本文研究了(C_(60))_2-[P(O)(OCH_3)]_2富勒烯双体内的笼间C―C键的热力学性质(该双体的结构详见文献,Chem.Commun.2011,47,6111)。原位、变温电子顺磁共振波谱实验结果表明,该C―C键的键离解能(BDE)为72.4 k J?mol^(-1)(17.3 kcal?mol^...本文研究了(C_(60))_2-[P(O)(OCH_3)]_2富勒烯双体内的笼间C―C键的热力学性质(该双体的结构详见文献,Chem.Commun.2011,47,6111)。原位、变温电子顺磁共振波谱实验结果表明,该C―C键的键离解能(BDE)为72.4 k J?mol^(-1)(17.3 kcal?mol^(-1)),仅约为常见氢键的两倍,或约为常见有机C―C键的五分之一。因此,该二聚体于较高温度时容易发生均裂反应,形成单体自由基;降温时又容易发生自由基聚合反应。基于该笼间C―C键所具有的这些热力学特性,我们对其可被用于制备有序的富勒烯分子元器件等材料作展开讨论。展开更多
The formation and qualification of redox sites in transition metal oxides are always the active fields related to electronics, catalysis, sensors, and energy-storage units. In the present study, the temperature depend...The formation and qualification of redox sites in transition metal oxides are always the active fields related to electronics, catalysis, sensors, and energy-storage units. In the present study, the temperature dependence of thermal reduction of MoO3 was surveyed at the range of 350℃ to 750℃. Upon reduction, the formed redox species characterized by EPR spectroscopy are the MoVion and superoxide anion radical (O2-) when the reduction was induced at the optimal temperature of 300-350℃. When heating-up from 350℃, the EPR signals started to decline in amplitude. The signals in the range of 400-450℃ decreased to half of that at 350℃, and then to zero at ~600℃. Further treatment at even higher temperature or prolonged heating time at 500℃ caused more reduction and more free electrons were released to the MoO3 bulk, which results in a delocalized means similar to the antiferromagnetic coupling. These data herein are helpful to prepare and study the metal-oxide catalysts.展开更多
Molecular qubits are promising as they can benefit from tailoring and versatile design of chemistry.It is essential to reduce the decoherence of molecular qubits caused by their interactions with the environment.Herei...Molecular qubits are promising as they can benefit from tailoring and versatile design of chemistry.It is essential to reduce the decoherence of molecular qubits caused by their interactions with the environment.Herein the dynamical decoupling(DD)technique is utilized to combat such decoherence.The coherence time for a transitionmetal complex(PPh_(4))_(2)[Cu(mnt)_(2)]is prolonged from 6.8μs to 1.4 ms.The ratio of the coherence time and the length ofπ/2 pulse,defined as the single qubit figure of merit(QM),reaches 1.4×10^(5),which is 40 times greater than what previously reported for this molecule.Our results show that molecular qubits,with milliseconds coherence time,are promising candidates for quantum information processing.展开更多
在绿色植物的放氧光合作用过程中,每个反应周期(即S态循环)都有两个底物水分子被氧化,释放出四个质子和四个电子,并最终释放一个氧气分子,这种化学反应机制维持着地球上的各种需氧生命活动。目前,人们已经清楚地知道,这个生物催化过程...在绿色植物的放氧光合作用过程中,每个反应周期(即S态循环)都有两个底物水分子被氧化,释放出四个质子和四个电子,并最终释放一个氧气分子,这种化学反应机制维持着地球上的各种需氧生命活动。目前,人们已经清楚地知道,这个生物催化过程是由光系统Ⅱ(photosystemⅡ,PSⅡ)中一个无机簇状结构(即锰簇Mn4O5Ca)催化完成的。然而,这两个底物水分子是在此反应同期的什么时候、什么地方、以什么方式结合到锰簇上的,目前仍旧是一个谜团。在探讨此问题的很多实验研究中,人们常用脉冲电子顺磁共振(electron paramagnetic resonance,EPR)波谱学方法,探测底物水分子在反应中间氧化态S2态锰簇中的结合方式和结合位点,即依据超精细耦合常数的大小来判断未成对电子与磁性核的距离。基于此前的实验数据和文献报道,EPR理论模拟的结果显示,中间S2态锰簇上仅仅可容纳一个可发生置换的底物水,并且已经发生完全去质子化。这个结合水可能就是研究人员使用时间分辨薄膜进样质谱(membrane-inlet mass spectrometry,MIMS)检测到的强磁性耦合氧。此结果排除了源自强磁性耦合14N信号的干扰。因此,理论和实验结果均说明,另一个底物水是在锰簇由S2态氧化到更高中间态S3态的过程中结合到锰簇上的,并最终参与了O2分子的形成。展开更多
