Cyclometalated Complexes Research Articles

Photofunction‐Directed Coordination Molecular Engineering

AbstractMolecular engineering has emerged as a highly interdisciplinary field of study on function‐directed molecular design, material synthesis, and property optimization, accompanied by a deep understanding of the structure‐property relationship. In this review, our recent progress on the design and preparations of photofunctional metal complexes and related materials is summarized from the perspective of coordination molecular engineering. In particular, a series of cyclometalated diruthenium complexes with near‐infrared (NIR) electrochromic property have been synthesized by engineering the bridging ligand structures. A group of ruthenium‐amine conjugated complexes with multistage NIR electrochromism are obtained on the basis of a multicenter strategy. By engineering the ligand structures, a series of new ruthenium and platinum complexes are synthesized to show switchable luminescence in response to various stimuli. In addition, photoluminescent ruthenium, iridium, and platinum complexes are assembled to afford micro/nanocrystals with well‐defined morphology and luminescent properties. What is the most favorite and original chemistry developed in your research group?Ruthenium‐triarylamine conjugated system is one of my favorite topics.How do you get into this specific field?Molecular materials with multistage redox processes and multiple near‐ infrared absorptions are a challenging task in the field of electrochromism and molecular switching. The combination of cyclometalated ruthenium complexes and triarylamines allows us to solve this issue by using a multicenter strategy with a great structural and functional diversity.What is the most important personality for scientific research?Personally, I consider honesty, curiosity, and persistence are the most important and fundamental personalities in carrying out scientific research.What's your hobbies?I enjoy playing basketball and watching basketball matches in leisuretime.How do you keep balance between research and family?I like managing time by prioritizing daily tasks. If time permits, I'm glad to join family activities in cooking, walking, exercising, etc. I always appreciate and support my wife's career and my daughter's studies, from which I receive their returns in support of my career.Could you please give us some advices on improving Chinese Journal of Chemistry?Chin. J. Chem. is a classical and influential journal of chemistry. The impact of the journal keeps increasing especially in recent years. In my point of view, it would be helpful for the journal by keeping a balance among different subjects of chemistry while welcoming manuscripts on material and energy‐related interdisciplinary researches. In addition, in order to further boost its global reputation, I would like to suggest inviting more international scientists to contribute to the journal.

Electronic Communication in Binuclear Osmium- and Iridium-Polyhydrides.

Reactions of polyhydrides OsH6(PiPr3)2 (1) and IrH5(PiPr3)2 (2) with rollover cyclometalated hydride complexes have been investigated in order to explore the influence of a metal center on the MHn unit of the other in mixed valence binuclear polyhydrides. Hexahydride 1 activates an ortho-CH bond of the heterocyclic moiety of the trihydride metal–ligand compounds OsH3{κ2-C,N-[C5RH2N-py]}(PiPr3)2 (R = H (3), Me (4), Ph (5)). Reactions of 3 and 4 lead to the hexahydrides (PiPr3)2H3Os{μ-[κ2-C,N-[C5RH2N-C5H3N]-N,C-κ2]}OsH3(PiPr3)2 (R = H (6), Me (7)), whereas 5 gives the pentahydride (PiPr3)2H3Os{μ-[κ2-C,N-[C5H3N-C5(C6H4)H2N]-C,N,C-κ3]}OsH2(PiPr3)2 (8). Pentahydride 2 promotes C—H bond activation of 3 and the iridium-dihydride IrH2{κ2-C,N-[C5H3N-py]}(PiPr3)2 (9) to afford the heterobinuclear pentahydride (PiPr3)2H3Os{μ-[κ2-C,N-[C5H3N-C5H3N]-N,C-κ2]}IrH2(PiPr3)2 (10) and the homobinuclear tetrahydride (PiPr3)2H2Ir{μ-[κ2-C,N-[C5H3N-C5H3N]-N,C-κ2]}IrH2(PiPr3)2 (11), respectively. Complexes 6–8 and 11 display HOMO delocalization throughout the metal–heterocycle-metal skeleton. Their sequential oxidation generates mono- and diradicals, which exhibit intervalence charge transfer transitions. This notable ability allows the tuning of the strength of the hydrogen–hydrogen and metal–hydrogen interactions within the MHn units.

