ir(toluene)(COD)]+ ion, the structure of which has not previously been reported. This product, which is a toluene solvate, namely, (η²:η²-cyclo­octa-1,5-diene)(η6-toluene)­iridium(I) tri-μ-chlorido-bis­({3-[(di-tert-butyl­phosphan­yl)­oxy]-9,10-dioxoanthracen-2-yl}hydridoiridium(III)) toluene monosolvate, [Ir(C7H8)(C8H12)][Ir2H2(C22H24O3P)2Cl3]·C7H8 or [Ir(toluene)(COD)][Ir(κ-P,C-tBuPOAQ)(H)]2(μ-Cl)3]·toluene, formed as small orange platelets at room temperature, crystallizing in the triclinic space group P1. The cation and anion are linked via weak C—H⋯O inter­actions. The stronger inter­molecular attractions are likely the offset parallel π–π inter­actions, which occur between the toluene ligands of pairs of inverted cations and between pairs of inverted anthra­quinone moieties, the latter of which are capped by toluene solvate mol­ecules, making for π-stacks of four mol­ecules each. The related ligand, 2-(di-tert-butyl­phosphinometh­yl)-anthra­quinone (tBuPCAQH), did not form crystals suitable for X-ray diffraction under analogous reaction conditions. However, when the reaction was conducted in chloro­form, yellow needles readily formed following addition of 1 atm of carbon monoxide. Diffraction studies revealed a neutral, dinuclear, di-μ-chlorido complex, di-μ-chlorido-bis­(carbon­yl{3-[(di-tert-butyl­phosphan­yl)­oxy]-9,10-dioxoanthracen-2-yl}hydridoiridium(I)), [Ir2H2(C23H26O2P)2Cl2(CO)2] or [Ir(κ-P,C-tBuPCAQ)(H)(CO)(μ-Cl)]2, Ir2C48H54Cl2O6P2, again crystallizing in space group P1. Offset parallel π–π inter­actions between anthra­quinone groups of adjacent mol­ecules link the mol­ecules in one dimension. [ABSTRACT FROM AUTHOR]

When reacted in dry, degassed toluene, [Ir(COD)Cl]2 (COD = cyclo­octa-1,5-diene) and 2 equivalents of 2-(di-tert-butyl­phosphinito)anthra­quinone (tBuPOAQH) were found to form a unique tri-iridium compound consisting of one monoanionic dinuclear tri-μ-chlorido complex bearing one bidentate tBuPOAQ ligand per iridium, which was charge-balanced by an outer sphere [Ir(toluene)(COD)]+ ion, the structure of which has not previously been reported. This product, which is a toluene solvate, namely, (η²:η²-cyclo­octa-1,5-diene)(η6-toluene)­iridium(I) tri-μ-chlorido-bis­({3-[(di-tert-butyl­phosphan­yl)­oxy]-9,10-dioxoanthracen-2-yl}hydridoiridium(III)) toluene monosolvate, [Ir(C7H8)(C8H12)][Ir2H2(C22H24O3P)2Cl3]·C7H8 or [Ir(toluene)(COD)][Ir(κ-P,C-tBuPOAQ)(H)]2(μ-Cl)3]·toluene, formed as small orange platelets at room temperature, crystallizing in the triclinic space group P[\overline{1}]. The cation and anion are linked via weak C--H⋯O inter­actions. The stronger inter­molecular attractions are likely the offset parallel π-π inter­actions, which occur between the toluene ligands of pairs of inverted cations and between pairs of inverted anthra­quinone moieties, the latter of which are capped by toluene solvate mol­ecules, making for π-stacks of four mol­ecules each. The related ligand, 2-(di-tert-butyl­phosphinometh­yl)-anthra­quinone (tBuPCAQH), did not form crystals suitable for X-ray diffraction under analogous reaction conditions. However, when the reaction was conducted in chloro­form, yellow needles readily formed following addition of 1 atm of carbon monoxide. Diffraction studies revealed a neutral, dinuclear, di-μ-chlorido complex, di-μ-chlorido-bis­(carbon­yl{3-[(di-tert-butyl­phosphan­yl)­oxy]-9,10-dioxoanthracen-2-yl}hydridoiridium(I)), [Ir2H2(C23H26O2P)2Cl2(CO)2] or [Ir(κ-P,C-tBuPCAQ)(H)(CO)(μ-Cl)]2, Ir2C48H54Cl2O6P2, again crystallizing in space group P[\overline{1}]. Offset parallel π-π inter­actions between anthra­quinone groups of adjacent mol­ecules link the mol­ecules in one dimension. [ABSTRACT FROM AUTHOR]

When reacted in dry, degassed toluene, [Ir(COD)Cl]2 (COD = cycloocta-1,5-diene) and 2 equivalents of 2-(di-tert-butylphosphinito)anthraquinone (tBuPOAQH) were found to form a unique tri-iridium compound consisting of one monoanionic dinuclear tri-μ-chlorido complex bearing one bidentate tBuPOAQ ligand per iridium, which was charge-balanced by an outer sphere [Ir(toluene)(COD)]+ ion, the structure of which has not previously been reported. This product, which is a toluene solvate, namely, (η2:η2-cycloocta-1,5-diene)(η6-toluene)iridium(I) tri-μ-chlorido-bis({3-[(di-tert-butylphosphanyl)oxy]-9,10-dioxoanthracen-2-yl}hydridoiridium(III)) toluene monosolvate, [Ir(C7H8)(C8H12)][Ir2H2(C22H24O3P)2Cl3]·C7H8 or [Ir(toluene)(COD)][Ir(κ-P,C-tBuPOAQ)(H)]2(μ-Cl)3]·toluene, formed as small orange platelets at room temperature, crystallizing in the triclinic space group P\overline{1}. The cation and anion are linked via weak C—H...O interactions. The stronger intermolecular attractions are likely the offset parallel π–π interactions, which occur between the toluene ligands of pairs of inverted cations and between pairs of inverted anthraquinone moieties, the latter of which are capped by toluene solvate molecules, making for π-stacks of four molecules each. The related ligand, 2-(di-tert-butylphosphinomethyl)-anthraquinone (tBuPCAQH), did not form crystals suitable for X-ray diffraction under analogous reaction conditions. However, when the reaction was conducted in chloroform, yellow needles readily formed following addition of 1 atm of carbon monoxide. Diffraction studies revealed a neutral, dinuclear, di-μ-chlorido complex, di-μ-chlorido-bis(carbonyl{3-[(di-tert-butylphosphanyl)oxy]-9,10-dioxoanthracen-2-yl}hydridoiridium(I)), [Ir2H2(C23H26O2P)2Cl2(CO)2] or [Ir(κ-P,C-tBuPCAQ)(H)(CO)(μ-Cl)]2, Ir2C48H54Cl2O6P2, again crystallizing in space group P\overline{1}. Offset parallel π–π interactions between anthraquinone groups of adjacent molecules link the molecules in one dimension.

