Cyclometalated Platinum Complexes Research Articles

Circularly Polarized Phosphorescence Properties of Binuclear Cyclometalated Platinum(II) Complexes Bearing Axially Chiral Schiff-Base Ligands.

The synthesis, structure, and circularly polarized phosphorescence (CPP) properties of axially chiral cyclometalated binuclear platinum(II) complexes were described. A series of optically pure binuclear platinum(II) complexes were synthesized in five steps from commercially available (R)- or (S)-1,1'-bi-2-naphthol (BINOL) as starting materials. Their three-dimensional molecular structures and square-planar coordination geometries were elucidated from X-ray diffraction and 2D NMR analysis. The complexes were found to exhibit red- to near-infrared photoluminescence in solution and in the solid state. Furthermore, dilute DMSO solutions of the enantiopure samples showed red CPP with relatively high luminescence dissymmetry factor (glum) values. Density functional theory (DFT) calculations were conducted to examine their three-dimensional molecular conformations and photophysical properties.

1D, 3D supramolecular assemblies of a series of cyclometalated platinum(II) complexes with deep-red aggregation-induced phosphorescent emission and anion turn-on sensing via Pt-Pt interaction

Controlling the size and morphology of supramolecular assemblies is still an enormous challenge for the development of novel functional materials. Herein, cyclometalated platinum(II) complexes were designed and used as effective theragnostic supramolecular nano agents. Benzoquinoline was used as the main C^N ligand, and the increased number of aromatic rings in the N^N ligand of Pt complexes could greatly improve lipophilicity and cytotoxicity towards cancer cells over normal cells. Moreover, the morphology of nanoparticles formed by self-assembly of Pta-d could change from one to three-dimensional (1-3D), which can form nanowires and nanospheres. Besides, complexes of Pta-c, the number of aromatic rings in the N^N ligand of which does not exceed 4, all exhibit significant aggregation-induced phosphorescent emission (AIPE) with 100 - 200-fold enhancement in red phosphoresce intensity recorded in the solvent of Pta-1 and Ptb. Pt-Pt interaction induced by coordination and electrostatic interaction between complex and anions, and a new deep red emission improvement was observed in aqueous solution of Pta and Ptb with the presence of ClO4−, and two similar deep red emissions induced by two different interactions can be told by new emerging MMLCT absorption band. Ptd of dppz ligand exhibits the highest efficiency in inducing apoptosis of HeLa and its anticancer mechanism was studied. Our work aims to promote the fundamental comprehension of the self-assembly behavior of cyclometalated platinum complex with AIPE in vitro and living cells.

Research Progress of Deep-Red to Near-Infrared Electroluminescent Materials Based on Organic Cyclometallated Platinum(II) Complexes.

In recent years, the near-infrared (NIR) light-emitting materials have attracted increasing attention due to the broad application prospects in the fields of military industry, aerospace, lighting, display and wearable devices. As the transition metal complexes, platinum(II) complexes have been shown to emit luminescence efficiently in NIR organic light-emitting diodes because of the unique d8 electron structure. This structure ensures that the platinum(II) complex molecules exhibit a high planarity, variety of excited states, and strong intermolecular interactions. This review summarizes the research progress of deep red to NIR organic light-emitting materials based on platinum(II) complexes in recent years and provides a certain reference for the further design and synthesis of NIR platinum(II) complex luminescent materials with superior performance.

Ancillary Ligand Steric Effects and Cyclometalating Ligand Substituents Control Excited-State Decay Kinetics in Red-Phosphorescent Platinum Complexes.