Rollover Cyclometalation as a Valuable Tool for Regioselective C-H Bond Activation and Functionalization.

Rollover cyclometalation constitutes a particular case of cyclometallation reaction. This reaction occurs when a chelated heterocyclic ligand loses its bidentate coordination mode and undergoes an internal rotation, after which a remote C–H bond is regioselectively activated, affording an uncommon cyclometalated complex, called “rollover cyclometalated complex”. The key of the process is the internal rotation of the ligand, which occurs before the C–H bond activation and releases from coordination a donor atom. The new “rollover” ligand has peculiar properties, being a ligand with multiple personalities, no more a spectator in the reactivity of the complex. The main reason of this peculiarity is the presence of an uncoordinated donor atom (the one initially involved in the chelation), able to promote a series of reactions not available for classic cyclometalated complexes. The rollover reaction is highly regioselective, because the activated C–H bond is usually in a symmetric position with respect to the donor atom which detaches from the metal stating the rollover process. Due to this novel behavior, a series of potential applications have appeared in the literature, in fields such as catalysis, organic synthesis, and advanced materials.

Synthesis and electronic coupling studies of cyclometalated diruthenium complexes bridged by 3,3',5,5'-tetrakis(benzimidazol-2-yl)-biphenyl.

Three cyclometalated diruthenium complexes bridged by 3,3',5,5'-tetrakis(benzimidazol-2-yl)biphenyl (H-tbibp) and capped with different terminal ligands have been synthesized and examined. In addition, two monoruthenium complexes with H-tbibp have been prepared for the purpose of comparison studies. The degree of Ru-Ru electronic coupling of these diruthenium complexes has been investigated by electrochemical and intervalence charge-transfer (IVCT) analyses. These results suggest that when the same or similar terminal ligands are used, the strength of H-tbibp in mediating the Ru-Ru coupling is enhanced with respect to that of the previously reported bridging ligand 3,3',5,5'-tetrakis(N-methylbenzimidazol-2-yl)biphenyl, but it is slightly inferior to that of the classical bridging ligand 3,3',5,5'-tetrakis(pyrid-2-yl)biphenyl. This trend is also supported by CNS analyses based on the hole-superexchange mechanism. In addition, DFT calculations have been performed to probe the spin density distributions of the singly-oxidized diruthenium complexes with H-tbibp and TDDFT calculations are used to reproduce the IVCT transitions.

Chiral cyclometalated iridium complexes for asymmetric reduction reactions.

A series of chiral cyclometalated iridium complexes have been synthesised by cyclometalating chiral 2-aryl-oxazoline and imidazoline ligands with [Cp*IrCl2]2. These iridacycles were studied for asymmetric transfer hydrogenation reactions with formic acid as the hydrogen source and were found to display various activities and enantioselectivities, with the most effective ones affording up to 63% ee in the asymmetric reductive amination of ketones and 77% ee in the reduction of pyridinium ions.

Synthesis, structure and reactivity of iridium complexes containing a bis-cyclometalated tridentate C^N^C ligand.