We report a class of isolable bis‐cyclometallated iridium precatalysts (ImIr) and their use in regioselective ortho−C−H borylation of aromatic, heteroaromatic, acrylic, and aliphatic systems. The catalysts consist of two imine ligands and an acetate coordinated to an iridium (III) center. The isolable character of ImIr warrants its compatibility with high‐throughput experimentation, a prerequisite for applications in late‐stage functionalization (LSF) of complex substrates. Initial mechanistic studies point towards an inner‐sphere mechanism involving bis‐cyclometallated species shedding light on the general mechanistic understanding of ortho‐selective C−H borylations. [ABSTRACT FROM AUTHOR]

Trinuclear metallacyclic oxidovanadium(V) complexes, [{VO(L3+2R)}3] (1–3) with asymmetric multidentate linking ligands (H3L3+2R: R = H, Me, Br), were synthesized. The molecular structure of 1 is characterized as a tripod structure, with each V(V) ion coordinated by ONO-atoms from a tridentate Schiff base site and ON-atoms from a bidentate benzoxazole site of two respective H3L3+2H ligands. The intramolecular V⋯V distances range from 8.0683 to 8.1791 Å. Complex 4 is a mononuclear dioxidovanadium(V) complex, (Et3NH)[VO2(HL3+2H)]. Cyclic voltammograms of 1−3 in DMF revealed redox couples attributed to three single-electron transfer processes. [ABSTRACT FROM AUTHOR]

Albeit sonodynamic therapy (SDT) has achieved encouraging progress in microbial sterilization, the scarcity of guidelines for designing highly effective sonosensitizers and the intricate biofilm microenvironment (BME), substantially hamper the therapeutic efficacy against biofilm infections. To address the bottlenecks, we innovatively design a Ru(II) metallacycle‐based sonosensitizer/sonocatalyst (named Ru‐A3‐TTD) to enhance the potency of sonotherapy by employing molecular engineering strategies tailored to BME. Our approach involves augmenting Ru‐A3‐TTD's production of ultrasonic‐triggered reactive oxygen species (ROS), surpassing the performance of commercial sonosensitizers, through a straightforward but potent π‐expansion approach. Within the BME, Ru‐A3‐TTD synergistically amplifies sonotherapeutic efficacy via triple‐modulated approaches: (i) effective alleviation of hypoxia, leading to increased ROS generation, (ii) disruption of the antioxidant defense system, which shields ROS from glutathione consumption, and (iii) enhanced biofilm penetration, enabling ROS production in deep sites. Notably, Ru‐A3‐TTD sono‐catalytically oxidizes NADPH, a critical coenzyme involved in antioxidant defenses. Consequently, Ru‐A3‐TTD demonstrates superior biofilm eradication potency against multidrug‐resistant Escherichia coli compared to conventional clinical antibiotics, both in vitro and in vivo. To our knowledge, this study represents the pioneering instance of a supramolecular sonosensitizer/sonocatalyst. It provides valuable insights into the structure‐activity relationship of sonosensitizers and paves a promising pathway for the treatment of biofilm infections. [ABSTRACT FROM AUTHOR]

Reactions of o‐alkyl naphthol compounds with ReCl3(PMePh2)3 produced naphtho‐rhenafuran complexes, which adapted different ground states (singlet S0 and triplet T0). These polycyclic structures have been characterized experimentally and theoretically. Their electronic behaviors have been studied by UV‐Vis absorption and DFT calculations. [ABSTRACT FROM AUTHOR]

The development of multimode photopatterning systems based on supramolecular coordination complexes (SCCs) is considerably attractive in supramolecular chemistry and materials science, because SCCs can serve as promising platforms for the incorporation of multiple functional building blocks. Herein, we report a light‐responsive liquid‐crystalline metallacycle that is constructed by coordination‐driven self‐assembly. By exploiting its fascinating liquid crystal features, bright emission properties, and facile photocyclization capability, a unique system with spatially‐controlled fluorescence‐resonance energy transfer (FRET) is built through the introduction of a photochromic spiropyran derivative, which led to the realization of the first example of a liquid‐crystalline metallacycle for orthogonal photopatterning in three‐modes, namely holography, fluorescence, and photochromism. [ABSTRACT FROM AUTHOR]

[Display omitted] It is still challenging to develop multi–step cascaded artificial light–harvesting systems (ALHSs) with tunable efficiency. Here, we designed novel cascaded ALHSs with AIE–active metallacycles as the light–harvesting antenna, Eosin Y (ESY) and sulforhodamine 101 (SR101) as conveyors, near–infrared emissive chlorin–e6 (Ce6) as the final acceptor. The close contact and fair spectral overlap between donor and acceptor molecules at each level ensured the efficient sequential three–step energy transfer. The excited energy was sequentially and efficiently funneled to Ce6 along the cascaded line MTPEPt1 → ESY → SR101 → Ce6. Additionally, a unique strategy for regulating the efficiency of ALHS was illustrated by adjusting hydrophilic and hydrophobic interactions. [ABSTRACT FROM AUTHOR]

The macrometallacyclic title compound, [Hg4Br4(C8H11N2S)4] or [((HgL2)(HgBr2))2] (1) where HL = 2-{[(pyridin-2-yl)methyl]amino}ethane-1-thiol, was prepared and structurally characterized. The Hg2+ complex crystallizes in the P21/c space group. The centrosymmetric Hg4S4 metallacycle is constructed from metal ions with alternating distorted tetrahedral Br2S2 and distorted seesaw N2S2 primary coordination environments with pendant pyridyl groups. The backfolded extended chair metallacycle conformation suggests interactions between each of the bis-chelated mercury atoms and Br atoms lying above and below the central Hg2S4 plane. Supramolecular interactions in 1 include a fourfold aryl embrace and potential hydrogen bonds with bromine as the acceptor. Hirshfeld surface analysis indicates that H...H (51.7%), Br...H/H...Br (23.0%) and C...H/H...C (9.5%) interactions are dominant.

