The synthesis,structure and luminescent property of a tetranuclear gold（Ⅰ）complex with doubly bridging diethyldithiocarbamate（Et2dtc）and 1,1-bis（diphenylphosphino）ethene（（Ph2P）2C=CH2）are described.The compl...The synthesis,structure and luminescent property of a tetranuclear gold（Ⅰ）complex with doubly bridging diethyldithiocarbamate（Et2dtc）and 1,1-bis（diphenylphosphino）ethene（（Ph2P）2C=CH2）are described.The complex crystallizes in monoclinic space group C2/c with a=26.785（7）,b=25.654（6）,c=12.277（3）A,β=106.879（5）°,V=8073（4）A^3,Z=8,C31H32Au2F6NO3P2S2Sb,Mr=1222.32,Dc=2.011 g/cm^3,F（000）=4592,Rint=0.0529,T=293（2）K,μ=8.157 mm^（-1）,the final R=0.0464 and wR=0.1444 for 5804 observed reflections with I〉2σ（Ⅰ）.The intramolecular and intermolecular Au¨Au distances are 2.8670（9）and 3.2367（9）A,respectively.Weak emission appears at 517 nm at room temperature in the solid state.展开更多
The electronic structure and electronic absorption spectra of binuclear Au(Ⅰ) complexes with bidentate phophines and a bidentate ylid ligand have been studied using quasirelativistic pseudopotential ab initio cal...The electronic structure and electronic absorption spectra of binuclear Au(Ⅰ) complexes with bidentate phophines and a bidentate ylid ligand have been studied using quasirelativistic pseudopotential ab initio calculations at the HF and MP2 levels by the LANL2DZ basis sets. The electronic properties of the spectral transition and Au(Ⅰ)—Au(Ⅰ) interaction were also discussed.展开更多
In this study,a new twisting gold（Ⅰ） isocyanide complex based on tetraphenylethene（TPE）,TPE-NC-Au.was designed and synthesized.It exhibits aggregation induced phosphorescence（AIP） characteristics,owing to the i...In this study,a new twisting gold（Ⅰ） isocyanide complex based on tetraphenylethene（TPE）,TPE-NC-Au.was designed and synthesized.It exhibits aggregation induced phosphorescence（AIP） characteristics,owing to the incorporation of Au moiety and conformation rigidification in the aggregated states.Moreover,the emission color of the crystalline solid of TPE-NC-Au changes from blue（454 nm） to green（500 nm） in response to mechanical grinding,due to the combined effects of conformation planarization,enhanced π…π stacking,as well as the emergence of aurophilic interactions in the ground amorphous state.Notably,the emission color can be restored upon solvent fuming,associating with the reconstruction of crystalline lattices.The AIP and switchable mechanochromism of TPE-NC-Au make it suitable for potential applications in bioimaging,sensing,and optoelectronic devices.展开更多
Photophysical properties of organic and organometallic luminophors are closely related with their molecular packings, enabling the exploitation of stimuli-responsive functional luminescent molecules.Mechanochromic mol...Photophysical properties of organic and organometallic luminophors are closely related with their molecular packings, enabling the exploitation of stimuli-responsive functional luminescent molecules.Mechanochromic molecules, which can change their luminescence characteristics after mechanical stimulus, have received an increasing interest due to their promising applications in multifunctional sensors and molecular switches. During the past two decades, the development of gold(Ⅰ) chemistry has been attracting the attention of plenty of researchers. Indeed, a variety of gold(I) complexes with fascinating photophysical behaviors have been discovered. This review focuses on the research progress in the different types of mechanoluminochromic gold(Ⅰ) complexes, including mono-, bi-and multi-nuclear gold(Ⅰ)systems. Their interesting luminescence behaviors of these gold(Ⅰ)-containing luminogens upon mechanical stimulus and the proposed mechanisms of their observed mechanochromic luminescence are summarized systematacially. Moreover, this review will put forward an outlook about the possible opportunities and challenges in this significative scientific field.展开更多