In an effort to synthesize cyclometalated iridium complexes containing a tridentate C^N^C ligand, transmetallation of [Hg(HC^N^C)Cl] (1) (H2C^N^C = 2,6-bis(4-tert-butylphenyl)pyridine) with various organoiridium starting materials has been studied. The treatment of 1 with [Ir(cod)Cl]2 (cod = 1,5-cyclooctadiene) in acetonitrile at room temperature afforded a hexanuclear Ir4Hg2 complex, [Cl(κ2C,N-HC^N^C)(cod)IrHgIr(cod)Cl2]2 (2), which features Ir-Hg-Ir and Ir-Cl-Ir bridges. Refluxing 2 with sodium acetate in tetrahydrofuran (thf) resulted in cyclometalation of the bidentate HC^N^C ligand and formation of trinuclear [(C^N^C)(cod)IrHgIr(cod)Cl2] (3). On the other hand, refluxing [Ir(cod)Cl]2 with 1 and sodium acetate in thf yielded [Ir(C^N^C)(cod)(HgCl)] (4). Chlorination of 4 with PhICl2 gave [Ir(C^N^C)(cod)Cl]·HgCl2 (5·HgCl2) that reacted with tricyclohexylphosphine to yield Hg-free [Ir(C^N^C)(cod)Cl] (5). Chloride abstraction of 5 with silver(i) triflate (AgOTf) gave [Ir(C^N^C)(cod)(H2O)](OTf) (6) that can catalyze the cyclopropanation of styrene with ethyl diazoacetate. Reaction of 1 and [Ir(CO)2Cl(py)] (py = pyridine) with sodium acetate in refluxing thf afforded [Ir(C^N^C)(HgCl)(py)(CO)] (7), in which the carbonyl ligand is coplanar with the C^N^C ligand. On the other hand, refluxing 1 with (PPh4)[Ir(CO)2Cl2] and sodium acetate in acetonitrile gave [Ir(C^N^C)(κ2C,N-HC^N^C)(CO)] (8), the carbonyl ligand of which is trans to the pyridyl ring of the bidentate HC^N^C ligand. Upon irradiation with UV light 8 in thf was isomerized to 8', in which the carbonyl is trans to a phenyl group of the bidentate HC^N^C ligand. The isomer pair 8 and 8' exhibited emission at 548 and 514 nm in EtOH/MeOH at 77 K with lifetime of 84.0 and 64.6 μs, respectively. Protonation of 8 with p-toluenesulfonic acid (TsOH) afforded the bis(bidentate) tosylate complex [Ir(κ2C,N-HC^N^C)2(CO)(OTs)] (9) that could be reconverted to 8 upon treatment with sodium acetate. The electrochemistry of the Ir(C^N^C) complexes has been studied using cyclic voltammetry. Reaction of [Ir(PPh3)3Cl] with 1 and sodium acetate in refluxing thf led to isolation of the previously reported compound [Ir(κ2P,C-C6H4PPh2)2(PPh3)Cl] (10). The crystal structures of 2-5, 8, 8', 9 and 10 have been determined.

BSA-encapsulated cyclometalated iridium complexes as nano-photosensitizers for photodynamic therapy of tumor cells.

Photodynamic therapy is a promising treatment method. The development of suitable photosensitizers can improve therapeutic efficacy. Herein, we report three iridium complexes (Ir1, Ir2, and Ir3), and encapsulate them within bovine serum albumin (BSA) to form nano-photosensitizers (Ir1@BSA, Ir2@BSA, and Ir3@BSA) for photodynamic therapy (PDT) of tumor cells. In the structures of Ir(iii) complexes, we use the pyrazine heterocycle as part of the C^N ligands and explore the effect of different ligands on the ability to generate singlet oxygen (1O2) by changing the conjugation length of the ligand and increasing the coplanarity of the ligand. Besides, the fabricated nano-photosensitizers are beneficial to improve water dispersibility and increase cellular uptake ability. Through studying photophysical properties, 1O2 generation capacity, and cellular uptake performance, the results show that Ir1@BSA has the best photodynamic therapeutic effect on 4T1 tumor cells. This study provides an effective research basis for the further design of new nano-photosensitizers.

Pd-catalyzed synthesis of 1-(hetero)aryl-2,2,2-trichloroethanols using chloral hydrate and (hetero)arylboroxines.

1-(Hetero)aryl-2,2,2-trichloroethanols are useful key intermediates for the synthesis of various bioactive compounds. Herein, we describe N-heterocyclic carbene (NHC)-coordinated cyclometallated palladium complex (CYP)-catalyzed (hetero)aryl addition of chloral hydrate using (hetero)arylboroxines, providing a new approach to 1-(hetero)aryl-2,2,2-trichloroethanols. Notably, PhS-IPent-CYP which coordinated the bulky yet flexible 2,6-di(pentan-3-yl)aniline (IPent)-based NHC showed good catalytic activities and promoted the transformation in 24–97% yields.