The macrometallacyclic title compound, [Hg4Br4(C8H11N2S)4] or [((HgL2)(HgBr2))2] (1) where HL = 2-{[(pyridin-2-yl)methyl]amino}ethane-1-thiol, was prepared and structurally characterized. The Hg2+ complex crystallizes in the P21/c space group. The centrosymmetric Hg4S4 metallacycle is constructed from metal ions with alternating distorted tetrahedral Br2S2 and distorted seesaw N2S2 primary coordination environments with pendant pyridyl groups. The backfolded extended chair metallacycle conformation suggests interactions between each of the bis-chelated mercury atoms and Br atoms lying above and below the central Hg2S4 plane. Supramolecular interactions in 1 include a fourfold aryl embrace and potential hydrogen bonds with bromine as the acceptor. Hirshfeld surface analysis indicates that H• • •H (51.7%), Br• • •H/ H• • •Br (23.0%) and C• • •H/H• • •C (9.5%) interactions are dominant. [ABSTRACT FROM AUTHOR]

Ruthenium complexes of phosphinocarboxamide ligands, and their use to form metallacycles using halide abstraction/deprotonation reactions are reported. Thus, [Ru(p-cym){PPh2C(=O)NHR}Cl2; R = iPr (1), Ph (2), p-tol (3)] and [Ru(p-cym){PPh2C(=O)N(R)C(=O)N(H)R}Cl2; R = Ph (4), p-tol (5)] were synthesized from [(p-cym)RuCl2]2 (p-cym = para-cymene) and phosphinocarboxamides or phosphinodicarboxamides, respectively. Single-crystal X-ray diffraction measurements on 1–5 reveal coordination to ruthenium through the phosphorus donor, with an intramolecular hydrogen bond between the amine-bound proton and a metal-bound chloride. Six-membered metallacycles formed by halide abstraction/deprotonation of complexes 4 and 5 afforded [Ru(p-cym){κ2-P,N-PPh2C(=O)N(R)C(=O)NR}Cl] [R = Ph (6), p-tol (7)]. These species exist as a mixture of two rotational isomers in solution, as demonstrated by NMR spectroscopy. [ABSTRACT FROM AUTHOR]

Addition of triphenylcyclopropenium bromide to the thiocarbonyl complex [RhCl(CS)(PPh3)2] affords novel bicyclic metalla‐3‐mercapto‐thiapyrylliums [Rh(κ2‐C,S‐C5S2Ph3)(PPh3)2X2] (X=Cl, Br) – heterocycles with no metal‐free isolobal precedent. Halide abstraction with silver triflate (AgOTf) in acetonitrile affords the salt [Rh(κ2‐C,S‐C5S2Ph3)(NCMe)2(PPh3)2{Ag(OH2)2}{Ag(OTf)3}]‐OTf which in turn reacts with sodium chloride to return [Rh(κ2‐C,S‐C5S2Ph3)(PPh3)2Cl2]. [ABSTRACT FROM AUTHOR]

Trinuclear metallacyclic oxidovanadium(V) complexes, [{VO(L3+2R)}3] (1–3) with asymmetric multidentate linking ligands (H3L3+2R: R = H, Me, Br), were synthesized. The molecular structure of 1 is characterized as a tripod structure, with each V(V) ion coordinated by ONO-atoms from a tridentate Schiff base site and ON-atoms from a bidentate benzoxazole site of two respective H3L3+2H ligands. The intramolecular V⋯V distances range from 8.0683 to 8.1791 Å. Complex 4 is a mononuclear dioxidovanadium(V) complex, (Et3NH)[VO2(HL3+2H)]. Cyclic voltammograms of 1−3 in DMF revealed redox couples attributed to three single-electron transfer processes.

Comprehensive Summary: Metallacyclopentadienes play a vital role in transition‐metal mediated and catalyzed cycloaddition reactions of alkynes. Though versatile reactions of metallacyclopentadienes with alkynes have been disclosed, [2+1] cycloadditions of metallacyclopentadienes and alkynes have never been discovered. In present work, we report the formal [2+1] cycloadditions of a metallacyclopentadiene unit with a broad scope of commercial alkynes, providing a facile strategy to construct tetracyclic conjugated compounds. The deuterated experiment indicates a metal vinylidene intermediate has been involved in [2+1] cycloaddition. Moreover, the electrophilic substitution reaction of the tetracyclic conjugated compound with the aid of density functional theory (DFT) calculated Fukui functions is investigated. These tetracyclic conjugated compounds exhibit broad absorption spectra in the whole visible region which could be employed as potential photovoltaic materials. [ABSTRACT FROM AUTHOR]

Macrocyclic molecule‐based host–guest systems, which provide contributions for the design and construction of functional supramolecular structures, have gained increasing attention in recent years. In particular, platinum(II) metallacycle‐based host–guest systems provide opportunities for chemical scientists to prepare novel materials with various functions and structures due to the well‐defined shapes and cavity sizes of platinum(II) metallacycles. However, the research on platinum(II) metallacycle‐based host–guest systems has been given little attention. In this article, we demonstrate the host–guest complexation between a platinum(II) metallacycle and a polycyclic aromatic hydrocarbon molecule, naphthalene. Taking advantage of metallacycle‐based host–guest interactions and the dynamic property of reversible Pt coordination bonds, a [2]rotaxane is efficiently prepared by employing a template‐directed clipping procedure. The [2]rotaxane is further applied to the fabrication of an efficient light‐harvesting system with multi‐step energy transfer process. This work comprises an important supplement to macrocycle‐based host–guest systems and demonstrates a strategy for efficient production of well‐defined mechanically interlocked molecules with practical values. [ABSTRACT FROM AUTHOR]

The performance of six newly synthesized benzo[h]quinoline‐derived acetonitrilo pentamethylcyclopentadienyl iridium(III) tetrakis(3,5‐bis‐trifluoromethylphenyl)borate salts bearing different substituents −X (−OMe, −H, −Cl, −Br, −NO2 and −(NO2)2) on the heterochelating ligand were evaluated in the dehydro‐O‐silylation of benzyl alcohol and the monohydrosilylation of 4‐methoxybenzonitrile by Et3SiH, two reactions involving the electrophilic activation of the Si−H bond. The benchmark shows a direct dependence of the catalytic efficiency with the electronic effect of −X, which is confirmed by theoretical assessment of the intrinsic silylicities Π of hydridoiridium(III)‐silylium adducts and by the theoretical evaluation of the propensity of hydridospecies to transfer the hydrido ligand to the activated substrate. The revisited analysis of the Ir−Si−H interactions shows that the most cohesive bond in hydridoiridium(III)‐silylium adducts is the Ir−H one, while the Ir−Si is a weak donor‐acceptor dative bond. The Si...H interaction in all the cases is noncovalent in nature and dominated by electrostatics confirming the heterolytic cleavage of the hydrosilane's Si−H bond in this key catalytically relevant species. [ABSTRACT FROM AUTHOR]

