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1.
Sergej Stipurin Prof. Dr. Thomas Strassner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202202227
A series of phosphorescent bimetallic platinum(II) complexes is presented, which were synthesized by the combination of bidentate cyclometalated N-heterocyclic carbene ligands and different bridging diphenylformamidinates. The complexes were characterized by standard techniques and additionally two solid-state structures could be obtained. Photoluminescence measurements revealed the strong emissive behavior of the compounds with quantum yields of up to 90 % and emission lifetimes of approx. 2 μs. The effect of the substitution pattern in the bridging ligands on the structural and photophysical properties of the complexes was examined in detail and rationalized by density functional theory calculations (PBE0/6-311G*). 相似文献
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Johannes Soellner Mario Tenne Dr. Gerhard Wagenblast Prof. Dr. Thomas Strassner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):9914-9918
The synthesis and characterization of eight unprecedented phosphorescent C^C* cyclometalated mesoionic aryl‐1,2,3‐triazolylidene platinum(II) complexes with different β‐diketonate ligands are reported. All compounds proved to be strongly emissive at room temperature in poly(methyl methacrylate) films with an emitter concentration of 2 wt %. The observed photoluminescence properties were strongly dependent on the substitution on the aryl system and the β‐diketonate ligand. Compared to acetylacetonate, the β‐diketonates with aromatic substituents (mesityl and duryl) were found to significantly enhance the quantum yield while simultaneously reducing the emission lifetimes. Characterization was carried out by standard techniques, as well as solid‐state structure determination, which confirmed the binding mode of the carbene ligand. DFT calculations, carried out to predict the emission wavelength with maximum intensity, were in excellent agreement with the (later) obtained experimental data. 相似文献
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Dr. Ángela Vivancos Dr. Delia Bautista Dr. Pablo González-Herrero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(23):6014-6025
The synthesis, structure, and photophysical properties of luminescent PtIV complexes that combine cyclometalated 1,2,3-triazolylidene and bi- or terdentate 2,6-diarylpyridine ligands are reported. The targeted complexes represent the first examples of PtIV species with a cyclometalated mesoionic aryl-NHC ligand. They exhibit moderate or weak emissions in fluid solution at 298 K arising from 3LC states, which become very intense in poly(methyl methacrylate) (PMMA) matrices at 298 K. DFT and TD-DFT calculations confirm that the chromophoric ligand is the cyclometalated 2,6-diarylpyridine and show that the aryl-NHC ligand exerts a beneficial effect on the emission efficiencies of these derivatives by increasing the energy of deactivating LMCT excited states with respect to comparable PtIV complexes with cyclometalated 2-arylpyridine ligands. 相似文献
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Phosphorescent Platinum(II) Complexes with C^C* Cyclometalated NHC Dibenzofuranyl Ligands: Impact of Different Binding Modes on the Decay Time of the Excited State 下载免费PDF全文
Dr. Alexander Tronnier Dr. Gerhard Wagenblast Dr. Ingo Münster Prof. Dr. Thomas Strassner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(37):12881-12884
Two C^C* cyclometalated platinum(II) N‐heterocyclic carbene (NHC) complexes with the general formula [(C^C*)Pt(O^O)] (C^C*=1‐dibenzofuranyl‐3‐methylbenzimidazolylidene; O^O=dimesitoylmethane) have been synthesized and extensively characterized, including solid‐state structure determination, 195Pt NMR spectroscopy, and 2D NMR (COSY, HSQC, HMBC, NOESY) spectroscopy to elucidate the impact of their structural differences. The two regioisomers differ in the way the dibenzofuranyl (DBF) moiety of the NHC ligand is bound to the metal center, which induces significant changes in their physicochemical properties, especially on the decay time of the excited state. Quantum yields of over 80 % and blue emission colors were measured. 相似文献