Cyclometalated Ir(III) complexes as potential electron acceptors for organic solar cells.

Cyclometalated iridium(iii) complexes have been investigated as promising electron donor (D) materials in organic solar cells (OSCs) due to their unique octahedral configuration for optimized morphology and their significantly long lifetimes potentially for enhanced exciton dissociation. However, the application as electron acceptor (A) materials has never been reported. In order to fill this blank, herein, two cyclometalated heteroleptic Ir complexes, TRIr and 2TRIr, based on electron donating-accepting type organic ligands with different π-conjugation lengths are reported as electron acceptor materials in comparison with their corresponding main organic ligands. The two Ir complexes exhibit suitable HOMO/LUMO energy levels of -5.55/-3.47 eV and -5.44/-3.48 eV, which are ∼0.1 eV higher in the HOMO and ∼0.15 eV deeper in the LUMO than the TR and 2TR ligands, respectively. 2TRIr with extended ligand π-conjugation displays a poor triplet feature, while TRIr demonstrates obvious metal-to-ligand charge transfer (MLCT) transition absorption, with a triplet component photoluminescence (PL) lifetime of 85 ns in neat films. When blended with PBDB-T in bulk heterojunction (BHJ) OSCs, the power conversion efficiencies (PCEs) are 2-3 times higher than their relevant ligands, with values of 1.20% and 1.62% for TRIr and 2TRIr, and 0.58% and 0.47% for the TR and 2TR ligand-based devices, respectively. TRIr and 2TRIr based active layer blends exhibit poorer hole and electron mobilities, whereas compared with their relatively linear planar ligands, both of the two octahedral Ir complexes exhibit an optimized surface morphology for less bimolecular recombination and more efficient exciton dissociation, thus contributing to improved photovoltaic performance.

Red to near-infrared phosphorescent Ir(iii) complexes with electron-rich chelating ligands.

The design of molecular phosphors with near-unity photoluminescence quantum yields in the low-energy regions of the spectrum, red to near-infrared, is a long-standing challenge. Because of the energy gap law and the quantum mechanical dependence of radiative decay rate on the excited-state energy, compounds which luminesce in this region of the spectrum typically suffer from low quantum yields. In this article, we highlight our group's advances in the design of top-performing cyclometalated iridium complexes which phosphoresce in red to near-infrared regions. The compounds we have introduced in this body of work have the general formula Ir(C^N)2(L^X), where C^N is a cyclometalating ligand that controls the photoluminescence color and L^X is a monoanionic chelating ancillary ligand. The Ir(C^N)2(L^X) structure type is among the most widely studied and technologically successful classes of molecular phosphors, particularly when L^X = acetylacetonate (acac). In our work we have pioneered the use of electron-rich, nitrogen containing ancillary (L^X) ligands as a means of controlling the excited-state dynamics and optimizing them to give record-breaking phosphorescence quantum yields. This paper progresses through our work in three distinct regions of the spectrum - red, deep-red, and near-infrared - and summarizes the many insights we have gained on the relationships between molecular structure, frontier orbital energies, and excited-state dynamics.

Tetranuclear rollover cyclometalated organoplatinum-rhenium compounds; C-I oxidative addition and C-C reductive elimination using a rollover cycloplatinated dimer.

The novel tetranuclear Pt(IV)-Re(VII) complex [Pt2Me4(OReO3)2(PMePh2)2(µ-bpy-2H)], 4, is synthesized through the reaction of silver perrhenate with a new rollover cycloplatinated(IV) complex [Pt2Me4I2(PMePh2)2(µ-bpy-2H)], 3. In complex 4, while 2,2'-bipyridine (bpy) acts as a linker between two Pt metal centers, oxygen acts as a mono-bridging atom between Pt and Re centers through an unsupported Pt(IV)-O-Re(VII) bridge. The precursor rollover cycloplatinated(IV) complex 3 is prepared by the MeI oxidative addition reaction of the rollover cycloplatinated(II) complex [Pt2Me2(PMePh2)2(µ-bpy-2H)], 2. Complex 2 shows a metal-to-ligand charge-transfer band in the visible region, which was used to investigate the kinetics and mechanism of its double MeI oxidative addition reaction. Based on the experimental findings, the classical SN2 mechanism was suggested for both steps and supported by computational studies. All complexes are fully characterized using multinuclear NMR spectroscopy and elemental analysis. Attempts to grow crystals of the rollover cycloplatinated(IV) dimer 3 yielded a new dimer rollover cyclometalated complex [Pt2I2(PMePh2)2(µ-bpy-2H)], 5, presumably from the C-C reductive elimination of ethane. The identity of complex 5 was confirmed by single crystal X-ray diffraction analysis.