Exploration of organometallic metallacycles has led to the development of various polycyclic compounds with fascinating structures, which could be used as functional materials. In this work, a new rhenanaphthalene isomer was isolated from the reaction of ReH5(PMe2Ph)3 with o‐ethynylphenyl alkyne in the presence of excess HCl. Its structure was then identified using the single‐crystal X‐ray diffraction and NMR spectroscopy. DFT studies suggest that its formation involves two protonation reactions and two migration reactions. This new rhenanaphthalene isomer enriches the family of metallacycles. [ABSTRACT FROM AUTHOR]

A series of dinuclear metallacycles of Mn(II), Co(II), Ni(II), Cu(II) and Cd(II) with 1,8-naphthalene dicarboxylic acid (H2NDC) with co-ligand such as 2,2′-bipyridine (bpy) or solvent molecules have been synthesized in a refluxed condition. One mononuclear Ni(II) complex has also been synthesized following the same synthetic procedure with NDC, bpy and pyridine. Among them two polymorphic structures have been isolated. The single crystal X-ray structures of all the metallacycles have been described along with Hirshfield surface analysis. [ABSTRACT FROM AUTHOR]

Assembling metallacycles with interesting topological arrangements is a critical task for chemists. We report here a novel dodecanuclear CuII compound, [{Cu3L(µ-N3)}4(Py)14]·2Py (Cu12) (where Py = pyridine and [H6L]Cl = tris(2-hydroxybenzylidine)triaminoguanidinium chloride, respectively), with the topology of a cycle accomplished by four two-connecting approximately flat C3-symmetric guanidine-based ligands. Each ligand affords three tridentate metal-binding cavities and the four node-to-node connections through single azido bridges are provided by pairs of metal centers. A theoretical investigation using CASSCF in addition to DFT calculations showed strong antiferromagnetic coupling within the Cu3-triangles, resulting in spin-frustrated systems. However, these calculations were not able to properly reproduce the very weak antiferromagnetic couplings between the triangle units, highlighting the challenge of describing the magnetic behavior of this compound. [ABSTRACT FROM AUTHOR]

The reactions of a terminal aluminium imide with a range of oxygen‐containing substrates have been probed with a view to developing its use as a novel main group transfer agent for the [NR]2− fragment. We demonstrate transfer of the imide moiety to [N2], [CO] and [Ph(H)C] units driven thermodynamically by Al−O bond formation. N2O reacts rapidly to generate the organoazide DippN3 (Dipp=2,6‐iPr2C6H3), while CO2 (under dilute reaction conditions) yields the corresponding isocyanate, DippNCO. Mechanistic studies, using both experimental and quantum chemical techniques, identify a carbamate complex K2[(NON)Al‐{κ2−(N,O)−N(Dipp)CO2}]2 (formed via [2+2] cycloaddition) as an intermediate in the formation of DippNCO, and also in an alternative reaction leading to the generation of the amino−dicarboxylate complex K2[(NON)Al{κ2−(O,O′)−(O2C)2N‐(Dipp)}] (via the take‐up of a second equivalent of CO2). In the case of benzaldehyde, a similar [2+2] cycloaddition process generates the metallacyclic hemi‐aminal complex, Kn[(NON)Al{κ2−(N,O)−(N(Dipp)C(Ph)(H)O}]n. Extrusion of the imine, PhC(H)NDipp, via cyclo‐reversion is disfavoured thermally, due to the high energy of the putative aluminium oxide co‐product, K2[(NON)Al(O)]2. However, addition of CO2 allows the imine to be released, driven by the formation of the thermodynamically more stable aluminium carbonate co‐product, K2[(NON)Al(κ2−(O,O′)−CO3)]2. [ABSTRACT FROM AUTHOR]

Integration of small organic fluorophores into supramolecular systems through coordination-driven self-assembly is gaining increasing interest in the areas of fluorescent materials, chemical sensors, and biomedical applications. Compared to systems modified with a single type of fluorophore, the introduction of two or more kinds of fluorophores can achieve multi-channel spectral changes in absorption and emission, enabling ratiometric detection and tunable light emission. Metal coordination not only allows precise control over the number and location of small organic fluorophores in supramolecular systems, but also enables integrating of small molecular fluorophores with specified light-absorbing and light-emitting properties, including single- or multi-step FRET, multi-channel ratio imaging, broader light-absorbing bands, and higher catalytic efficiency. This review focuses on constructing supramolecular assemblies through coordination-driven self-assembly with ligands modified by small organic fluorophores as core skeleton, and summaries recent progress in developing and applying these assemblies for artificial light-harvesting systems, biological applications, assembly kinetics study and cancer theranostics. [ABSTRACT FROM AUTHOR]

The reactivity of the 2‐phenylpyridine‐derived [Cp*CoI(phpy‐κC,N)] metallacycle towards Et3SiH and hydrides was evaluated. The treatment of the same Co(III) complex with Na[BHEt3] resulted in its decomposition into cobalt nanoparticles. The hydride‐promoted decomposition of the metallacycle involves the transient formation of an elusive hydrido‐cobalt(III) intermediate, the traces of which were detected by 1H NMR spectroscopy at sub‐ambient temperature. The Co nanoparticles produced from a 5 mol% and 10 mol% load of cobaltacycle and Na[BHEt3] respectively contain Co(0) that is responsible for the hydrosilylation by Et3SiH of arylketones into silylalkyl ethers. To minimize the residual side reduction of carbonyls by Na[BHEt3], a mixture of 5 mol% of the latter with 5 mol% of BEt3 was found to produce optimal hydrosilylation yields at 40 °C in 2 h. Under similar conditions, several arylnitriles were mono‐hydrosilylated into N‐silyl‐imines in yields ranging from 68 to 100 %. [ABSTRACT FROM AUTHOR]