Achieving high-efficiency red phosphorescence remains a significant challenge, especially in cyclometalated platinum complexes where radiative rates are inherently slower than their iridium counterparts. In this work, six red-emitting cyclometalated platinum complexes of the formula Pt(C∧N)[(Ar)acNac] (C∧N is the cyclometalating ligand, and (Ar)acNac is an aryl-substituted β-ketoiminate ancillary ligand) were synthesized and characterized. Two C∧N ligands were employed, 1-phenylisoquinoline (piq) and its cyano-substituted analogue 1-phenylisoquinoline-4-carbonitrile (piqCN), which both result in red phosphorescence in cyclometalated platinum complexes. These were paired with three (Ar)acNac ligands that are sterically differentiated via the N-aryl group, which is phenyl in the unsubstituted analogue (Ph)acNac and 2,6-dimethylphenyl or 2,6-diisopropylphenyl in the sterically encumbered analogues. An in-depth photophysical analysis of all compounds was performed and compared to the related compounds with the acetylacetonate (acac) ancillary ligand. While quantum yields are modest in the unsubstituted (Ph)acNac complexes, steric bulk on the β-ketoiminate has a pronounced effect on the excited-state dynamics and can lead to photoluminescence quantum yields of more than 0.50 in both solution and transparent polymer films, with the photoluminescence λmax ∼ 630 nm. We show that both steric effects on the electron-rich β-ketoiminate ancillary ligands and the cyano substituent on the cyclometalating ligand play a role in achieving high-efficiency phosphorescence in the red region.

Combined Nucleophilic and Electrophilic Functionalization to Optimize Blue Phosphorescence in Cyclometalated Platinum Complexes.

Ligand-based functionalization strategies have emerged as powerful approaches to tune and optimize blue phosphorescence, which can involve nucleophilic addition to coordinated ligands or electrophilic functionalization via the coordination of exogenous Lewis acids. Whereas both have been used separately to enhance the photophysical properties of organometallic compounds with high-energy triplet states, in this work, we show that these two strategies can be used together on the same platform. Isocyanide-supported cyclometalated platinum compounds undergo nucleophilic addition with diethylamine to form a strong σ-donor acyclic diaminocarbene-supporting ligand. In a subsequent step, a cyanide ancillary ligand is converted into a more strongly π-acidic isocyanoborate via the coordination of a borane Lewis acid. Importantly, both of these ligand-based functionalization steps improve the quantum yields and lifetimes of the blue-phosphorescent complexes. This synergy results in complexes with photoluminescence quantum yields up to 0.40 for deep blue and 0.75 for sky blue regions and PL lifetimes on the order of 10-5 s.

Turn-on Near-Infrared Phosphorescent Recognition of Anion Based on Self-Assembly of Cyclometalated Platinum Complexes That Induce Oncosis and Monitor Living Cells.

The design of bio-responsive functional molecular materials that can undergo self-assembly to form nanostructures within cells in response to cellular endogenous stimuli and the clarification of their prospective reaction mechanisms are of paramount significance. This work aims to elucidate the spatiotemporal generation of subcellular nanostructures and their influence on cellular functionality. Three sets of cyclometalated platinum complexes have been designed and synthesized as near-infrared phosphorescent turn-on probes for specific anions based on dynamic self-assembly in aqueous solution. The augmentation of the quantity of aromatic rings in the NN bidentate ligand of the complex modifies both the intensity of the intermolecular Pt-Pt interaction and the capacity to generate self-assembled nanowires with near-infrared emission. Besides, we explored the impact of the CN ligand's substituent effect on anion recognition, which revealed that complexes with electron-absorbing F atom substitution exhibit superior selectivity for Br-. These complexes display vivid green turn-on luminescence upon interaction with cellular biomolecules, enabling dynamic monitoring of their subcellular distribution and their interaction on diverse conditions. Furthermore, our complexes were observed to induce oncosis in cancer cells, underscoring the potential of our work in facilitating in vitro diagnosis and developing effective theranostic agents for cancer therapy.