Steric effects on acetate-assisted cyclometallation of meta-substituted N-phenyl and N-benzyl imidazolium salts at [MCl2Cp*]2 (M = Ir, Rh).

meta-Substituted N-phenyl,N'-methyl and N-benzyl,N'-methyl imidazolium salts undergo acetate-assisted cyclometallation to provide mixtures of ortho and para substituted cyclometallated complexes. The effect of the substituents on the isomer ratios is discussed; steric effects are more important in the 6-membered rings derived from the N-benzyl imidazolium salts than 5-membered rings from the N-phenyl salts. Comparisons are made to steric effects with some other common directing groups.

Regioselective B—H/C—H Bond Activation at Azo‐Substituted Carboranes Induced by Half‐Sandwich Iridium(III) Complex

Main observation and conclusionWe report herein a practical approach for regio‐selective B—H/C—H bond activation at azo‐substituted carboranes. The reaction proceeded through Iridium(III)‐induced selective B—H/C—H bond activations based on an azo directing group. Through this strategy, a series of mononuclear, trinuclear and tetranuclear cyclometalated iridium complexes containing Cp*Ir—B or Cp*Ir—C bonds were successfully isolated in a high yield. In this work, efficient routes are developed through one‐pot reactions to prepare polynuclear organometallic complexes.

Modulation of Metallophilic and π-π Interactions in Platinum Cyclometalated Luminophores with Halogen Bonding.

Luminescent cyclometalated complexes [M(C^N^N)CN] (M=Pt, Pd; HC^N^N=pyridinyl- (M=Pt 1, Pd 5), benzyltriazolyl- (M=Pt 2), indazolyl- (M=Pt 3, Pd 6), pyrazolyl-phenylpyridine (M=Pt 4)) decorated with cyanide ligand, have been explored as nucleophilic building blocks for the construction of halogen-bonded (XB) adducts using IC6 F5 as an XB donor. The negative electrostatic potential of the CN group afforded CN⋅⋅⋅I noncovalent interactions for platinum complexes 1-3; the energies of XB contacts are comparable to those of metallophilic bonding according to QTAIM analysis. Embedding the chromophore units into XB adducts 1-3⋅⋅⋅IC6 F5 has little effect on the charge distribution, but strongly affects Pt⋅⋅⋅Pt bonding and π-stacking, which lead to excited states of MMLCT (metal-metal-to-ligand charge transfer) origin. The energies of these states and the photoemissive properties of the crystalline materials are primarily determined by the degree of aggregation of the luminophores via metal-metal interactions. The adduct formation depends on the nature of the metal and the structure of the metalated ligand, the variation of which can yield dynamic XB-supported systems, exemplified by thermally regulated transition 3↔3⋅⋅⋅IC6 F5 .

AIPE-active Ir(Ⅲ) complexes with reversible piezochromic behavior and its application for data security protection

Three cyclometalated iridium complexes bearing different electron donating or electron withdraw group substitutes (Ir-OCH3), (Ir-H), (Ir-CF3) were synthesized and characterized. All complexes exhibit obvious aggregation-induced phosphorescence emission (AIPE) behavior in CH3CN-water mixtures, and relatively high absolute quantum efficiency in solid-states (ΦF =0.12-0.35). In addition, complexes Ir-OCH3 and Ir-CF3 show distinct revisable mechanochromic response. Upon grinding, the emission color of Ir-OCH3 and Ir-CF3 in solid state can be tuned from yellow to orange and green to yellow (both of Ir-OCH3 and Ir-CF3 show about 30 nm red-shift), respectively. Powder X-ray diffraction spectroscopy (PXRD) were also used to confirm the phase transition of different complexes in their different colored solid state. Moreover, complex Ir-CF3 was conducted as smart luminescent materials in a model of data security protection.

