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91.
Photoisomerization Mechanism of Ruthenium Sulfoxide Complexes: Role of the Metal‐Centered Excited State in the Bond Rupture and Bond Construction Processes
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Dr. Huifang Li Lisheng Zhang lvyin Zheng Dr. Xun Li Dr. Xiaolin Fan Dr. Yi Zhao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(40):14285-14292
Phototriggered intramolecular isomerization in a series of ruthenium sulfoxide complexes, [Ru(L)(tpy)(DMSO)]n+ (where tpy=2,2’:6’,2’’‐terpyridine; DMSO=dimethyl sulfoxide; L=2,2’‐bipyridine (bpy), n=2; N,N,N’,N’‐tetramethylethylenediamine (tmen) n=2; picolinate (pic), n=1; acetylacetonate (acac), n=1; oxalate (ox), n=0; malonate (mal), n=0), was investigated theoretically. It is observed that the metal‐centered ligand field (3MC) state plays an important role in the excited state S→O isomerization of the coordinated DMSO ligand. If the population of 3MCS state is thermally accessible and no 3MCO can be populated from this state, photoisomerization will be turned off because the 3MCS excited state is expected to lead to fast radiationless decay back to the original 1GSS ground state or photodecomposition along the Ru2+?S stretching coordinate. On the contrary, if the population of 3MCS (or 3MCO) state is inaccessible, photoinduced S→O isomerization can proceed adiabatically on the potential energy surface of the metal‐to‐ligand charge transfer excited states (3MLCTS→3MLCTO). It is hoped that these results can provide valuable information for the excited state isomerization in photochromic d6 transition‐metal complexes, which is both experimentally and intellectually challenging as a field of study. 相似文献
92.
Dynamical Bifurcation in Gas‐Phase XH− + CH3Y SN2 Reactions: The Role of Energy Flow and Redistribution in Avoiding the Minimum Energy Path
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Yaicel G. Proenza Prof. Miguel A. F. de Souza Prof. Ricardo L. Longo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(45):16220-16229
The gas‐phase reactions of XH? (X=O, S) + CH3Y (Y=F, Cl, Br) span nearly the whole range of SN2 pathways, and show an intrinsic reaction coordinate (IRC) (minimum energy path) with a deep well owing to the CH3XH???Y? (or CH3S????HF) hydrogen‐bonded postreaction complex. MP2 quasiclassical‐type direct dynamics starting at the [HX???CH3???Y]? transition‐state (TS) structure reveal distinct mechanistic behaviors. Trajectories that yield the separated CH3XH+Y? (or CH3S?+HF) products directly are non‐IRC, whereas those that sample the CH3XH???Y? (or CH3S????HF) complex are IRC. The IRCIRC/non‐IRC ratios of 90:10, 40:60, 25:75, 2:98, 0:100, and 0:100 are obtained for (X, Y)=(S, F), (O, F), (S, Cl), (S, Br), (O, Cl), and (O, Br), respectively. The properties of the energy profiles after the TS cannot provide a rationalization of these results. Analysis of the energy flow in dynamics shows that the trajectories cross a dynamical bifurcation, and that the inability to follow the minimum energy path arises from long vibration periods of the X?C???Y bending mode. The partition of the available energy to the products into vibrational, rotational, and translational energies reveals that if the vibrational contribution is more than 80 %, non‐IRC behavior dominates, unless the relative fraction of the rotational and translational components is similar, in which case a richer dynamical mechanism is shown, with an IRC/non‐IRC ratio that correlates to this relative fraction. 相似文献
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Dr. Kai-Stephan Feichtner Dr. Lennart T. Scharf Dr. Thorsten Scherpf Dr. Bert Mallick Nils Boysen Prof. Dr. Viktoria H. Gessner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(69):17351-17360
The use of iminophosphoryl-tethered ruthenium carbene complexes to activate secondary phosphine P−H bonds is reported. Complexes of type [(p-cymene)-RuC(SO2Ph)(PPh2NR)] (with R = SiMe3 or 4-C6H4−NO2) were found to exhibit different reactivities depending on the electronics of the applied phosphine and the substituent at the iminophosphoryl moiety. Hence, the electron-rich silyl-substituted complex undergoes cyclometallation or shift of the imine moiety after cooperative activation of the P−H bond across the M=C linkage, depending on the electronics of the applied phosphine. Deuteration experiments and computational studies proved that cyclometallation is initiated by the activation process at the M=C bond and triggered by the high electron density at the metal in the phosphido intermediates. Consistently, replacement of the trimethylsilyl (TMS) group by the electron-withdrawing 4-nitrophenyl substituent allowed the selective cooperative P−H activation to form stable activation products. 相似文献
98.
Four new coordination polymers, [Cd(3-TPTP)Cl]2 (3-HTPTP = 4′-(3-tetrazolylphenyl)2,2′:6′2′′-terpyridine, 1), {[Cd(3-TPTP)(pBDC)0.5]?4H2O}n (pH2BDC = 1,4-benzenedicarboxylic acid, 2), {[Mn(3-TPTP)(mBDC)0.5]?5H2O}n (mH2BDC = 1,3-benzenedicarboxylic acid, 3), and [Pb(3-TPTP)(H2O)2]?OH (4), were obtained. Compounds 1–3 are composed of binuclear [M2(3-TPTP)2] ring as building unit. In 1, the binuclear rings pack into a 3-D supramolecular framework via various hydrogen bonds. In 2 and 3, the binuclear rings are connected by mBDC2? and pBDC2?, respectively, resulting in two types of 1-D chains. In 4, the mononuclear [Pb(3-TPTP)] units are connected by Pb?N weak interactions, giving a chiral 1-D coordination chain, which is further connected by O–H?N interaction to form a chiral 3-D supramolecular framework. The phase purity of 1–4 and luminescence properties of 1, 2, and 4 were also investigated. 相似文献
99.
Dr. Shiyong Zuo Dr. Xijun Xu Prof. Shaomin Ji Zhuosen Wang Dr. Zhengbo Liu Prof. Jun Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(3):830-860
As concerns about the safety of lithium-ions batteries (LIBs) increases, aqueous zinc-ion batteries (ZIBs) with a lower cost, higher safety, and higher co-efficiency have attracted more and more interest. However, finding suitable cathode materials is still an urgent problem in ZIBs. In recent years, a lot of significant works have been reported, including manganese-based cathodes, vanadium-based cathodes, Prussian blue analog-based materials, and sustainable quinone cathodes. In this review, some typical cathode materials are introduced. The detailed storage mechanisms and methods for improving the reaction kinetics of the zinc ions are summarized. Finally, the issues, challenges, and the research directions are provided. 相似文献
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