Although metal-based chemical agents have demonstrated promising bacteriostatic effects in phototherapy, their short excitation/emission wavelengths and inadequate phototherapy efficiencies make their application in vivo difficult. We therefore synthesized a novel Pt(II) metallacycle (Pt1110) that can be activated with a 980 nm laser for photodiagnosis/treatment in deep tissue. We found that Pt1110 significantly improved photothermal conversion (95% improvement) and 1O2 generation (ΦΔ 75% increase) compared to the ligand itself 1 and was well capable of light-induced sterilization under safe laser irradiation (0.72 W/cm2). In addition, Pt1110 has little to no toxicity to cells. After incorporated into liposome, Pt1110 NPs was effective in wound healing in infection and keratitis models upon laser irradiation, which was accurately observed by NIR-II fluorescence imaging. This novel metal-coordinated supramolecular material has a potential to become a universal platform for phototherapy in deep tissue. [ABSTRACT FROM AUTHOR]

Ruthenium complexes of phosphinocarboxamide ligands, and their use to form metallacycles using halide abstraction/deprotonation reactions are reported. Thus, [Ru(p-cym){PPh2C(=O)NHR}Cl2; R = iPr (1), Ph (2), p-tol (3)] and [Ru(p-cym){PPh2C(=O)N(R)C(=O)N(H)R}Cl2; R = Ph (4), p-tol (5)] were synthesized from [(p-cym)RuCl2]2 (p-cym = para-cymene) and phosphinocarboxamides or phosphinodicarboxamides, respectively. Single-crystal X-ray diffraction measurements on 1–5 reveal coordination to ruthenium through the phosphorus donor, with an intramolecular hydrogen bond between the amine-bound proton and a metal-bound chloride. Six-membered metallacycles formed by halide abstraction/deprotonation of complexes 4 and 5 afforded [Ru(p-cym){κ2-P,N-PPh2C(=O)N(R)C(=O)NR}Cl] [R = Ph (6), p-tol (7)]. These species exist as a mixture of two rotational isomers in solution, as demonstrated by NMR spectroscopy.

Supramolecular polymers based on supramolecular coordination complexes (SCCs) have received extensive attention because of their good stimulus responsiveness, processability and other properties. Herein, we report metallacycle-crosslinked supramolecular polymers via amino–yne click reaction, which were employed as well-performing elastomer materials. The supramolecular polymers cross-linked by the metallacycle not only maintained the aggregation induced emission (AIE) properties of the metallacycle, which were used to detect nitroaromatic explosives, but also had enhanced mechanical strength and toughness and exhibited elastomeric properties. This study provides a feasible strategy for the preparation of metallacycle-based supramolecular polymers with better mechanical properties.

Industry-produced hydrazine (N 2 H 4 ) is released into the environment, posing a major risk to human health and the ecosystem. Therefore, it is imperative to develop an effective and convenient method for the detection of N 2 H 4 . Herein, artificial light-harvesting systems (ALHSs) for N 2 H 4 detection were constructed by applying an aggregation-induced emission-active platinum(II) metallacycle ( TPEMc ) as the energy donor and rhodols ( P1 , P2 , and P3 ) as the energy acceptors. The ratiometric fluorescence probes based on ALHSs for N 2 H 4 showed obvious signal amplification and lower limits of detection compared to those of rhodols ( P1 , P2 , P3 ) alone. The TPEMc -rhodols systems clearly demonstrated a noticeable increase in fluorescence intensity at 550 nm and an obvious fluorescent color shift from cyan to yellow in the presence of N 2 H 4 . Fascinatingly, N 2 H 4 could be visually and quantitatively detected in water by the TPEMc -rhodol systems paired with smartphone RGB analysis. Therefore, the combination of platinum(II) metallacycle with rhodols is a promising strategy for simple, sensitive, and visual detection of N 2 H 4 .

When reacted in dry, degassed toluene, [Ir(COD)Cl] 2 (COD = cyclo-octa-1,5-diene) and 2 equivalents of 2-(di- tert -butyl-phosphinito)anthra-quinone ( tBu POAQH) were found to form a unique tri-iridium compound consisting of one monoanionic dinuclear tri-μ-chlorido complex bearing one bidentate tBu POAQ ligand per iridium, which was charge-balanced by an outer sphere [Ir(toluene)(COD)] + ion, the structure of which has not previously been reported. This product, which is a toluene solvate, namely, (η 2 :η 2 -cyclo-octa-1,5-diene)(η 6 -toluene)-iridium(I) tri-μ-chlorido-bis-({3-[(di- tert -butyl-phosphan-yl)-oxy]-9,10-dioxoanthracen-2-yl}hydridoiridium(III)) toluene monosolvate, [Ir(C 7 H 8 )(C 8 H 12 )][Ir 2 H 2 (C 22 H 24 O 3 P) 2 Cl 3 ]·C 7 H 8 or [Ir(toluene)(COD)][Ir(κ- P , C - tBu POAQ)(H)] 2 (μ-Cl) 3 ]·toluene, formed as small orange platelets at room temperature, crystallizing in the triclinic space group P . The cation and anion are linked via weak C-H⋯O inter-actions. The stronger inter-molecular attractions are likely the offset parallel π-π inter-actions, which occur between the toluene ligands of pairs of inverted cations and between pairs of inverted anthra-quinone moieties, the latter of which are capped by toluene solvate mol-ecules, making for π-stacks of four mol-ecules each. The related ligand, 2-(di- tert -butyl-phosphinometh-yl)-anthra-quinone ( tBu PCAQH), did not form crystals suitable for X-ray diffraction under analogous reaction conditions. However, when the reaction was conducted in chloro-form, yellow needles readily formed following addition of 1 atm of carbon monoxide. Diffraction studies revealed a neutral, dinuclear, di-μ-chlorido complex, di-μ-chlorido-bis-(carbon-yl{3-[(di- tert -butyl-phosphan-yl)-oxy]-9,10-dioxoanthracen-2-yl}hydridoiridium(I)), [Ir 2 H 2 (C 23 H 26 O 2 P) 2 Cl 2 (CO) 2 ] or [Ir(κ- P , C - tBu PCAQ)(H)(CO)(μ-Cl)] 2 , Ir 2 C 48 H 54 Cl 2 O 6 P 2 , again crystallizing in space group P . Offset parallel π-π inter-actions between anthra-quinone groups of adjacent mol-ecules link the mol-ecules in one dimension., (© Thackeray et al. 2024.)