Synthesis and redox properties of cyclometallated iridium (III) complexes modified with arylamino groups

We present herein the synthesis, structure, redox and electronic absorption studies of a series of cyclometalated iridium-triarylamine complexes 1−7. For complexes 1-4 where the amine nitrogen is in the meta position to the Ir–CC^N bond, the electronic nature of the triarylamine units is varied by using different substituents (H, Me, OMe and Cl). In order to study the relationship between the connection mode and the intramolecular electron coupling properties, the amine nitrogen is placed in the para position with respect to the Ir–CC^N bond in complexes 5 and 6. And it should be noted that all of these complexes exhibit two well-defined redox processes (N/N•+ and IrIII/IV) within the available potential window at appreciably low potentials. The neutral, one-electron-oxidized states of complexes 3 and 6 were investigated by cyclic voltammetry (CV) and square-wave voltammetry (SWV), UV-vis-NIR spectroelectrochemistry and theoretical calculations. Experimental results show that the above mentioned four different substituents does not have a significant effect on the potential splitting ΔE between the two anodic redox waves of complexes 1-4. But, the ΔE of complex 6 is larger than that of complex 3, indicating that the electron coupling of arylamine and iridium units in the para position (6) is stronger than that in the meta position (3), which is also verified by in-situ absorption spectroelectrochemistry. It is worth noting that the directions of intramolecular charge-transfer in complexes 1 and 5 is reversed due to the different arylamine groups attachment sites (either meta or para to the Ir–CC^N bond).

New Organometallic Ruthenium(II) Compounds Synergistically Show Cytotoxic, Antimetastatic and Antiangiogenic Activities for the Treatment of Metastatic Cancer.

In this study, we newly designed and synthesized a small library of ten structurally related C,N-cyclometalated ruthenium(II) complexes containing various pyridine-functionalized NHC ligand and chelating bipyridyl ligands (e.g., 2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, and 1,10-phenanthroline (phen)). The complexes were well characterized by NMR, electrospray ionization-mass spectrometry, and single-crystal X-ray structure analyses. Among the new ruthenium(II) derivatives, we identified that the complex Ru8 bearing bulky moieties (i.e., phen and pentamethyl benzene) had the most potent cytotoxicity against all tested cancer cell lines, generating dose- and cell line-dependent IC50 values at the range of 3.3-15.0 μm. More significantly, Ru8 not only efficiently inhibited the metastasis process against invasion and migration of tumor cells but also exhibited potent antivascular effects by suppressing HUVEC cells migration and tube formation in vitro and blocking vessel generation in vivo (chicken chorioallantoic membrane model). In a metastatic A2780 tumor xenograft-bearing mouse model, administration of Ru8 outperformed antimetastatic agent NAMI-A and clinically approved cisplatin in terms of antitumor efficacy and inhibition of metastases to other organs. Overall, these data provided compelling evidence that the new cyclometalated ruthenium complex Ru8 is an attractive agent because of synergistically suppressing bulky tumors and metastasized tumor nudes. Therefore, the complex Ru8 deserves further investigations.

Application of Hemilabile Ligands to “At-Metal Switching” Hydrogenation Catalysis

