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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Solid-state NMR spectra and long, intra-dimer bonding in the π-[TTF]_2~(2+) (TTF = Tetrathiafulvalene) dication
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Solid-state NMR spectra and long, intra-dimer bonding in the π-[TTF]_2~(2+) (TTF = Tetrathiafulvalene) dication

机译：π-[TTF] _2〜（2+）（TT​​F =四硫富瓦烯）指示中的固态NMR光谱和长的二聚物内键

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摘要

The ~(13)C chemical-shift tensor principal values for TTF and π-[TTF]_2~(2+) (TTF = tetrathiafulvalene) dimer dications have been measured in order to better understand the electronic structure and long intradimer bonding of these TTF-based dimer structures. The structure of π-[TTF]_2~(2+) is abnormal due to its two C-C and four S-S ca. 3.4 ? intradimer separations, which is less than the sum of the sulfur van der Waals radii, and has a singlet ~1A_(1g) electronic ground state. This study of TTF and [TTF]_2~(2+) was conducted to determine how the NMR chemical-shift tensor principal values change as a function of electronic structure. This study also establishes a better understanding of the interactions that lead to spin-pairing of the monomeric radical units. The density functional theory (DFT) calculated nuclear shielding tensors are correlated with the experimentally determined principal chemical-shift values. The embedded ion method (EIM) was used to investigate the electrostatic lattice potential in [TTF]_2~(2+). These theoretical methods provide information on the tensor magnitudes and orientations of their tensor principal values with respect to the molecular frame. The experimental chemical-shift principal values agree with the calculated quantum mechanical chemical-shielding principal values, within typical errors commonly seen for this class of molecular system. Relatively weak Wiberg bond orders between the two [TTF]~+ components of the dimer dication correlate with the long bonds linking the two [TTF]~+ monomers and substantiate the claim that there is weak multicenter bonding present.
机译：为了更好地理解它们的电子结构和长的二聚体键合，已测量了TTF和π-[TTF] _2〜（2+）（TT​​F =四硫富瓦烯）二聚体的〜（13）C化学位移张量主值。基于TTF的二聚体结构。 π-[TTF] _2〜（2+）的结构由于其两个C-C和四个S-S ca而异常。 3.4？二聚体内分离，其小于硫范德华半径的总和，并且具有单峰〜1A_（1g）电子基态。进行了TTF和[TTF] _2〜（2+）的研究，以确定NMR化学位移张量主值如何随电子结构变化。这项研究还建立了对导致单体自由基单元自旋配对的相互作用的更好理解。密度泛函理论（DFT）计算的核屏蔽张量与实验确定的主要化学位移值相关。采用嵌入离子法（EIM）研究了[TTF] _2〜（2+）中的静电晶格势。这些理论方法提供有关张量主值的张量大小和方向相对于分子框架的信息。实验化学位移主值与计算出的量子力学化学屏蔽主值相符，在此类分子系统常见的典型误差范围内。二聚体的两个[TTF]〜+组分之间相对较弱的Wiberg键序与连接两个[TTF]〜+单体的长键相关，并证实存在弱多中心键的说法。

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