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Pincer‐Type Platinum(II) Complexes Containing N‐Heterocyclic Carbene (NHC) Ligand: Structures,Photophysical and Anion‐Binding Properties,and Anticancer Activities 下载免费PDF全文
Dr. Kai Li Dr. Taotao Zou Prof. Dr. Yong Chen Dr. Xiangguo Guan Prof. Dr. Chi‐Ming Che 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(20):7441-7453
Two classes of pincer‐type PtII complexes containing tridentate N‐donor ligands ( 1 – 8 ) or C‐deprotonated N^C^N ligands derived from 1,3‐di(2‐pyridyl)benzene ( 10 – 13 ) and auxiliary N‐heterocyclic carbene (NHC) ligand were synthesized. [Pt(trpy)(NHC)]2+ complexes 1 – 5 display green phosphorescence in CH2Cl2 (Φ: 1.1–5.3 %; τ: 0.3–1.0 μs) at room temperature. Moderate‐to‐intense emissions are observed for 1 – 7 in glassy solutions at 77 K and for 1 – 6 in the solid state. The [Pt(N^C^N)(NHC)]+ complexes 10 – 13 display strong green phosphorescence with quantum yields up to 65 % in CHCl3. The reactions of 1 with a wide variety of anions were examined in various solvents. The tridentate N‐donor ligand of 1 undergoes displacement reaction with CN? in protic solvents. Similar displacement of the N^C^N ligand by CN? has been observed for 10 , leading to a luminescence “switch‐off” response. The water‐soluble 7 containing anthracenyl‐functionalized NHC ligand acts as a light “switch‐on” sensor for the detection of CN? ion with high selectivity. The in vitro cytotoxicity of the PtII complexes towards HeLa cells has been evaluated. Complex 12 showed high cytotoxicity with IC50 value of 0.46 μM , whereas 1 – 4 and 6 – 8 are less cytotoxic. The cellular localization of the strongly luminescent complex 12 traced by using emission microscopy revealed that it mainly localizes in the cytoplasmic structures rather than in the nucleus. This complex can induce mitochondria dysfunction and subsequent cell death. 相似文献
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Dr. Jia Wang Dr. Yong Chen Dr. Yuen‐Chi Law Meiyi Li Dr. Ming‐Xin Zhu Dr. Wei Lu Dr. Stephen Sin‐Yin Chui Dr. Nianyong Zhu Prof. Dr. Chi‐Ming Che 《化学:亚洲杂志》2011,6(11):3011-3019
A series of phosphorescent terpyridyl platinum(II) complexes with ancillary biphenylacetylide ligands, namely, [(R3tpy)PtC≡C(biphenyl)]X (R=tBu, H, or Et2N; tpy=2,2′;6′,2′′‐terpyridyl; X is an anion) were synthesized and structurally characterized by various spectroscopic techniques and X‐ray diffraction methods. Despite a lack of long alkyl chain(s) or hydrogen‐bonding motif(s), complexes [(tpy)PtC≡C(biphenyl)]Cl and [(tBu3tpy)PtC≡C(biphenyl)]X (X=Cl, ClO4, PF6, or BF4) were found to gelate water and organic solvents, respectively. The self‐aggregation of these complexes in solutions and the resulting gels were investigated with variable‐temperature (VT) 1H NMR spectroscopy, polarized optical microscopy, and absorption/emission spectroscopy. SEM micrographs on dry gels revealed entangled nanofibers with diameters of 20–40 nm and lengths of tens of micrometers. Powder X‐ray diffraction (PXRD) study revealed various degrees of crystallinity of these fibrillar nanostructures. The substituents on both the terpyridyl and acetylide ligands and counterion of these complexes play a profound but concerted role in tuning the intermolecular metal???metal and/or π–π interactions, and hence the gelation properties. 相似文献
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Zaoli Luo Dr. Yungen Liu Dr. Ka-Chung Tong Dr. Xiao-Yong Chang Dr. Wai-Pong To Prof. Dr. Chi-Ming Che 《化学:亚洲杂志》2021,16(19):2978-2992
A series of platinum(II) complexes supported by terphenyl diacetylide as well as diimine or bis-N-heterocyclic carbene (NHC) ligands have been prepared. The diacetylide ligands adopt a cis coordination mode featuring non-planar terphenyl moieties as revealed by X-ray crystallographic analyses. The electrochemical, photophysical and photochemical properties of these platinum(II) complexes have been investigated. These platinum(II) diimine complexes show broad emission with peak maxima from 566 nm to 706 nm, with two of them having emission quantum yields >60% and lifetimes <2 μs in solutions at room temperature, whereas the platinum(II) diacetylide complexes having bis-N-heterocyclic carbene instead of diimine ligand display photoluminescence with quantum yields of up to 28% in solutions and excited state lifetimes of up to 62 μs at room temperature. Application studies revealed that one of the complexes can catalyze photoinduced aerobic dehydrogenation of alcohols and alkenes, and a relatively non-toxic water-soluble Pt(II) complex displays anti-angiogenic activity. 相似文献