The paper describes the development of switchable catalysts: i.e., precatalysts that are activated by a reagent and the resulting active catalyst can be shut off with a second reagent. A concept is introduced involving oxidative addition of a rhodium(I) catalyst with trityl chloride and reductive activation of dichlororhodium(III) phosphines with cobaltocene. Part 1 of the paper describes the development of the catalytic platforms, which are 2-diphenylphosphinoanisole (PPh2An) complexes of Rh and Ir. Part 2 describes the proof of concept as applied to the hydrogenation of styrene, including mechanistic investigations. The rhodium catalysts were developed from Rh2Cl2(C2H4)4, which was converted to Rh2Cl2(C2H4)2(κ1-PPh2An)2 and RhCl(κ1-PPh2An)(κ2-PPh2An). This charge-neutral chloride is a precursor to [Rh(κ2-PPh2An)2]BArF4 and the precatalyst [RhCl2(κ2-PPh2An)2]BArF4. The iridium catalysts were developed from Ir2Cl2(coe)4, which reacts with PPh2An to give IrClH(κ2-PPh2C6H4OCH2)(κ2-PPh2An). This cyclometalated complex behaves equivalently to IrCl(PPh2An)2. IrClH(κ2-PPh2C6H4OCH2)(κ2-PPh2An) readily reacts with H2 to form IrClH2(κ1-PPh2An)(κ2-PPh2An), which is a viable precursor to the off-state catalyst [IrCl2(κ2-PPh2An)2]BArF4. In part 2, we demonstrate that the complexes [MCl2(κ2-PPh2An)2]BArF4 (M = Rh, Ir) are inactive for styrene hydrogenation, in contrast with the other M-PAn compounds. Especially in the case of Rh, the hydrogenation is well controlled by the addition of selected reagents. Details of oxidative addition/reductive activation (OA/RA) are elucidated using cyclic voltammetry and stoichiometric chemical redox experiments.

Synthesis and physical property studies of cyclometalated Pt(II) and Pd(II) complexes with tridentate ligands containing pyrazole and pyridine groups

Novel substituted tridentate ligands, which contains a series of pyrazole and pyridine groups as donors, and their cyclometalated complexes have been successfully synthesized. The ligands and complexes were completely characterized by a variety of techniques, such as 1H NMR, UV–Vis, FT-IR, mass spectrometry and elemental analysis. Meanwhile, the single crystal structures of ligand 7 and complex 11 were determined by X-ray crystallography. For ligand 7, due to the effect of delocalization, the C(6)-C(7) bond length in the pyrazole ring is 0.05 Å shorter than a normal C-C bond. After coordinating with the metal centre, the configuration was limited by the coordination sphere, so the bond lengths and bond angles of complex 11 are different from those of ligand 7. Through photoluminescence in acetonitrile solution at ambient temperature, two emission bands have been found between 500 and 600 nm for complexes 9 and 10. Moreover, there are several absorbing bands respectively located at 240 to 250 nm and 300 to 310 nm for ligands 7 and 8 (π(L) → π*(L) and n → π*(L)). A red-shift was observed in the UV spectra, on comparing the complexes with electron-donating and electron-withdrawing groups on the ligand, which is due to the electronic effect of the substituent. One absorbing band is also found at 375 to 425 nm for complexes 9 and 10, and this band is attributed to a MLCT (dπ(Pt) → π*(L)).

Stereoselective Formation of Facial Tris-Cyclometalated PtIV Complexes: Dual Phosphorescence from Heteroleptic Derivatives.

A stereoselective synthetic route to homo- and heteroleptic facial tris-cyclometalated PtIV complexes is reported, involving the oxidative addition of 2-(2-pyridyl)- or 2-(1-isoquinolinyl)benzenediazonium salts to cis-[Pt(C^N)2 ] precursors, with C^N=cyclometalated 2-(p-tolyl)pyridine (tpy), 2-phenylquinoline (pq), 2-(2-thienyl)pyridine or 1-phenylisoquinoline (piq), to produce labile diazenide intermediates that undergo photochemical or thermal elimination of N2 . The method allows the preparation of derivatives bearing cyclometalated ligands of low π-π* transition energies. The new complexes exhibit phosphorescence in fluid solution at room temperature arising from triplet ligand-centered (3 LC) excited states, which, in the cases of the heteroleptic derivatives, involve the ligand with the lowest π-π* gap. The heteroleptic piq derivatives exhibit fluorescence and dual phosphorescence from different ligand-centered excited states in rigid media, demonstrating the potential of cyclometalated PtIV complexes as multi-emissive materials.