A series of (C^S)-cyclometallated Au(III) cationic complexes of general formula [Au(dppta)(dtc)] + , [Au(dppta)(azmtd)] + and [Au(dppta)(azc)Cl] + (dppta = N,N-diisopropyl-P,P-diphenylphosphinothioic amide-κ 2 C,S; dtc = dithiocarbamate-κ 2 S,S'; azc = azolium-2-dithiocarboxylate-κ 1 S; azmdt = azol(in)ium-2-(methoxy)methanedithiol-κ 2 S,S') were synthetized and tested against a panel of bacterial strains belonging to different Gram-positive and Gram-negative species of the ESKAPE group of pathogens. Among the tested compounds, complex 4c had the higher Therapeutic Index (TI) against multidrug resistant strains of S. aureus, S. epidermidis and A. baumannii, showing a more favourable cytotoxicity profile than the reference gold metalloantibiotic Auranofin. © 2024 xxxxxxxx. Hosting by Elsevier B.V. All rights reserved., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Sara M. Soto has patent A gold(III) complex, a conjugate of the gold(III) complex, a pharmaceutical composition comprising the gold(III) complex and uses and a process for preparing the gold(III) complex issued to Institute of Global Health of Barcelona. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Ruthenium (Ru) complexes are developed as latent emissive photosensitizers for cancer and pathogen photodiagnosis and therapy. Nevertheless, most existing Ru complexes are limited as photosensitizers in terms of short excitation and emission wavelengths. Herein, we present an emissive Ru(II) metallacycle (herein referred to as 1) that is excited by 808-nm laser and emits at a wavelength of ~1,000 nm via coordinationdriven self-assembly. Metallacycle 1 exhibits good optical penetration (~7 mm) and satisfactory reactive oxygen species production properties. Furthermore, 1 shows broadspectrum antibacterial activity (including against drug-resistant Escherichia coli) as well as low cytotoxicity to normal mammalian cells. In vivo studies reveal that 1 is employed in precise, second near-infrared biomedical window fluorescent imaging-guided, photo-triggered treatments in Staphylococcus aureus-infected mice models, with negligible side effects. This work thus broads the applications of supramolecular photosensitizers through the strategy of lengthening their wavelengths. [ABSTRACT FROM AUTHOR]

Although boron dipyrromethene (BODIPY)-based metallacycles are expected to be promising candidates for imaging probes and therapeutic agents, their biomedical applications are restricted by their short absorption/emission wavelengths. In this work, we report a rhombic metallacycle M with broad absorption in the near-infrared (NIR) range and emissions at wavelengths >800 nm, which exhibits an efficient photothermal conversion capacity. Metallacycle M was encapsulated via Pluronic F127 to fit the biotic environment, resulting in the generation of F127/M nanoparticles (NPs) with high hydrophilicity and biocompatibility. In vitro studies demonstrated that the F127/M NPs underwent efficient cellular uptake and exhibited satisfactory photothermal therapeutic activity. Furthermore, in vivo experiments revealed that tumor growth was effectively inhibited, and the degree of undesirable biological damage was minimal in treatment with F127/M NPs and laser irradiation. Finally, the F127/M NPs could be visualized through NIR fluorescence imaging in living mice, thereby allowing their distribution to be monitored in order to enhance treatment accuracy during photothermal therapy. We envision that such BODIPY-based metallacycles will provide emerging opportunities for the development of novel therapeutic agents for biomedical applications. [ABSTRACT FROM AUTHOR]

Although platinum-based anticancer drugs have prevailed in traditional chemotherapy, the severe side effects and drug resistance hampered their clinical applications. Combinational therapies have exhibited promises in antitumor treatments. However, the integration of different anticancer modalities is often challenging because of the conflicts between maximal synergy of therapeutic effects and reduction of side effects. Here, we report a multifunctional platform composed of metallacycle-based star polymer and gold nanorods for synergistic photochemotherapy. We applied the Pt-based metallacycle-cored star polymers as both a photodynamic photosensitizer and a Pt-based anticancer drug. The gold nanorods play the dual role of photothermal converter and energy acceptor of fluorescence resonance energy transfer effect from the star polymers. The photothermal effect enhanced tumor permeability of reactive oxygen species and Pt-based drug molecules and the photodynamic effect destructed heat shock proteins to prevent the mechanism of cellular self-protection response to heat. This mutually beneficial strategy results in high therapeutic efficacy and negligible side effects verified by both in vitro and in vivo studies. This study offers a new avenue in designing a multifunctional platform for the synergy of different antitumor modalities.

Assembling metallacycles with interesting topological arrangements is a critical task for chemists. We report here a novel dodecanuclear CuII compound, [{Cu3L(µ-N3)}4(Py)14]·2Py (Cu12) (where Py = pyridine and [H6L]Cl = tris(2-hydroxybenzylidine)triaminoguanidinium chloride, respectively), with the topology of a cycle accomplished by four two-connecting approximately flat C3-symmetric guanidine-based ligands. Each ligand affords three tridentate metal-binding cavities and the four node-to-node connections through single azido bridges are provided by pairs of metal centers. A theoretical investigation using CASSCF in addition to DFT calculations showed strong antiferromagnetic coupling within the Cu3-triangles, resulting in spin-frustrated systems. However, these calculations were not able to properly reproduce the very weak antiferromagnetic couplings between the triangle units, highlighting the challenge of describing the magnetic behavior of this compound.

Bacterial infection is one of the greatest threats to public health. In vivo real‐time monitoring and effective treatment of infected sites through non‐invasive techniques, remain a challenge. Herein, we designed a PtII metallacycle‐based supramolecular photosensitizer through the host‐guest interaction between a pillar[5]arene‐modified metallacycle and 1‐butyl‐4‐[4‐(diphenylamino)styryl]pyridinium. Leveraging the aggregation‐induced emission supramolecular photosensitizer, we improved fluorescence performance and antimicrobial photodynamic inactivation. In vivo studies revealed that it displayed precise fluorescence tracking of S. aureus‐infected sites, and in situ performed image‐guided efficient PDI of S. aureus without noticeable side effects. These results demonstrated that metallacycle combined with host‐guest chemistry could provide a paradigm for the development of powerful photosensitizers for biomedicine. [ABSTRACT FROM AUTHOR]