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Bimetallic Cyclometalated Iridium(III) Diastereomers with Non‐Innocent Bridging Ligands for High‐Efficiency Phosphorescent OLEDs 下载免费PDF全文
Dr. Yonghao Zheng Dr. Andrei S. Batsanov Dr. Mark A. Fox Dr. Hameed A. Al‐Attar Khalid Abdullah Dr. Vygintas Jankus Prof. Martin R. Bryce Prof. Andrew P. Monkman 《Angewandte Chemie (International ed. in English)》2014,53(43):11616-11619
Two phosphorescent dinuclear iridium(III) diastereomers (ΛΔ/ΔΛ) and (ΛΛ/ΔΔ) are readily separated by making use of their different solubilities in hot hexane. The bridging diarylhydrazide ligand plays an important role in the electrochemistry and photophysics of the complexes. Organic light‐emitting devices (OLEDs) that use these complexes as the green‐emissive dopants in solution‐processable single‐active‐layer architectures feature electroluminescence efficiencies that are remarkably high for dinuclear metal complexes, achieving maximum values of 37 cd A?1, 14 lm W?1, and 11 % external quantum efficiency. 相似文献
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Robert Malmberg Dr. Tobias von Arx Monirul Hasan Dr. Olivier Blacque Atul Shukla Dr. Sarah K. M. McGregor Prof. Shih-Chun Lo Prof. Ebinazar B. Namdas Prof. Koushik Venkatesan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(25):7265-7274
N-Heterocyclic carbene (NHC) cyclometalated gold(III) complexes remain very scarce and therefore their photophysical properties remain currently underexplored. Moreover, gold(III) complexes emitting in the blue region of the electromagnetic spectrum are rare. In this work, a series of four phosphorescent gold(III) complexes was investigated bearing four different NHC monocyclometalated (C^C*)-type ligands and a dianionic (N^N)-type ancillary ligand ((N^N)=5,5’-(propane-2,2-diyl)bis(3-(trifluoromethyl)-1 H-pyrazole) (mepzH2)). The complexes exhibit strong phosphorescence when doped in poly(methyl methacrylate) (PMMA) at room temperature, which were systematically tuned from sky-blue [λPL=456 nm, CIE coordinates: (0.20, 034)] to green [λPL=516 nm, CIE coordinates: (0.31, 0.54)] by varying the monocyclometalated (C^C*) ligand framework. The complexes revealed high quantum efficiencies (ϕPL) of up to 43 % and excited-state lifetimes (τ0) between 15–266 μs. The radiative rate constant values found for these complexes (kr=103–104 s−1) are the highest found in comparison to previously known best-performing monocyclometalated gold(III) complexes. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations of these complexes further lend support to the excited-state nature of these complexes. The calculations showed a significant contribution of the gold(III) metal center in the lowest unoccupied molecular orbitals (LUMOs) of up to 18 %, which was found to be unique for this class of cyclometalated gold(III) complexes. Additionally, organic light-emitting diodes (OLEDs) were fabricated by using a solution process to provide the first insight into the electroluminescent (EL) properties of this new class of gold(III) complexes. 相似文献
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Dr. Yanyu Wu Dr. Zhili Wen Prof. Judy I-Chia Wu Prof. Thomas S. Teets 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(68):16028-16035
Here we report five blue-phosphorescent platinum bis-phenylacetylide complexes with an investigation of their photophysical and electrochemical attributes. Three of the complexes ( 1 – 3 ) are of the general formula cis-Pt(CNR)2(C≡CPh)2, in which CNR is a variably substituted isocyanide and C≡CPh is phenylacetylide. These isocyanide complexes serve as precursors for complexes of the general formula cis-Pt(CNR)(ADC)(C≡CPh)2 ( 4 and 5 ), in which ADC is an acyclic diaminocarbene installed by amine nucleophilic addition to one of the isocyanides. All of the complexes exhibit deep blue phosphorescence with λmax ∼430 nm in poly(methyl methacrylate) (PMMA) thin films. Whereas isocyanide complexes 1 – 3 exhibit modest photoluminescence quantum yields (ΦPL), incorporation of one acyclic diaminocarbene ligand results in a three-fold to 16-fold increase in ΦPL while still maintaining an identical deep blue color profile. 相似文献
13.