Cationic cyclometalated platinum (II) complexes of metformin with self-assembly and AIE behavior as nuclear and mitochondrial targeted anticancer theragnostic agents

Self-assembly and AIE (Aggregation-induced emission) of cyclometalated platinum (II) complexes have attracted lots of attention. The high hydrophilia and low permeability of metformin (Met) has greatly hindered its further clinical application, herein, our work rationally designed and synthesized a pair of theragnostic cyclometalated platinum (II) - metformin complexes. Pt1 and Pt2 can improve bioactivity of Met significantly, and AIE deep-red emission can be mediated by tuning chemical structure of auxiliary ligand in compounds. Moreover, self-assembly of two Pt (II) complexes was revealed, as well as mitochondria and nuclear targeting ability of Pt2 were newly obtained during an AIE process. Meanwhile, Pt2 exhibits 186- and 53-fold enhanced antiproliferative activity compared with Met and Met-free complex analogue, their anticancer mechanisms were also investigated. Herein, our work provides a novel strategy for designing multi-functional platinum-based anticancer theragnostic agents.

Exploring structural and optical properties of a new series of soft salts based on cyclometalated platinum complexes.

A series of nine new soft salts based on two platinum(II) complexes, namely ([Pt(C^N)(CN)2]-[Pt(C^N)(en)]+) (en = ethane-1,2-diamine), has been developed and synthesized. Their photophysical properties in both solution and the solid state were described. All soft salt complexes exhibit phosphorescence emission with PLQY in the solid state up to 0.36. Most of these materials displayed aggregation-induced emission (AIE) or aggregation-induced emission enhancement (AIEE) in water/DMSO solutions as the water ratio increased. Structure-property relationships were analyzed in relation to emission properties. The presence of the free nitrogen atoms in soft salt complexes with a C^N pyrimidine-based ligand allowed for reversible sensitivity to acidic vapors, resulting in the quenching of phosphorescence emission. Additionally, for selected soft salts, we described reversible vapochromism behaviour, making these new materials interesting for multi-detection purposes in anti-counterfeiting applications.

π-Extended ligands with dual-binding behavior: hindered rotation unlocks unexpected reactivity in cyclometalated Pt complexes.

Cyclometalated platinum complexes play a crucial role in catalysis, bioimaging, and optoelectronics. Phenylpyridines are widespread cyclometalating ligands that generate stable and highly emissive Pt complexes. While it is common practice to modify these ligands to fine-tune their photophysical properties, the incorporation of polycyclic aromatic hydrocarbons into the ligand's structure has been largely overlooked. This report describes the cyclometalation of naphthalenyl- and anthracenylpyridine ligands, which has resulted in ten new luminescent PtII and PtIV complexes. These species are enabled by a dual-binding behavior discovered in our polyaromatic-containing ligands. The introduction of naphthalenyl and anthracenyl groups unlocks dual binding modes, with the Pt center bonding to either of two distant carbon atoms within the ligand. These complexes exhibit both symmetric structures with two 5-membered metallacycles and asymmetric structures with 5- and 6-membered metallacycles. This work presents a strategy for the regioselective synthesis of Pt complexes with bespoke structures and photophysical properties. Our findings offer new opportunities in platinum chemistry and beyond, with potential implications for materials and technologies.

Mechanochromism and circularly polarized luminescence of chiral cyclometalated platinum(II) complexes with different configurations and aggregated forms

Using a new synthesis method, we have prepared two different coordination configurations of chiral cyclometalated N^C^N-coordinated and C^N-coordinated Pt(II) complexes by controlling the Cl− source. Single-crystal X-ray diffraction determines the tridentate and bidentate structures. All N^C^N-coordinated and C^N-coordinated Pt(II) complexes emit green-yellow light in CH2Cl2 solutions. Square-planar N^C^N-Coordinated complexes (−)-1 and (−)-2 show remarkable aggregation-induced emission behaviors in mixed CH2Cl2/n-hexane solutions with the emission quantum yield (Φem) intensified significantly. In addition, the luminescent color could change from green-yellow to red by varying the volumetric fraction of n-hexane. Complex (−)-2 grafted with long alkyl chains could form helical stacking aggregates, inducing enhanced ECD signals and measurable CPL activity. The yellow and orange solids of complex (−)-1 can be separated, and a high-contrast mechanochromic luminescence is found for the yellow form. Furthermore, the potential utility has been attempted in anti-counterfeiting applications based on the yellow solid of (−)-1. This study provides a new design strategy for the preparation of chiral cyclometalated Pt(II) complexes with specific configurations and aggregated forms that have various optical and electronic properties.

