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In this work, we report the syntheses of three Pt(II) emitters, namely, Pt4N1, Pt4N2, and Pt4N3, to which their tetradentate chelates were assembled by linking two pyrazolate chelates with a single xylenylamino entity. Functionalization of Pt4N1 was achieved upon addition of electronegative CF3 substituent on pyridinyl groups and switching to more electron deficient pyrazinyl groups in giving Pt4N2 and Pt4N3, respectively. The vertical arranged xylenylamino entity has effectively suppressed the inter-molecular π-π stacking and Pt···Pt interaction, as shown by the single crystal X-ray structural analyses. Upon fabrication of OLED devices, Pt4N2 and Pt4N3 based devices delivered efficient cyan and green emission, with an EQEmax of 15.2% and 11.2%, respectively, affirming the successfulness of the tetradentate chelating strategy., (© 2024 Wiley‐VCH GmbH.)

Ir(III) carbene complexes have been explored as one of the best blue phosphors for their high performance. Herein, the authors designed and synthesized a series of blue-emitting Ir(III) phosphors (f-ct9a-c), featuring fac-coordinated cyano-imidazo[4,5-b]pyridin-2-ylidene cyclometalates. These Ir(III) complexes exhibit true-blue emission with a peak maximum spanning 448-467 nm, with high photoluminescence quantum yields of 81-88% recorded in degassed toluene. Moreover, OLED devices bearing phosphors f-ct9a and f-ct9b deliver maximum external quantum efficiencies (EQE max ) of 25.9% and 30.3%, together with Commission Internationale de L'Eclairage (CIE x,y ) coordinates of (0.157, 0.225) and (0.142, 0.169), respectively. Remarkably, the f-ct9b-based device displays an incredible EQE of 29.0% at 5000 cd·m -2 . The hyper-OLED device based on f-ct9b and ν-DABNA exhibits an EQE max of 34.7% and CIE x,y coordinates of (0.122, 0.131), affirming high potentials in achieving efficient blue electroluminescence., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

Efficient blue phosphors remain a formidable challenge for organic light-emitting diodes (OLEDs). To circumvent this obstacle, a series of Ir(III)-based carbene complexes bearing asymmetric di-N-aryl 6-(trifluoromethyl)-2H-imidazo[4,5-b]pyridin-2-ylidene chelates, namely, f-ct6a‒c, are synthesized, and their structures and photophysical properties are comprehensively investigated. Moreover, these emitters can undergo interconversion in refluxing 1,2,4-trichlorobenzene, catalyzed by a mixture of sodium acetate (NaOAc) and p-toluenesulfonic acid monohydrate (TsOH·H 2 O) without decomposition. All Ir(III) complexes present good photoluminescence quantum yield (Φ PL = 83-88%) with peak maximum (max.) at 443-452 nm and narrowed full width at half maximum (FWHM = 66-73 nm). Among all the fabricated OLED devices, f-ct6b delivers a max. external quantum efficiency (EQE) of 23.4% and Commission Internationale de L'Eclairage CIE x , y coordinates of (0.14, 0.12), whereas the hyper-OLED device based on f-ct6a and 5H,9H,11H,15H-[1,4] benzazaborino [2,3,4-kl][1,4]benzazaborino[4',3',2':4,5][1,4]benzazaborino[3,2-b]phenazaborine-7,13-diamine, N7,N7,N13,N13,5,9,11,15-octaphenyl (ν-DABNA) exhibits max. EQE of 26.2% and CIE x , y of (0.12, 0.13). Finally, the corresponding tandem OLED with f-ct6b as dopant gives a max. luminance of over 10 000 cd m -2 and max. EQE of 42.1%, confirming their candidacies for making true-blue OLEDs., (© 2023 Wiley‐VCH GmbH.)

Systematic investigations on the reactions between cis-[M(dppm) 2 Cl 2 ] (M=Ru/Os; dppm=1,1-bis(diphenylphosphino)methane) and pyridine/quinoline substituted homopropargylic alcohols uncovered the diverse Ru(II)/Os(II)-induced alkyne activation pathways. The alkynes underwent cyclization on M via a "non-vinylidene" pathway at lower temperatures, resulting in alkenyl intermediates which might further metallacyclize to give metallapyrroloindolizines. Conversely, reactions at higher temperatures induced alkyne cyclization on M via a "vinylidene" pathway, affording cyclic oxacarbene complexes. Additionally, a rare decyclization mechanism was observed during the transformation of a metallacyclization-resistant alkenyl complex into a cyclic oxacarbene complex. DFT calculations were employed to validate the experimental findings. Overall, these results not only provide insights into controlling alkyne activation pathways, but also offer new strategies for preparing metalated heterocyclic and metallacyclic complexes., (© 2023 Wiley-VCH GmbH.)