Felix Wurl Sergej Stipurin Joshua Immanuel Kollar Prof. Dr. Thomas Strassner 《Angewandte Chemie (International ed. in English)》2023,62(22):e202301225
A novel class of cyclometalated platinum(II) complexes—previously considered to be inaccessible—was synthesized by an improved synthetic route utilizing ligands predicted by density functional theory calculations. Based on a concise quantum chemical screening three model ligands with varying steric demand were chosen and a series of six photoluminescent C^C* cyclometalated platinum(II) formamidinate complexes was obtained. The least sterically demanding ligand led to a bimetallic complex in two isomeric forms, which could be separated and confirmed by the corresponding solid-state structures. Sterically more hindered amidinate ligands gave the monometallic complexes supporting the theoretical predictions. The monometallic complexes show a significant hypsochromic shift of the emission wavelength, explained by the loss of the metal-metal interactions. Depending on the cyclometalating ligand quantum yields up to 87 % with short decay times were found for this new class of phosphorescent green-blue to pure blue platinum(II) emitters. 相似文献
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Dr. Miguel A. Soto Dr. Veronica Carta Ryan J. Andrews Mohammad T. Chaudhry Prof. Mark. J. MacLachlan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(26):10434-10438
We report the synthesis, characterization, and spectroscopic investigations of a new responsive-at-metal cyclometalated platinum(II) complex. With mild chemical oxidants and reductants, it was possible to obtain the same complex in three different oxidation states and each of these complexes was structurally characterized by single-crystal X-ray diffraction. We discovered that the platinum(II) complex displays strong solvatochromism in the solid state, which can be attributed to modulation of Pt⋅⋅⋅Pt interactions that results in switching between optical and photoluminescent states. Incorporating responsive-at-metal species as dynamic components in nanostructured materials might facilitate response amplification, sensing, actuation, or self-healing processes. 相似文献
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Dr. Ester Rossi Dr. Alessia Colombo Dr. Claudia Dragonetti Dr. Stefania Righetto Prof. Dr. Dominique Roberto Prof. Dr. Renato Ugo Dr. Adriana Valore Prof. Dr. J. A. Gareth Williams Dr. Maria Grazia Lobello Dr. Filippo De Angelis Dr. Simona Fantacci Prof. Dr. Isabelle Ledoux‐Rak Dr. Anu Singh Prof. Dr. Joseph Zyss 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(30):9875-9883
Appropriate functionalization of the cyclometalated ligand, L , and the choice of the ancillary ligand, X, allows the dipolar second‐order nonlinear optical response of luminescent [Pt L X] complexes—in which L is an N^C^N‐coordinated 1,3‐di(2‐pyridyl)benzene ligand and X is a monodentate halide or acetylide ligand—to be controlled. The complementary use of electric‐field‐induced second‐harmonic (EFISH) generation and harmonic light scattering (HLS) measurements demonstrates how the quadratic hyperpolarizability of this appealing family of multifunctional chromophores, characterized by a good transparency throughout much of the visible region, is dominated by an octupolar contribution. 相似文献
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Alejandro Cervantes-Reyes Dr. Frank Rominger Dr. Matthias Rudolph Prof. Dr. A. Stephen K. Hashmi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(50):11745-11757
Nine- and ten-membered N-heterocyclic carbene (NHC) ligands have been developed and for the first time their gold(I) complexes were synthesized. The protonated NHC pro-ligands 2 a – h were prepared by the reaction of readily available N,N′-diarylformamidines with bis-electrophilic building blocks, followed by anion exchange. In situ deprotonation of the tetrafluoroborates 2 a – h with tBuOK in the presence of AuCl(SMe2) provided fast access to NHC-gold(I) complexes 3 – 10 . These new NHC-gold(I) complexes show very good catalytic activity in a cycloisomerization reaction (0.1 mol % catalyst loading, up to 100 % conversion) and their solid-state structures reveal high steric hindrance around the metal atom (%Vbur up to 53.0) which is caused by their expanded-ring architecture. 相似文献