A Series of Planar Phosphorescent Cyclometalated Platinum(II) Complexes as New Anticancer Theranostic Agents That Induce Oncosis.

Herein, four planar cyclometalated platinum(II) complexes with a main ligand of enlarged aromatic rings have been assessed as effective anticancer theranostic agents for the first time. With an increased number of aromatic rings in the N∧N ligand, 1a-1d exhibit increased lipophilicity and cytotoxicity selectivity. The intensity of the Pt-Pt interaction of each complex can be indicated by an enhanced near-infrared (NIR) emission in phosphate-buffered saline (PBS), their binding activity with biomolecules of bovine serum albumin (BSA) is accompanied by a vivid turn-on green emission, and the intensity gradually decreased from 1a to 1d, which is consistent with the docking of two complexes with BSA. Both "turn-on" NIR and green emission of 1d can be mainly observed in nuclei of living cell within 24 h, while two phosphorescence traces of 1b were recorded in lysosomes by confocal imaging. Moreover, 1d shows the highest efficiency in inducing oncosis of Hela cells, and the relative process was investigated.

Cyclometallated Platinum(II) Complexes Featuring an Unusual, C^N‐Coordinating Pyridyl‐pyridylidene Ligand and L X Coligands: Synthesis, Structures and Dual Luminescence Behavior

AbstractThanks to an unusual protodemethylation reaction, a series of luminescent cyclometallated platinum(II) complexes can be prepared, which incorporate a rare NC‐chelating, pyridyl‐pyridylidene ligand, in combination with OO‐coordinating acetylacetonate (acac) or NO‐coordinating 2‐picolinate (pic) or 8‐hydroxyquinolate. The acac and pic complexes show unusual dual emission in a frozen glass.A series of cyclometallated platinum(II) complexes incorporating a rare, N^C‐chelating, pyridyl‐pyridylidene ligand are described, in which the coordination sphere is completed by two chlorides or an L X co‐ligand, namely O O‐coordinating acetylacetonate (acac), or N^O‐coordinating 2‐picolinate (pic) or 8‐hydroxyquinolinate. The acac and pic complexes have been structurally characterized in the solid state by single‐crystal X‐ray diffraction. These two complexes display red phosphorescence in the solid state at room temperature. In a frozen glass at 77 K, all four complexes show two broad emission bands that span much of the visible spectrum, apparently from two unequilibrated excited states.

Platinum(II)-Based Optical Probes for Imaging Quadruplex DNA Structures via Phosphorescence Lifetime Imaging Microscopy.

G-quadruplex DNA is a non-canonical structure that forms in guanine-rich regions of the genome. There is increasing evidence showing that G-quadruplexes have important biological functions, and therefore molecular tools to visualise these structures are important. Herein we report on a series of new cyclometallated platinum(II) complexes which, upon binding to G-quadruplex DNA, display an increase in their phosphorescence, acting as switch-on probes. More importantly, upon binding to G-quadruplexes they display a selective and distinct lengthening of their emission lifetime. We show that this effect can be used to selectively visualise these structures in cells using Phosphorescence Lifetime Imaging Microscopy (PLIM).

Platinum(II)-Based Optical Probes for Imaging Quadruplex DNA Structures via Phosphorescence Lifetime Imaging Microscopy.

G-quadruplex DNA is a non-canonical structure that forms in guanine-rich regions of the genome. There is increasing evidence showing that G-quadruplexes have important biological functions, and therefore molecular tools to visualise these structures are important. Herein we report on a series of new cyclometallated platinum(II) complexes which, upon binding to G-quadruplex DNA, display an increase in their phosphorescence, acting as switch-on probes. More importantly, upon binding to G-quadruplexes they display a selective and distinct lengthening of their emission lifetime. We show that this effect can be used to selectively visualise these structures in cells using Phosphorescence Lifetime Imaging Microscopy (PLIM).

