Studies on Synthesis and Properties of Molecular Crystalline Organopolysilanes

分子结晶有机聚硅烷的合成及性能研究

• 批准号: 06453034
• 负责人: MATSUMOTO Hideyuki
• 金额: $ 4.42万
• 依托单位: Gunma University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06453034/
• 关键词: Molecular crystalline polysilane; Ladder polysilanes; Octasilacubane; Ladder polysilane anion radicals; Ring-opening halogenation; Oxidation; Cyclotetrasilane; 分子結晶; ポリシクロシラン; 合成

1.The pentacyclic ladder polysilane, anti, anti, anti-hexadecaisopropylpentacyclo [6.4.0.0^<2,7>.0^<3,6>.0^<9,12>] -dodecasilane was prepared and the structure was determined by X-ray crystallography. Two linear hexasilane chains of the ladder polysiane screw on one way, and the molecule has the partially double helical structure ; the helical structure results from the systematic catenation that the folded cyclotetrasilane rings are connected up and down alternatively. The anion radical of the pentacycle, which was generated by the reduction with K,persisted over several months at room temperature ; the intensity loss in the ESR Signal after one month is 19%, and the half-life time is too long to be measured. This remarkable stability is unprecedented for polysilane anion radicals. 2.Reaction of decaisopropylbicyclo [2.2.0] hexasilane with the divalent palladium PdCl_2 (PhCN) _2led to the formation of 1,4-dichlorodecaisopropylbicyclohexasilane. 3.Treatment of decaisopropylbicyclo [2.2 … More .0] hexasilane with MCPBA afforded decaisopropyl-7-oxabicyclo- [2.2.1] heptasilane and decaisopropy1-2-oxabicyclo [3.2.0] -heptasilane as monoxidation products. The 7-oxa compound showed unusual properties in the UV spectrum due to the interaction of the n orbital of the oxygen atom and the Si-Si sigma bonds. The compound also showed far stronger fluorescence than the bicyclohexasilane. 4.The ring-opening reaction of anti-dodcaisopropyltricyclo [4.2.0.0^<2,5>] octasilane with PdCl_2 (PhCN) _2 gave the new bicyclic systems, dodocaisoproybicyclo [3.3.0] octasilane and dodoca-isopropylbicyclo [4.2.0] octasilane. 5.The ring-opening halogenation of octathexyloctasilacubane resulted in skeletal rearrangement with concomitant formation of stereoisomeric 4,8-dihalooctathexyltetracyclo- [3.3.0.0^<2,7>.0^<3,6>] octasilanes. The reductive dehalogenation of the 4,8-dihalotracyclooctasilanes with sodium metal led to unusual skeletal rearrangement, forming the octasilacubane. 6.Photooxidation of the octasila-cubane with dimethylsulfoxide resulted in formation of the new polyhedral systems, the oxaoctasila-homocubane, octathexylpentacyclo [4.3.0.0^<2,5>.0^<3,8>.0^<4,7>] -9-oxanonasilane and the dioxaoctasilabishomo-cubane, octathexylpentacyclo [5.3.0.0^<2,6>.0^<3,9>.0^<4,8>] -5,10-dioxadecasilane. 7.The reaction of di-tert-butyl-dichlorosilane with lithium produced hepta-tert-butylcyclotetrasilane and trans-1,1,2,3,3,4-hexa-tert-butylcyclotetrasilane. Less