Although multitargeted Pt IV anticancer prodrugs have shown significant activities in reducing drug resistance, the types of bioactive ligands and drugs that can be conjugated to the Pt center remain limited to O-donors. Herein, we report the synthesis of Pt IV complexes bearing axial pyridines via ligand exchange reactions. Unexpectedly, the axial pyridines are quickly released after reduction, indicating their potential to be utilized as axial leaving groups. We further expand our synthetic approach to obtaining two multitargeted Pt IV prodrugs containing bioactive pyridinyl ligands: a PARP inhibitor and an EGFR tyrosine kinase inhibitor; these conjugates exhibit great potential for overcoming drug resistance, and the latter conjugate inhibits the growth of Pt-resistant tumor in vivo. This research adds to the array of synthetic methods for accessing Pt IV prodrugs and significantly increases the types of bioactive axial ligands that can be conjugated to a Pt IV center., (© 2023 Wiley-VCH GmbH.)

Upon fusing the pyrazinyl pyrazole entity in giving pyrazolo[3,4-f]quinoxaline chelate, the corresponding Os(II) based NIR emitter exhibited "invisible" and efficient electroluminescence with a peak maximum at 811 nm. A maximum external quantum efficiency of 0.97 % and a suppressed efficiency roll-off till a current density of 300 mA cm -2 was also exhibited., (© 2021 Wiley-VCH GmbH.)

Delicately designed dopant-free hole-transporting materials (HTMs) with ordered structure have become one of the major strategies to achieve high-performance perovskite solar cells (PSCs). In this work, we report two donor-π linker-donor (D-π-D) HTMs, N01 and N02, which consist of facilely synthesized 4,8-di(n-hexyloxy)-benzo[1,2-b:4,5-b']dithiophene as a π linker, with 10-bromohexyl-10H-phenoxazine and 10-hexyl-10H-phenoxazine as donors, respectively. The N01 molecules form a two-dimensional conjugated network governed by C-H⋅⋅⋅O and C-H⋅⋅⋅Br interaction between phenoxazine donors, and synchronously construct a three-dimension lamellar structure with the aid of interlaminar π-π interaction. Consequently, N01 as a dopant-free small-molecule HTM exhibits a higher intrinsic hole mobility and more favorable interfacial properties for hole transport, hole extraction and perovskite growth, enabling an inverted PSC to achieve a very impressive power conversion efficiency of 21.85 %., (© 2021 Wiley-VCH GmbH.)