Efficient detection of picric acid with aggregation-induced phosphorescent emission neutral cyclometalated platinum(II) complexes in aqueous media

Three neutral cyclometalated platinum(II) complexes have been synthesized and fully characterized. All complexes show aggregation-induced phosphorescent emission properties in THF/H2O. These complexes can detect picric acid efficiently in aqueous media with limits of detection of 0.17, 0.03 and 0.15 μM, respectively. Moreover, the complexes exhibit high selectivity for picric acid in the presence of other competitive compounds and perform well in real water samples. The results show that photo-induced electron transfer is responsible for the luminescence quenching of the complexes.

Synthese und photophysikalische Eigenschaften monometallischer C^C* Platin(II)‐Formamidinatkomplexe mit sterisch anspruchsvollen Liganden

AbstractEine neuartige – bisher als unzugänglich angesehene – Klasse von zyklometallierten Platin(II)‐Komplexen wurde durch eine verbesserte Syntheseroute unter Verwendung von Liganden, die durch Dichtefunktionaltheorieberechnungen vorhergesagt wurden, hergestellt. Basierend auf einem gezielten quantenchemischen Screening wurden drei Modellliganden mit unterschiedlichem sterischem Anspruch ausgewählt und eine Serie von sechs photolumineszenten Platin(II)‐Formamidinatkomplexen mit C^C* zyklometallierten Liganden hergestellt. Der Ligand mit dem geringsten sterischen Anspruch führte zu einem bimetallischen Komplex in zwei isomeren Formen, die voneinander getrennt und durch die entsprechenden Kristallstrukturen bestätigt werden konnten. Wie durch die quantenchemischen Rechnungen vorhergesagt, lieferten die sterisch stärker gehinderten Amidinatliganden die monometallischen Komplexe. Aufgrund des Verlusts der Metall‐Metall‐Wechselwirkungen zeigen diese Komplexe eine signifikante hypsochrome Verschiebung der Emissionswellenlänge. In Abhängigkeit vom zyklometallierten Ligand zeigt diese neue Klasse von Platin(II)‐Emittern grün‐blaue bis rein blaue Phosphoreszenz mit Quantenausbeuten von bis zu 87 % und kurzen Abklingzeiten.

An oxygen-sensitive cyclometalated platinum(II) complex with a triphenylamine modified acetylacetone derivative

A cyclometalated Pt(II) complex [Pt(ppy)(TPA-dpa)] Pt2 with a triphenylamine (TPA) substituted diphenyl-1,3-propanedionate (dpa) as auxiliary ligand was designed and synthesized. The effects of the TPA moiety on the photophysical, electrochemical and oxygen sensing properties of the corresponding Pt(II) complex were systematically investigated compared with non-TPA-modified complexes [Pt(ppy)(dpa)] Pt1 and Pt(ppy)(acac). The maximum emission wavelength of Pt2 exhibits a notable redshift (71 nm) with respect to Pt(ppy)(acac). More importantly, the lifetime (25.52 µs) of Pt2 is significantly prolonged compared with those of Pt1 (0.32 µs) and Pt(ppy)(acac) (2.60 µs). Pt2 is highly sensitive to molecular oxygen when immobilized in an ethyl cellulose film. In addition, the oxygen sensing films have excellent reversibility during the quenching and recovering processes.