1.合成了五环梯形聚硅烷，反十六异丙基五环[6.4.0.0^<2，7>.0^<3，6>.0^<9，12>] -十二硅烷，用X射线单晶衍射法测定了其结构。梯形聚硅烷的两条直链六硅烷链单向螺旋，分子具有部分双螺旋结构，螺旋结构是由折叠的环四硅烷环上下交替连接的系统链合产生的。通过用K还原产生的pentaclitazone的阴离子自由基在室温下持续数月;一个月后ESR信号的强度损失为19%，半衰期太长而无法测量。这种显著的稳定性对于聚硅烷阴离子自由基来说是前所未有的。2.十异丙基双环[2.2.0]六硅烷与二价钯PdCl_2（PhCN）_2反应生成1，4-二氯十异丙基双环六硅烷。3.十异丙基双环[2.2]的处理 ...更多信息 .0]己硅烷与MCPBA反应得到十异丙基-7-氧杂双环[2.2.1]七硅烷和十异丙基-2-氧杂双环[3.2.0]七硅烷的单氧化产物。由于氧原子的n轨道和Si-Si σ键的相互作用，7-氧杂化合物在UV光谱中显示出不寻常的性质。该化合物还显示出比双环己硅烷强得多的荧光。4.反十二烷异丙基三环[4.2.0.0 ^<2，5>]八硅烷与PdCl_2（PhCN）_2开环反应，得到了新的双环体系：十二烷异丙基双环[3.3.0]八硅烷和十二烷异丙基双环[4.2.0]八硅烷。5.八乙氧基辛硅立方烷的开环卤化导致骨架重排，伴随形成立体异构的4，8-二卤代八乙氧基四环- [3.3.0.0 ^<2，7>.0^<3，6>]八硅烷。4，8-二卤杂环辛硅烷与金属钠的还原脱卤导致不寻常的骨架重排，形成octasilucobane。6.用二甲基亚砜光氧化八硅立方烷导致形成新的多面体体系，氧杂八硅高立方烷，八己基五环[4.3.0.0 ^<2，5>.0^<3，8>.0^<4，7>] -9-氧杂壬硅烷和二氧杂八硅双立方烷，八己基五环[5.3.0.0 ^<2，6>.0^<3，9>.0^<4，8>]-5，10-二氧杂癸硅烷。7.二叔丁基二氯硅烷与锂反应生成七叔丁基环四硅烷和反式1，1，2，3，3，4-六叔丁基环四硅烷。少

项目成果

Soichiro Kyushin: "Selective Si-Si bond cleavage in decaisopropylbicyclo[2. 2. 0]hexasilane. A route to sterically hindered 1, 4-dichlorocyclohexasilanes" Chem. Lett.221-224 (1994)

Soichiro Kyushin：“十异丙基双环[2.2.0]六硅烷中的选择性 Si-Si 键断裂。空间位阻 1, 4-二氯环己硅烷的途径” Chem。

Yoshihiko Kanemitsu: "Luminescence from a cubic silicon cluster" Solid State Commun.89. 619-621 (1994)

Yoshihiko Kanemitsu：“立方硅团簇的发光”Solid State Commun.89。

Y.Kanemitsu, K.Suzuki, Y.Masumoto, and H.Matsumoto: "Optical Properties of Quasi-One-Dimensional Silicon Poylmers with Different Backbone Structures." J.Luminescence. 60&61. 462-464 (1994)

Y.Kanemitsu、K.Suzuki、Y.Masumoto 和 H.Matsumoto：“具有不同主链结构的准一维硅聚合物的光学特性。”

M.Unno, H.Shioyama, M.Ida, and H.Matsumoto: "Reductive dehalogenation of 4,8-dihalooctakis (1,1,2-trimethyl-propyl) tetracyclo [3.3.0^<2,7>.0^<3,6>] octasilanes with sodium : Formation of octasilacubane." Organometallics. 14. 4004-4009 (1995)

M.Unno、H.Shioyama、M.Ida 和 H.Matsumoto：“4,8-dihalooctakis（1,1,2-三甲基-丙基）四环的还原脱卤[3.3.0^<2,7>.0

S.Kyushin: "Syntheses, Structures,Properties and Photoluminescence of Landder Polysilanes and Octasilacubanes." J.Phys.Soc.Jpn.,Suppl.B. 3. 46-55 (1994)

S.Kyushin：“Landder 聚硅烷和 Octasilacubanes 的合成、结构、性质和光致发光。”