Predictive catalysis must be the tool that does not replace experiments, but acts as a selective agent, so that synthetic strategies of maximum profitability are used in the laboratory in a surgical way. Here, nanotechnology has been used in olefin metathesis from homogeneous Ru‐NHC catalysts, specifically annulating a C60 fullerene to the NHC ligand. Based on results with the C60 in the backbone, a sterile change with respect to the catalysis of the metal center, an attempt has been made to bring C60 closer to the metal, by attaching it to one of the two C−N bonds of the imidazole group of the SIMes (1,3‐bis(2,4,6‐trimethylphenyl)imidazolin‐2‐ylidene) ligand (reference NHC ligand of the 2nd generation Grubbs catalysts) to increase the steric pressure of C60 in the first sphere of reactivity of the metal. The DFT calculated thermodynamics and the kinetics of SIMes‐derived systems show that they are efficient catalysts for olefin metathesis. [ABSTRACT FROM AUTHOR]

Theory‐driven organic synthesis is a powerful tool for developing new organic transformations. A palladacycle(II), generated from 8‐methylquinoline via C(sp3)−H activation, is frequently featured in the scientific literature, albeit that the reactivity toward CO2, an abundant, inexpensive, and non‐toxic chemical, remains elusive. We have theoretically discovered potential carboxylation pathways using the artificial force induced reaction (AFIR) method, a density‐functional‐theory (DFT)‐based automated reaction path search method. The thus obtained results suggest that the reduction of Pd(II) to Pd(I) is key to promote the insertion of CO2. Based on these computational findings, we employed various one‐electron reductants, such as Cp*2Co, a photoredox catalyst under blue LED irradiation, and reductive electrolysis ((+)Mg/(−)Pt), which afforded the desired carboxylated products in high yields. After screening phosphine ligands under photoredox conditions, we discovered that bidentate ligands such as dppe promoted this carboxylation efficiently, which was rationally interpreted in terms of the redox potential of the Pd(II)‐dppe complex as well as on the grounds of DFT calculations. We are convinced that these results could serve as future guidelines for the development of Pd(II)‐catalyzed C(sp3)−H carboxylation reactions with CO2. [ABSTRACT FROM AUTHOR]

Transition metal-mediated templating and self-assembly have shown great potential to construct mechanically interlocked molecules. Herein, we describe the formation of the bimetallic [3]catenane and [4]catenane based on neutral organometallic scaffolds via the orthogonality of platinum-to-oxygen coordination-driven self-assembly and copper(I) template–directed strategy of a [2]pseudorotaxane. The structures of these bimetallic [3]catenane and [4]catenane were characterized by multinuclear NMR {1H and 31P} spectroscopy, electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS), and PM6 semiempirical molecular orbital theoretical calculations. In addition, single-crystal X-ray analyses of the [3]catenane revealed two asymmetric [2]pseudorotaxane units inside the metallacycle. It was discovered that tubular structures were formed through the stacking of individual [3]catenane molecules driven by the strong π–π interactions.

A cyclic alkyne polymerization catalyst undergoes, with heat or a Lewis base, a rearrangement to form a vanadium imido monoazabutadieneallenyl complex, which is no longer an active catalyst. [Display omitted] We show in this study how the catalyst for the cyclic polymerization of phenylacetylene, a high-spin vanadium(III) complex supported by the β-diketiminate (BDI) scaffold, [(BDI)V(κ2-C,C-Me 3 SiC 3 SiMe 3)] (1) (BDI = [ArNC(CH 3)] 2 , Ar = 2,6- i Pr 2 C 6 H 3), can convert thermally or with a Lewis base to a low-spin [VIII] complex [{ArNC(CH 3)CHC(CH 3)C(SiMe 3)CC(SiMe 3)}V=NAr] (2). Complex 2 was characterized spectroscopically by multinuclear NMR (1H, 13C, 29Si, 51V), IR, and UV–Vis in addition to single crystal X-ray diffraction analysis. Complex 2 was found to be inactive towards the polymerization of phenylacetylene, unlike its predecessor 1 , therefore suggesting that such rearrangement might be the modus operandi for catalyst deactivation. We propose the 1 → 2 transformation to involve a denticity change from κ2-C,C-Me 3 SiC 3 SiMe 3 to a κ1-alkylidene-alkylnyl, followed by an intra-molecular cross-metathesis pathway involving the V=C bond of the alkylidene-alkynyl ligand with the imine group of the BDI ligand to eventually form the vanadium imido ligand and monoazabutadieneallenyl (MADA−) moiety. [ABSTRACT FROM AUTHOR]

• Exocyclic alkenyl ylide phenolate and benzoate Re (V) complexes. • Polycyclic rhenacycloprop-2-ene Re (III) complexes. • P-C bond cleavage during reductions of alkenyl ylide phenolate Re (V) complexes. Additions of nucleophiles like phosphines to coordinated alkynes are important processes in organometallic synthesis. In this work, exocyclic alkenyl ylide phenolate (1–2) and benzoate (5) Re(V) complexes are obtained from the reactions of internal 2-alkynylphenols, and 2-ethynylbenzoic acid with ReOCl 2 (OEt)(PPh 3) 2 , respectively. The Re(V) complexes 1–2 can be reduced to η 2-alkyne Re(III) complexes 3–4 with P-C bond cleavage. Exocyclic alkenyl ylide phenolate Re (V) complexes and polycyclic rhenacycloprop-2-ene Re (III) complexes have been produced from the reactions of internal 2-alkynylphenols with ReOCl 2 (OEt)(PPh 3) 2 under different conditions. The alkenyl ylide Re (V) complexes can be reduced to η 2-alkyne Re (III) complexes with P-C bond cleavage. [Display omitted] [ABSTRACT FROM AUTHOR]

Although boron dipyrromethene (BODIPY)-based metallacycles are expected to be promising candidates for imaging probes and therapeutic agents, their biomedical applications are restricted by their short absorption/emission wavelengths. In this work, we report a rhombic metallacycle M with broad absorption in the near-infrared (NIR) range and emissions at wavelengths >800 nm, which exhibits an efficient photothermal conversion capacity. Metallacycle M was encapsulated via Pluronic F127 to fit the biotic environment, resulting in the generation of F127/M nanoparticles (NPs) with high hydrophilicity and biocompatibility. In vitro studies demonstrated that the F127/M NPs underwent efficient cellular uptake and exhibited satisfactory photothermal therapeutic activity. Furthermore, in vivo experiments revealed that tumor growth was effectively inhibited, and the degree of undesirable biological damage was minimal in treatment with F127/M NPs and laser irradiation. Finally, the F127/M NPs could be visualized through NIR fluorescence imaging in living mice, thereby allowing their distribution to be monitored in order to enhance treatment accuracy during photothermal therapy. We envision that such BODIPY-based metallacycles will provide emerging opportunities for the development of novel therapeutic agents for biomedical applications.