The synthesis and X-ray structure of a new manganese(V) mesitylimido complex with a tetraamido macrocyclic ligand (TAML), [Mn V (TAML)(N-Mes)] - (1), are reported. Compound 1 is oxidized by [(p-BrC 6 H 4 ) 3 N] +. [SbCl 6 ] - and the resulting Mn VI species readily undergoes H-atom transfer and nitrene transfer reactions., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Metallafuran complexes with a fused five-membered phosphonium ring were synthesized from reactions between terminal ynones HC≡C(C=O)R and cis-[Ru/Os(dppm) 2 Cl 2 ] (dppm=1,1-bis(diphenylphosphino)methane). A metal-vinylidene-involving pathway was found to be an energetically feasible formation mechanism for these complexes. These phosphonium-containing metallafurans, like many phosphonium-functionalized drugs, have the ability to induce mitochondrial dysfunction. They also exhibit stronger cytotoxicity against several human cancer cell lines in comparison with their metal precursors and the classic anticancer drug cisplatin. Overall, this work provides structural and mechanistic insights for the rational design of functional metallacycles via activation of alkynes by Ru II and Os II centers., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The Os VI nitrido complex, Os VI (N)(quin) 2 (OTs) (1, quin=2-quinaldinate, OTs=tosylate), is a highly selective and efficient catalyst for the ring hydroxylation of alkylbenzenes with H 2 O 2 at room temperature. Oxidation of various alkylbenzenes occurs with ring/chain oxidation ratios ranging from 96.7/3.3 to 99.9/0.1, and total product yields from 93 % to 98 %. Moreover, turnover numbers up to 6360, 5670, and 3880 can be achieved for the oxidation of p-xylene, ethylbenzene, and mesitylene, respectively. Density functional theory calculations suggest that the active intermediate is an Os VIII nitrido oxo species., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Seven-coordinate ruthenium oxo species have been proposed as active intermediates in catalytic water oxidation by a number of highly active ruthenium catalysts, however such species have yet to be isolated. Reported herein is the first example of a seven-coordinate group 8 metal-oxo species, [Os(V)(O)(qpy)(pic)Cl](2+) (qpy = 2,2':6',2'':6'',2'''-quaterpyridine, pic = 4-picoline). The X-ray crystal structure of this complex shows that it has a distorted pentagonal bipyramidal geometry with an Os=O distance of 1.7375 Å. This oxo species undergoes facile O-atom and H-atom-transfer reactions with various organic substrates. Notably it can abstract H atoms from alkylaromatics with C-H bond dissociation energy as high as 90 kcal mol(-1). This work suggests that highly active oxidants may be designed based on group 8 seven-coordinate metal oxo species., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A new series of neutral isocyanoborato rhenium(I) diimine complexes [Re(CO)3 (N^N)(CNBR3 )], where N^N=bpy, 4,4'-Me2 bpy, phen, 4,7-Me2 phen, 2,9-Me2 phen, 3,4,7,8-Me4 phen; R=C6 F5 , C6 H5 , Cl, 4-ClC6 H4 , 3,5-(CF3 )2 C6 H3 , with various isocyanoborate and diimine ligands of diverse electronic and steric nature have been synthesized and characterized. The X-ray crystal structures of six complexes have also been determined. These complexes displayed intense bluish green to yellow phosphorescence at room temperature in dichloromethane solution. The photophysical and electrochemical properties of these complexes had been investigated. To elucidate the electronic structures and transitions of these complexes, DFT and TD-DFT calculations have been performed, which revealed that the lowest-energy electronic transition associated with these complexes originates from a mixture of MLCT [dπ(Re)→π*(N^N)] and LLCT [π(CNBR3 )→π*(N^N)] transitions., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Polypyridyl and related ligands have been widely used for the development of water oxidation catalysts. Supposedly these ligands are oxidation-resistant and can stabilize high-oxidation-state intermediates. In this work a series of ruthenium(II) complexes [Ru(qpy)(L)2 ](2+) (qpy=2,2':6',2'':6'',2'''-quaterpyridine; L=substituted pyridine) have been synthesized and found to catalyze Ce(IV) -driven water oxidation, with turnover numbers of up to 2100. However, these ruthenium complexes are found to function only as precatalysts; first, they have to be oxidized to the qpy-N,N'''-dioxide (ONNO) complexes [Ru(ONNO)(L)2 ](3+) which are the real catalysts for water oxidation., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Exploring new reactivity of metal nitrides is of great interest because it can give insights to N2 fixation chemistry and provide new methods for nitrogenation of organic substrates. In this work, reaction of a (salen)ruthenium(VI) nitrido complex with various alkynes results in the formation of novel (salen)ruthenium(III) imine complexes. Kinetic and computational studies suggest that the reactions go through an initial ruthenium(IV) aziro intermediate, followed by addition of nucleophiles to give the (salen)ruthenium(III) imine complexes. These unprecedented reactions provide a new pathway for nitrogenation of alkynes based on a metal nitride., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