Bisisocyanide cyclometallated platinum(II) complexes: synthesis, structure, photophysical properties, and mechanochromic behavior

A series of cyclometallated platinum(II) complexes [Pt(ppy){CNAr}2]X with two isocyanide ligands (Hppy = 2-phenylpyridine, Ar = C6H2-2,4,6-Me3, C6H3-2-Cl-6-Me , C6H3-2,6-Cl2, C6H4-4-NMe2, C6H4-4-Me, C6H4 4-Cl, C6H4-4-Br, C6H4-4-I, C6H4-4-CF3, C6H4-3-CF3; X = BF4, OTf) was synthesized by the reaction of the [{Pt(ppy)Cl}2] dimer with isocyanides (yield 52-70%). The structure of the resulting complexes was determined using mass spectrometry, 1H, 13C{1H}, 195Pt{1H}, 1H-1H COSY, 1H-1H NOESY, 1H-13C HSQC, and 1H-13C HMBC NMR spectroscopy in solution and solid-state CP/MAS 13C and 195Pt NMR spectroscopy, IR spectroscopy and X-ray diffraction analysis in the solid phase. The photophysical properties of the obtained complexes in the solid phase and the mechanochromic luminescence behavior were studied. In the solid phase, all synthesized compounds phosphoresce in the green or orange range of visible light, while photoluminescence quantum yields reach 26%. Green phosphors exhibit a reversible mechanochromic luminescence change achieved by mechanical grinding (green to orange) and solvent adsorption (orange to green).

Cyclometalated platinum(II) complexes with acyclic diaminocarbene ligands for OLED application.

A novel series of cyclometalated platinum(II) complexes bearing acyclic diaminocarbene (ADC) ancillary ligands were designed and prepared. Their photophysical properties were systematically studied through experimental and theoretical investigations. All complexes exhibit green phosphorescence with a quantum efficiency of up to 45% in 2 wt% doped PMMA film at room temperature. The complexes are used as light-emitting dopants for organic light-emitting diode (OLED) fabrication. The devices displayed a green emission with a maximum current efficiency of 2.9 cd A-1 and a luminance of 2700 cd m-2. These results show that these cyclometalated platinum(II) complexes can be used as efficient green emitting components of OLED devices.

Luminescent cyclometalated platinum compounds with N, P, and O^O ligands: Density‐functional theory studies and analysis of the anticancer potential

Luminescent platinum cyclometalated complexes are species of interest mainly due to their applications in the optoelectronic and biological fields, especially with regard to their anticancer activity. Given this level of interest, a series of cyclometalated (2‐[2′‐thienyl]pyridinate, thpy and 2‐[2,4‐difluorophenyl]pyridinate, dfppy) platinum complexes with N‐donor, PTA (1,3,5‐triaza‐7‐phosphaadamantane) or chrysin‐derived ligands (incorporating piperidine, HL1, or morpholine, HL2, fragments) were synthesized. The complexes are luminescent with tunable emission wavelengths. Aggregation in solution was observed for [Pt(dfppy)L1], 5. Density‐functional theory (DFT) studies provided descriptions of the highest occupied molecular orbital (HOMO) and least unoccupied molecular orbital (LUMO) characteristics and their influence on the photophysical properties. The orbitals of 5–6 were different in nature to those of 1–4. Time‐dependent DFT (TD‐DFT) calculations showed that for 1–4 the excited states S1 and T1 reflect metal‐to‐ligand charge transfer (MLCT) and ligand‐centered (LC) (C^N) contributions while for 5–6 these states are an LC transition centered on L1 or L2. The speciation in DMSO and DMSO/H2O was evaluated. Biological studies showed that [Pt(thpy)Cl(Hthpy)], 1, [Pt(dfppy)Cl(Hdfppy)], 2, and 5 exert significant cytotoxic activity against human cervical (HeLa) and lung (A549) carcinoma cells. The cytotoxicity of 1 increased 2.84‐fold upon irradiation (blue). Microscopy assays on 5 showed that this compound accumulates in cytoplasmic organelles, preferentially in mitochondria. Mitochondrial metabolism was disrupted by the activity of the complexes, leading to a decline in the adenosine triphosphate (ATP) cellular content. Overall, the results show an alternative anticancer activity for complexes 1, 2, and 5, which could be of great interest for the treatment of tumors with acquired resistance to conventional DNA‐targeted anticancer drugs.