The crystal structures of the complexes of [Au(Et XA)(PPh3)2] (1), and [Cu(Et XA)(PPh3)2] (2), have been determined by X ray crystallography. They are isomorphous. The crystal structures are very similar and consist o...The crystal structures of the complexes of [Au(Et XA)(PPh3)2] (1), and [Cu(Et XA)(PPh3)2] (2), have been determined by X ray crystallography. They are isomorphous. The crystal structures are very similar and consist of discrete molecules of [Au(Et XA)(PPh3)2] and [Cu(Et XA)(PPh3)2], respectively. They all display distorted tetrahedral geometry around the central metal atom. In the complexes, the ethylxanthate ions act as bidentate ligands with their S atoms coordinated to metal. Each forms a four member chelate ring. The P atoms from two triphenylphosphine ligands are coordinated to the metal atom. The Au P bond lengths are 0.2295(2)nm and 0.2329(2)nm, and the Au S bond lengths are 0.2620(3)nm and 0.2846(3)nm, respectively. The Cu P and Cu S bond lengths are 0.2254(1)nm, 0.2273(2)nm, and 0.2375(1)nm, 0.2495(2)nm, respectively. Elemental analysis, electronic and IR spectra are in agreement with the structural data. CCDC: 1, 208728; 2, 208903.展开更多
The efficient harvesting of triplet excitons is crucial to the realization of high-performance organic light-emitting diodes(OLEDs).Herein,we show that coordination of donor-acceptor(D-A)type molecules to a metal atom...The efficient harvesting of triplet excitons is crucial to the realization of high-performance organic light-emitting diodes(OLEDs).Herein,we show that coordination of donor-acceptor(D-A)type molecules to a metal atom in a monodentate fashion can lead to thermally activated delayed fluorescence(TADF)emissions with wide color tunability only through varying the noncoordinating acceptor moiety.A panel of TADF gold(Ⅰ)complexes with emission maxima(λmax)of 545–645 nm from metal perturbed intraligand charge-transfer(MPICT)excited states have been developed.Synergetic effects of heavy atom-induced spin-orbit coupling(SOC),steric-induced donor-acceptor twisting and suppressed intramolecular motions lead to high emission efficiencies of 65%-85%in doped films with delayed fluorescence lifetime of as short as 2.0μs.Transient absorption spectroscopic studies on selected complexes determined the kISCto be 6.5×10^(9)s^(-1).Theoretical calculations confirmed the participation of minor d orbital into the lowest excited state,which led to an SOC value of 5.19 cm^(-1)between the lowest-lying singlet and triplet excited states.The yellow to deep red solution-processed OLEDs based on the new gold(Ⅰ)complexes incorporated with various D-A ligands demonstrated promising performances.This study validates a modular design for TADF metal complexes,which will broaden the choices of metal centers and allow for facile color tuning via simple ligand synthesis.展开更多
基金financial supports from the NNSFC(20931006,U0934003,and 91122006)the NSF of Fujian Province(2011J01065)
文摘The synthesis,structure and luminescent property of a tetranuclear gold（Ⅰ）complex with doubly bridging diethyldithiocarbamate（Et2dtc）and 1,1-bis（diphenylphosphino）ethene（（Ph2P）2C=CH2）are described.The complex crystallizes in monoclinic space group C2/c with a=26.785（7）,b=25.654（6）,c=12.277（3）A,β=106.879（5）°,V=8073（4）A^3,Z=8,C31H32Au2F6NO3P2S2Sb,Mr=1222.32,Dc=2.011 g/cm^3,F（000）=4592,Rint=0.0529,T=293（2）K,μ=8.157 mm^（-1）,the final R=0.0464 and wR=0.1444 for 5804 observed reflections with I〉2σ（Ⅰ）.The intramolecular and intermolecular Au¨Au distances are 2.8670（9）and 3.2367（9）A,respectively.Weak emission appears at 517 nm at room temperature in the solid state.
文摘The electronic structure and electronic absorption spectra of binuclear Au(Ⅰ) complexes with bidentate phophines and a bidentate ylid ligand have been studied using quasirelativistic pseudopotential ab initio calculations at the HF and MP2 levels by the LANL2DZ basis sets. The electronic properties of the spectral transition and Au(Ⅰ)—Au(Ⅰ) interaction were also discussed.