To improve the emission and excited-state properties of luminescent cyanometalates, new classes of highly solvatochromic luminescent cyanoruthenium(II) and cyanoruthenate(II) complexes of the general formulae [Ru(PR3)2(CN)2(NN)] and K[Ru(PR3)(CN)3(NN)], respectively, were developed. These complexes could be readily synthesized through the ligand-substitution reaction of K2[Ru(CN)4(PR3)2] with a diimine ligand. The geometrical isomerism of these complexes was characterized by using various spectroscopic techniques. Their photophysical properties, solvatochromism, and electrochemistry have also been investigated. Our detailed study showed that many of these complexes exhibited extremely environmentally sensitive emissions and significantly improved emission quantum efficiencies and lifetimes compared with the well-studied tetracyanoruthenate systems., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The development of molecular frameworks derived from binuclear platinum(II) aromatic Schiff base (salphen) complexes and their supramolecular chemistry have been undertaken. A series of axially rotating (Pt-salphen)2 luminophores, tethered in a cofacial manner by a rigid linker (xanthene, 1; dibenzofuran, 2; biphenylene, 3), was synthesized in which the O(salphen) groups are potentially amenable for guest-binding. The molecular structures of 1 and 3 have been determined by X-ray crystallography, revealing intra- and intermolecular π-stacking interactions, as well as contrasting syn (1) and anti (3) configurations, for the (Pt-salphen)2 moiety. All complexes are luminescent in solution at room temperature. Their photophysical and solvatochromic properties have been examined, and the emissions are assigned to mixed triplet O(p)/Pt(d)→π*(diimine) excited states. The red-shifted fluid emissions and lower quantum yields of 1 and 3, relative to 2, are ascribed to enhanced intramolecular π-stacking interactions. Photophysical changes and selective responses to metal ions (particularly Pb(2+)) have been investigated by using various spectroscopic methods and DFT calculations, and through comparative studies with control complexes. A plausible binding mechanism is proposed based on occupation of the O(salphen)-binding cavity, which induces perturbation of intramolecular π-π interactions, and hence the self-quenching and emission properties, of the (Pt-salphen)2 unit., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Kinetic and mechanistic studies on the intermolecular activation of strong C-H bonds of alkanes by a (salen)ruthenium(VI) nitride were performed. The initial, rate-limiting step, the hydrogen atom transfer (HAT) from the alkane to Ru(VI)≡N, generates Ru(V)=NH and RC·HCH(2)R. The following steps involve N-rebound and desaturation., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Reaction of [Os(VI)(N)(L(1))(Cl)(OH(2))] (1) with CN(-) under various conditions affords (PPh(4))[Os(VI)(N)(L(1))(CN)(Cl)] (2), (PPh(4))(2)[Os(VI)(N)(L(2))(CN)(2)] (3), and a novel hydrogen cyanamido complex, (PPh(4))(2)[Os(III){N(H)CN}(L(3))(CN)(3)] (4). Compound 4 reacts readily with both electrophiles and nucleophiles. Protonation and methylation of 4 produce (PPh(4))[Os(III)(NCNH(2))(L(3))(CN)(3)] (5) and (PPh(4))[Os(III)(NCNMe(2))(L(3))(CN)(3)] (6), respectively. Nucleophilic addition of NH(3), ethylamine, and diethylamine readily occur at the C atom of the hydrogen cyanamide ligand of 4 to produce osmium guanidine complexes with the general formula [Os(III){N(H)C(NH(2))NR(1)R(2)}(L(3))(CN)(3)](-) , which have been isolated as PPh(4) salts (R(1) = R(2) = H (7); R(1) = H, R(2) = CH(2)CH(3) (8); R(1) = R(2) = CH(2)CH(3) (9)). The molecular structures of 1-5 and 7 and 8 have been determined by X-ray crystallography., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A new class of readily tunable isocyano rhenium(I) diimine luminophores, cis,cis-[Re(CO)(2)(CNR)(2)(N-N)](+) (R=2,4,6-Cl(3)C(6)H(2), 4-ClC(6)H(4), 4-Br-2,6-(CH(3))(2)C(6)H(2), 2,6-(CH(3))(2)C(6)H(3), 4-[(CH(3))(2)N]C(6)H(4), 4-(C(6)H(5))C(6)H(4), 4-nBuC(6)H(4), tBu), has been synthesized in high yield by a highly selective photochemical substitution reaction. These complexes were characterized by (1)H NMR and IR spectroscopy, mass spectrometry, and elemental analysis. The X-ray crystal structures of one of the complexes and one of the precursor complexes for the photosubstitution reaction were also determined. As the isocyanide ligands are readily tunable, complexes with excellent solubility in benzene or other nonpolar solvents could be designed through slight modification of the isocyanide ligands with a short nBu substituent. With the characteristic strong infrared absorptions of the carbonyl (C≡O) and isocyanide (C≡N) stretches as well as the high solubility of the reactant and product in benzene, which is the solvent for the photoreaction, the photosubstitution reaction of [Re(CO)(3)(nBuC(6)H(4)NC)(2)Br] with 4,4'-di-tert-butyl-2,2'-bipyridine was also studied by in situ IR spectroscopy. The photophysical and electrochemical properties of these complexes were also investigated. Except for the complex with [(CH(3))(2)N]C(6)H(4)NC ligands, all complexes displayed intense luminescence with quantum yields of up to 0.37 in degassed CH(2)Cl(2) solution at room temperature. These emissions were assigned as the phosphorescence derived from the metal-to-ligand charge transfer [dπ(Re)→π*(N-N)] excited state. The emissive excited states of these complexes have also been characterized by transient absorption spectroscopic studies. The capability of tuning the emissive excited-state energy through the modification of the isocyanide ligands could be reflected by the significant shifting of the phosphorescence from 530 to 620 nm with the same phenanthroline ligand.