.png){kind=icon}
返回
Boronated Cyanometallates
.png){kind=icon}
OA
AI
DOI：10.1021/acs.inorgchem.2c03066.png)
.png){kind=icon}
原文求助.png){kind=icon}
分享.png){kind=icon}
收藏
摘要
En 中文
Thirteen boronated cyanometallates [M(CN-BR3)6]3/4/5- [M = Cr, Mn, Fe, Ru, Os; BR3 = BPh3, B(2,4,6,-F3C6H2)3, B(C6F5)3] and one metalloboratonitrile [Cr(NC-BPh3)6]3- have been characterized by X-ray crystallography and spectroscopy [UV-vis-near-IR, NMR, IR, spectroelectrochemis-try, and magnetic circular dichroism (MCD)]; CASSCF+NEVPT2 methods were employed in calculations of electronic structures. For (t2g)5 electronic configurations, the lowest-energy ligand-to-metal charge-transfer (LMCT) absorptions and MCD C-terms in the spectra of boronated species have been assigned to transitions from cyanide pi + B-C borane sigma orbitals. CASSCF+NEVPT2 calculations including t1u and t2u orbitals reproduced t1u/t2u -> t2g excitation energies. Many [M(CN-BR3)6]3/4- complexes exhibited highly electrochemically reversible redox couples. Notably, the reduction formal potentials of all five [M(CN-B(C6F5)3)6]3- anions scale with the LMCT energies, and Mn(I) and Cr(II) compounds, [K(18-crown-6)]5[Mn(CN-B(C6F5)3)6] and [K(18-crown-6)]4[Cr(CN-B(C6F5)3)6], are surprisingly stable. Continuous-wave and pulsed electron paramagnetic resonance (EPR; hyperfine sublevel correlation) spectra were collected for all Cr(III) complexes; as expected, 14N hyperfine splittings are greater for (Ph4As)3[Cr(NC-BPh3)6] than for (Ph4As)3[Cr(CN-BPh3)6].
Keyword:
MAGNETIC CIRCULAR-DICHROISM
CHARGE-TRANSFER TRANSITIONS
ELECTRONIC-STRUCTURES
MOLECULAR-STRUCTURE
ABSORPTION-SPECTRA
EXCITED-STATE
REDUCTION POTENTIALS
COORDINATION SPHERE
PHYSICAL-PROPERTIES
CYCLIC VOLTAMMETRY
期刊
IF:
4.7
论文数:
4.9W
被引数:
10.5W
机构
引用论文
Self-assembly of five new organic–inorganic hybrids based on two new flexible tricationic templates基于两个新的柔性三阳离子模板的五个新的有机-无机杂化物的自组装
PREAI
分享收藏Photostable Ruthenium(II) Isocyanoborato Luminophores and Their Use in Energy Transfer and Photoredox Catalysis.png)
JACS AU
OAAI
JACS AUIF8.7
OAAI分享收藏[CrIII(NCM)6]3+-a labile CrIII source enabling formation of Cr[M(CN)6] (M=V, Cr, Mn, Fe) Prussian blue-type magnetic materialsINORGANIC CHEMISTRY
INORGANIC CHEMISTRYIF4.7
PREAI
分享收藏Practical Aspects of Cyclic Voltammetry: How to Estimate Reduction Potentials When Irreversibility Prevails循环伏安法的实际方面: 当不可逆性盛行时如何估算还原电位
PREAI
分享收藏Borylation in the Second Coordination Sphere of FeII Cyanido Complexes and Its Impact on Their Electronic Structures and Excited-State DynamicsINORGANIC CHEMISTRYOAAI
INORGANIC CHEMISTRYIF4.7
OAAI分享收藏
查看更多内容