基金financially supported by the National Natural Science Foundation of China(No.51473092)the Shanghai Rising-Star Program(No.15QA1402500)
文摘In this study,a new twisting gold（Ⅰ） isocyanide complex based on tetraphenylethene（TPE）,TPE-NC-Au.was designed and synthesized.It exhibits aggregation induced phosphorescence（AIP） characteristics,owing to the incorporation of Au moiety and conformation rigidification in the aggregated states.Moreover,the emission color of the crystalline solid of TPE-NC-Au changes from blue（454 nm） to green（500 nm） in response to mechanical grinding,due to the combined effects of conformation planarization,enhanced π…π stacking,as well as the emergence of aurophilic interactions in the ground amorphous state.Notably,the emission color can be restored upon solvent fuming,associating with the reconstruction of crystalline lattices.The AIP and switchable mechanochromism of TPE-NC-Au make it suitable for potential applications in bioimaging,sensing,and optoelectronic devices.
基金financial support from the National Natural Science Foundation of China (Nos. 22061018, 21702079 and 21772054)the startup funding from South-Central University for Nationalities (No. YZZ19005)。
文摘Photophysical properties of organic and organometallic luminophors are closely related with their molecular packings, enabling the exploitation of stimuli-responsive functional luminescent molecules.Mechanochromic molecules, which can change their luminescence characteristics after mechanical stimulus, have received an increasing interest due to their promising applications in multifunctional sensors and molecular switches. During the past two decades, the development of gold(Ⅰ) chemistry has been attracting the attention of plenty of researchers. Indeed, a variety of gold(I) complexes with fascinating photophysical behaviors have been discovered. This review focuses on the research progress in the different types of mechanoluminochromic gold(Ⅰ) complexes, including mono-, bi-and multi-nuclear gold(Ⅰ)systems. Their interesting luminescence behaviors of these gold(Ⅰ)-containing luminogens upon mechanical stimulus and the proposed mechanisms of their observed mechanochromic luminescence are summarized systematacially. Moreover, this review will put forward an outlook about the possible opportunities and challenges in this significative scientific field.
文摘The crystal structures of the complexes of [Au(Et XA)(PPh3)2] (1), and [Cu(Et XA)(PPh3)2] (2), have been determined by X ray crystallography. They are isomorphous. The crystal structures are very similar and consist of discrete molecules of [Au(Et XA)(PPh3)2] and [Cu(Et XA)(PPh3)2], respectively. They all display distorted tetrahedral geometry around the central metal atom. In the complexes, the ethylxanthate ions act as bidentate ligands with their S atoms coordinated to metal. Each forms a four member chelate ring. The P atoms from two triphenylphosphine ligands are coordinated to the metal atom. The Au P bond lengths are 0.2295(2)nm and 0.2329(2)nm, and the Au S bond lengths are 0.2620(3)nm and 0.2846(3)nm, respectively. The Cu P and Cu S bond lengths are 0.2254(1)nm, 0.2273(2)nm, and 0.2375(1)nm, 0.2495(2)nm, respectively. Elemental analysis, electronic and IR spectra are in agreement with the structural data. CCDC: 1, 208728; 2, 208903.
基金supported by the National Natural Science Foundation of China(22322505,22271196,22301226)the Shenzhen Science and Technology Program(ZDSYS20210623091813040)support from the Department of Science and Technology of Guangdong Province(2019QN01C617)。
文摘The efficient harvesting of triplet excitons is crucial to the realization of high-performance organic light-emitting diodes(OLEDs).Herein,we show that coordination of donor-acceptor(D-A)type molecules to a metal atom in a monodentate fashion can lead to thermally activated delayed fluorescence(TADF)emissions with wide color tunability only through varying the noncoordinating acceptor moiety.A panel of TADF gold(Ⅰ)complexes with emission maxima(λmax)of 545–645 nm from metal perturbed intraligand charge-transfer(MPICT)excited states have been developed.Synergetic effects of heavy atom-induced spin-orbit coupling(SOC),steric-induced donor-acceptor twisting and suppressed intramolecular motions lead to high emission efficiencies of 65%-85%in doped films with delayed fluorescence lifetime of as short as 2.0μs.Transient absorption spectroscopic studies on selected complexes determined the kISCto be 6.5×10^(9)s^(-1).Theoretical calculations confirmed the participation of minor d orbital into the lowest excited state,which led to an SOC value of 5.19 cm^(-1)between the lowest-lying singlet and triplet excited states.The yellow to deep red solution-processed OLEDs based on the new gold(Ⅰ)complexes incorporated with various D-A ligands demonstrated promising performances.This study validates a modular design for TADF metal complexes,which will broaden the choices of metal centers and allow for facile color tuning via simple ligand synthesis.