Self-assembly of nickle acetate and N,N'-di[1-(2-hydroxyphenyl)- ethylidene]hydrazone (H2L) ligand in a 2:1 ratio in DMF and methanol afforded a dodecanuclear wheel-like coordination cluster: [Ni12L6(OAc)6 (HCOO) 6(DMF)6]•4DMF•5H2O (1), in which the formate ions were likely in situ originated from the oxidation of methanol molecules and each deprotonate ligand (L2-) adopting the μ4-η²,η¹,η¹,η² coordination mode with a large C=N_ N=C torsion angle of 94.1° ligates four different Ni(II) ions. Magnetic study revealed that 1 showed the long-range antiferromagnetic order with the Neer temperature of 9.0 K while the intracluster interaction between the neighboring Ni centers is alternately ferro- and antiferromagnetic (J= +5.0/ -9.2 K in the one J), mainly depending on the oxo-bridging angles. [ABSTRACT FROM AUTHOR]

Herein, we describe the mechanistic details on the oxidatively induced reductive elimination of isolated methyl iridium and ruthenium metallacycle complexes. It was demonstrated that the otherwise challenging C─C bond formation is indeed facilitated by external oxidation, being enabled under mild conditions. Computational analyses supported the proposed high‐valent pathway, where the energy barrier for reductive elimination significantly decreases upon the metallic oxidation to facilitate the desired C─C bond formation. [ABSTRACT FROM AUTHOR]

Despite the widespread clinical application of chemotherapeutic anticancer drugs, their adverse side effects and inefficient performances remain ongoing issues. A drug delivery system (DDS) designed for a specific cancer may therefore overcome the drawbacks of single chemotherapeutic drugs and provide precise and synergistical cancer treatment by introducing exclusive stimulus responsiveness and combined chemotherapy properties. Herein, we report the design and synthesis of a supramolecular drug delivery assembly 1 constructed by orthogonal self-assembly technique in aqueous media specifically for application in liver cancer therapy. Complex 1 incorporates the β-cyclodextrin host moleculefunctionalized organoplatinum(II) metallacycle 2 with two specific stimulus-responsive motifs to the signaling molecule nitric oxide (NO), in addition to the three-armed polyethylene glycol (PEG) functionalized ferrocene 3 with redox responsiveness. With this molecular design, the particularly low critical aggregation concentration (CAC) of assembly 1 allowed encapsulation of the commercial anticancer drug doxorubicin (DOX). Controlled drug release was also achieved by morphological transfer via a sensitive response to the endogenous redox and NO stimuli, which are specifically related to the microenvironment of liver tumor cells. Upon combination of these properties with the anticancer ability from the platinum acceptor, in vitro studies demonstrated that DOX-loaded 1 is able to codeliver anticancer drugs and exhibit therapeutic effectiveness to liver tumor sites via a synergistic effect, thereby revealing a potential DDS platform for precise liver cancer therapeutics. [ABSTRACT FROM AUTHOR]

Platinum(II) binds to 21,23‐ditelluraporphyrin forming a side‐on complex, which can be easily transformed into an aromatic metallaporphyrin, that is, 21‐platina‐23‐telluraporphyrin, with a platinacyclopentadiene unit built in the porphyrin skeleton in place of one pyrrole ring. The central platinum(II) ion with a CCNTe square‐planar coordination sphere can be oxidized to platinum(IV) by chlorine, bromine, methyl iodide or allyl chloride to yield octahedral complexes. All platinatelluraporphyrins show dynamic behavior involving the platinum ion coordination sphere fluxionality and the porphyrin skeleton deformation, both in‐plane and out‐of‐plane, as demonstrated by 1H NMR spectroscopy. [ABSTRACT FROM AUTHOR]

Optimised drug delivery systems with low toxicity and high efficacy for suppressing cancer cells are urgently needed. In this study, a quinolone derivative-based organoplatinum(II) supramolecular coordination complex (SCC) was synthesised by [2 + 2] coordination-driven self-assembly. Using this molecular design, synergistic chemotherapeutic effects were achieved by combining the anticancer agent platinum acceptor and quinolone derivative at a fixed ratio. Importantly, the well-defined rhomboidal shape and size of the SCC metallacycle self-assembled into nanoparticles with an average diameter of 38 nm in aqueous solution, conferring improved passive targeting and internalisation abilities towards tumour cells via the enhanced permeability and retention effect. In vitro evaluation with HepG2 cells showed that integration of the quinolone derivative and organoplatinum(II) acceptor improved antitumor activity compared with each independent component. These properties reveal the potential of Pt(II)-based SCCs for use in antitumor applications as a supramolecular chemotherapy self-delivery platform. A Pt(II) metallacycle-based supramolecular self-delivery nanocarrier platform through coordination-driven self-assembly of a dipyridine-functionalised quinolone derivative donor (QD) and 60° Pt (II) acceptor (PhenPt) was successfully constructed. This nanocarrier considerably enhanced the internalisation and anticancer efficacy, as shown by in vitro studies. [ABSTRACT FROM AUTHOR]

We synthesized a bidentate bispyridylhydrazone functionalized copillar[5]arene (BACP5A), which can self‐assemble through strong intermolecular hydrogen bonds. BACP5A self‐assembled into size‐controllable vesicles, with the synergistic interactions of intermolecular hydrogen bonding and internal amphiphilicity, which are responsive to pH, temperature and solvent. BACP5A was used to form a bidentate metal‐ligand coordinated complex with Zinc trifluoromethanesulfonate in which a new rectangular cavity containing hexacoordinated zinc ions occurred between two adjacent BACP5A. This type of coordinated complex may be employed for the development of new macrocyclic‐based artificial enzymes. [ABSTRACT FROM AUTHOR]

A recent article in Angewandte Chemie International Edition discusses a new system for photopatterning using a light-responsive liquid-crystalline metallacycle. This system allows for holographic, fluorescent, and photochromic patterning, which has potential applications in optical storage devices for information storage, encryption, and anticounterfeiting. The authors of the article, Haiyan Peng, Lin Xu, and others, explain the concept and its implications in their research. [Extracted from the article]

A recent article in Angewandte Chemie discusses a new system for photopatterning using a light-responsive liquid-crystalline metallacycle. This system allows for the creation of holographic, fluorescent, and photochromic patterns, which could have applications in optical storage devices for information storage, encryption, and anticounterfeiting. The authors of the article, Haiyan Peng, Lin Xu, and others, explain the potential of this technology in their research. [Extracted from the article]