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Tridentate Complexes of Palladium(II) and Platinum(II) Bearing bis‐Aryloxide Triazole Ligands: A Joint Experimental and Theoretical Investigation 下载免费PDF全文
Dr. Georges Dahm Dr. Etienne Borré Changkan Fu Dr. Stéphane Bellemin‐Laponnaz Dr. Matteo Mauro 《化学:亚洲杂志》2015,10(11):2368-2379
A novel class of palladium(II) and platinum(II) complexes bearing tridentate bis‐aryloxide triazole ligands was prepared by using straightforward and high‐yielding synthetic routes. The complexes were fully characterized and the molecular structures of four derivatives were unambigously determined by single‐crystal X‐ray diffractometric analyses. For the most promising luminescent PtII derivatives, further experimental investigations were carried out to characterize their photophysical features and to ascertain the nature of the emitting excited state by means of electronic absorption, steady‐state, and time‐resolved emission techniques in different conditions. In degassed fluid solution the complexes displayed broad and featureless photoluminescence with λem=522–585 nm, excited‐state lifetime up to few microseconds and quantum yield (PLQY) up to 17 %, depending on the nature of both ancillary ligand and substituent on the tridentate ligand. Computational investigation using density functional theory and time‐dependent DFT were performed to gain insight into the electronic processes responsible for optical transitions and structure–photoluminescence relationship. Jointly, experimental and theoretical characterization indicated that the radiative transition arises from an excited state with admixed triplet‐manifold metal‐to‐ligand charge transfer and ligand‐centered (3MLCT/3LC) character. We elucidated the modulation of the photophysical properties upon variation of substituents for this new family of complexes. 相似文献
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Youming Zhang Jingsheng Miao Jinfan Xiong Kai Li Chuluo Yang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2022,134(1):e202113718
A molecular design to high-performance red and near-infrared (NIR) organic light-emitting diodes (OLEDs) emitters remains demanding. Herein a series of dinuclear platinum(II) complexes featuring strong intramolecular Pt???Pt and π–π interactions has been developed by using N-deprotonated α-carboline as a bridging ligand. The complexes in doped thin films exhibit efficient red to NIR emission from short-lived (τ=0.9–2.1 μs) triplet metal-metal-to-ligand charge transfer (3MMLCT) excited states. Red OLEDs demonstrate high maximum external quantum efficiencies (EQEs) of up to 23.3 % among the best PtII-complex-doped devices. The maximum EQE of 15.0 % and radiance of 285 W sr?1 m?2 for NIR OLEDs (λEL=725 nm) are unprecedented for devices based on discrete molecular emitters. Both red and NIR devices show very small efficiency roll-off at high brightness. Appealing operational lifetimes have also been revealed for the devices. This work sheds light on the potential of intramolecular metallophilicity for long-wavelength molecular emitters and electroluminescence. 相似文献
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Thibault Cauwenbergh Nikolaos V. Tzouras Dr. Thomas Scattolin Dr. Subhrajyoti Bhandary Andreas Simoens Prof. Dr. Kristof Van Hecke Prof. Dr. Christian V. Stevens Prof. Dr. Steven P. Nolan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(53):13342-13345
The use of weak and inexpensive bases has recently opened promising perspectives towards the simpler and more sustainable synthesis of Au(I)-aryl complexes with valuable applications in catalysis, medicinal chemistry, and materials science. In recent years, continuous manufacturing has shown to be a reliable partner in establishing sustainable and controlled process scalability. Herein, the first continuous flow synthesis of a range of Au(I)-aryl starting from widely available boronic acids and various [Au(NHC)Cl] (NHC=N-heterocyclic carbene) complexes in unprecedentedly short reaction times and high yields is reported. Successful synthesis of previously non- or poorly accessible complexes exposed fascinating reactivity patterns. Via a gram-scale synthesis, convenient process scalability of the developed protocol was showcased. 相似文献