基金supported by the National Key Basic Research Program of China(973)(2013CB921802)Fundamental Research Funds for the Central Universities,China,State Key Laboratory for Conservation and Utilization of Subtropical Agro-bioresources,China(KSL-CUSAb-2012-03)~~
基金supported by the National Key Basic Research Program of China(973)(2013CB921802)~~
文摘本文研究了(C_(60))_2-[P(O)(OCH_3)]_2富勒烯双体内的笼间C―C键的热力学性质(该双体的结构详见文献,Chem.Commun.2011,47,6111)。原位、变温电子顺磁共振波谱实验结果表明,该C―C键的键离解能(BDE)为72.4 k J?mol^(-1)(17.3 kcal?mol^(-1)),仅约为常见氢键的两倍,或约为常见有机C―C键的五分之一。因此,该二聚体于较高温度时容易发生均裂反应,形成单体自由基;降温时又容易发生自由基聚合反应。基于该笼间C―C键所具有的这些热力学特性,我们对其可被用于制备有序的富勒烯分子元器件等材料作展开讨论。
基金supported by the National Key R&D Program of China(No.2018YFA0306600)AnHui Initiative in Quantum Information Technologies(No.AHY050000)
文摘The formation and qualification of redox sites in transition metal oxides are always the active fields related to electronics, catalysis, sensors, and energy-storage units. In the present study, the temperature dependence of thermal reduction of MoO3 was surveyed at the range of 350℃ to 750℃. Upon reduction, the formed redox species characterized by EPR spectroscopy are the MoVion and superoxide anion radical (O2-) when the reduction was induced at the optimal temperature of 300-350℃. When heating-up from 350℃, the EPR signals started to decline in amplitude. The signals in the range of 400-450℃ decreased to half of that at 350℃, and then to zero at ~600℃. Further treatment at even higher temperature or prolonged heating time at 500℃ caused more reduction and more free electrons were released to the MoO3 bulk, which results in a delocalized means similar to the antiferromagnetic coupling. These data herein are helpful to prepare and study the metal-oxide catalysts.
基金Supported by the National Key R&D Program of China(Grant Nos.2018YFA0306600 and 2016YFB0501603)the Chinese Academy of Sciences(Grant Nos.GJJSTD20170001,QYZDY-SSW-SLH004,and QYZDB-SSW-SLH005)+2 种基金Anhui Initiative in Quantum Information Technologies(Grant No.AHY050000)the Youth Innovation Promotion Association of Chinese Academy of Sciences for their supportthe support from Wuhan National High Magnetic Field Center(Grant No.2015KF06)。
文摘Molecular qubits are promising as they can benefit from tailoring and versatile design of chemistry.It is essential to reduce the decoherence of molecular qubits caused by their interactions with the environment.Herein the dynamical decoupling(DD)technique is utilized to combat such decoherence.The coherence time for a transitionmetal complex(PPh_(4))_(2)[Cu(mnt)_(2)]is prolonged from 6.8μs to 1.4 ms.The ratio of the coherence time and the length ofπ/2 pulse,defined as the single qubit figure of merit(QM),reaches 1.4×10^(5),which is 40 times greater than what previously reported for this molecule.Our results show that molecular qubits,with milliseconds coherence time,are promising candidates for quantum information processing.
文摘在绿色植物的放氧光合作用过程中,每个反应周期(即S态循环)都有两个底物水分子被氧化,释放出四个质子和四个电子,并最终释放一个氧气分子,这种化学反应机制维持着地球上的各种需氧生命活动。目前,人们已经清楚地知道,这个生物催化过程是由光系统Ⅱ(photosystemⅡ,PSⅡ)中一个无机簇状结构(即锰簇Mn4O5Ca)催化完成的。然而,这两个底物水分子是在此反应同期的什么时候、什么地方、以什么方式结合到锰簇上的,目前仍旧是一个谜团。在探讨此问题的很多实验研究中,人们常用脉冲电子顺磁共振(electron paramagnetic resonance,EPR)波谱学方法,探测底物水分子在反应中间氧化态S2态锰簇中的结合方式和结合位点,即依据超精细耦合常数的大小来判断未成对电子与磁性核的距离。基于此前的实验数据和文献报道,EPR理论模拟的结果显示,中间S2态锰簇上仅仅可容纳一个可发生置换的底物水,并且已经发生完全去质子化。这个结合水可能就是研究人员使用时间分辨薄膜进样质谱(membrane-inlet mass spectrometry,MIMS)检测到的强磁性耦合氧。此结果排除了源自强磁性耦合14N信号的干扰。因此,理论和实验结果均说明,另一个底物水是在锰簇由S2态氧化到更高中间态S3态的过程中结合到锰簇上的,并最终参与了O2分子的形成。
