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  本文選題：鹵鍵 + Tetrel�。� 參考：《煙臺大學》2017年碩士論文

【摘要】：Tetrel bond作為一種新型的分子間相互作用,在構建晶體材料、調控化學反應和分子識別中有著重要的應用。本論文利用理論計算方法對tetrel bond的形成、性質和作用規(guī)律進行了研究。主要內容如下:二甲亞砜(DMSO)與TF_3X(T=C,Si;X=鹵素原子)不僅可以形成tetrel bond,也可以形成鹵鍵。除DMSO···CF_4體系外,DMSO更易于與CF_3X形成鹵鍵,而DMSO更易于與SiF_3X形成tetrel bond。鹵原子對DMSO···CF_3X體系中的tetrel bond影響較小,但DMSO···SiF_3X體系中的tetrel bond受鹵原子的影響非常大。DMSO···SiF_3X體系中的tetrel bond具有部分共價鍵的性質,其比陰離子形成的tetrel bond還強。研究了DMSO與苯基三氟硅烷體系中取代基對tetrel bond的影響。當取代基是推電子基NH_3,OCH_3,CH_3和OH時,tetrel bond作用減弱;當取代基是吸電子基F,CHO,CN,NO_2和SO_3H時,tetrel bond作用增強。在p-HO_3S-PhSiF_3···DMSO復合物中作用最強,作用能為-122 kJ/mol。Tetrel bond主要由靜電作用主導,不過由O的孤對電子軌道向Si的空p軌道的電荷轉移也非常重要。當取代基為NH_2和OH時,其更易于形成氫鍵;當取代基為CHO和NO_2時,tetrel bond比π-hole作用更強。在PhTH_3···H_3ZO和PhSiF_3···H_3ZO(T=Si,Ge和Sn;Z=N,P和As)復合物中,除了主要的T···O tetrel bond外,還存在其它弱相互作用。這些復合物的結合能從11到220 kJ/mol,T···O距離從1.89到3.09?。對于給定的PhTH_3/PhSiF_3,復合物的穩(wěn)定性按Z=PAsN順序增加;對于給定的H_3ZO,結合能還與PhTH_3/PhSiF_3有關。由O的孤對電子軌道到C-T和T-H反鍵軌道的電荷轉移使得這些復合物穩(wěn)定。PhTH_3/PhSiF_3···H_3ZO中的T···O作用具有很大程度的共價性質,在PhSiF_3···H_3NO中C-Si鍵和Si-O鍵的鍵長幾乎相等。
[Abstract]:As a new type of intermolecular interaction, Tetrel bond plays an important role in the construction of crystal materials, the regulation of chemical reactions and molecular recognition. In this paper, the formation, properties and action law of tetrel bond are studied by theoretical calculation method. The main contents are as follows: dimethyl sulfoxide (DMSOs) and TF3XT (CX SiX = halogen atoms) can not only form tetrel bond, but also form halogen bond. In addition to the DMSO CF_4 system, it is easier for DMSO to form a halogen bond with CF_3X, and for DMSO to form tetrel bond with SiF_3X. The effect of halide atoms on tetrel bond in DMSO CF_3X system is small, but tetrel bond in DMSO SiF_3X system is greatly influenced by halide atoms. Tetrel bond in DMSO SiF_3X system has the property of partial covalent bond, which is stronger than tetrel bond formed by anion. The effect of substituents on tetrel bond in the system of DMSO and phenyl trifluorosilane was studied. The effect of tetrel bond is weakened when the substituent is a push-electron group NH _ 3O _ Ch _ 3C _ T _ 3 and OH, while the effect of tetrel bond is enhanced when the substituent is an electron absorbing group. The interaction energy of -122 kJ/mol.Tetrel bond is dominated by electrostatic interaction, but the charge transfer from O's lone pair electron orbital to Si's empty p orbital is also very important. When the substituents are NH_2 and OH, it is easier to form hydrogen bonds, and when the substituents are CHO and NO_2, the effect of tetrel bond is stronger than that of 蟺 -hole. In addition to the main T O tetrel bond, there are other weak interactions in the complexes of PhTH_3 H_3ZO and PhSiF_3 H3ZOTZOGe. The binding energies of these complexes range from 11 to 220 KJ / mol / O from 1.89 to 3.09. For a given PhTH3 / PhSiF3, the stability of the complex increases in Z=PAsN order, and for a given Hs 3ZO, the binding energy is also related to PhTH_3/PhSiF_3. The charge transfer from the solitary pair electron orbital of O to the C-T and T-H antibonding orbitals makes these complexes stable. The T-O interaction in PhTH3 / PhSiFSP _ 3 H_3ZO has a great degree of covalent property. In PhSiF_3 H_3NO, the bond lengths of C-Si bond and Si-O bond are almost equal.
【學位授予單位】：煙臺大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O641.3

【參考文獻】

相關期刊論文 前1條

1 陳安尚,李亞明,張華;取代基對4-N,N-二苯胺基均二苯乙烯類電致發(fā)光材料光電特性的影響[J];化學學報;2005年06期

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本文編號：1814748