ハロゲン架橋一次元M(II)-M(IV)混合原子価錯体における熱膨脹係数の異常

卤桥一维M(II)-M(IV)混合价配合物热膨胀系数的异常

• 批准号: 61540345
• 负责人: 鳥海 幸四郎
• 金额: $ 1.09万
• 依托单位: Okazaki National Research Institutes
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1986
• 资助国家: 日本
• 起止时间: 1986 至 无数据
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-61540345/
• 关键词: ハロゲン架橋一次元混合原子価錯体; 負の熱膨脹; 一次相転移; 一次元金属錯体; 混合原子価錯体; 相転移前後の構造解析

ハロゲン架橋一次元【M^(II)】-【M^(IV)】混合原子価錯体は、強い電子格子結合をもつ一次元化合物として発光スペクトルなどの興味深い光物性を示す。我々はこの種の混合原子価錯体の一つ、〔Pt【(NH-3)-4】〕〔【PtX_2】【(NH-3)-4】〕【(HSO-4)-4】(X=Cl,Br)において一次元鎖方向で負の熱膨脹を示す現象をすでに報告した。この現象がどのような原因によって起るのか、特に電子格子相互作用との関連を究明するために、一連の〔M【(en-2)】〕〔【MX_2】【(en-2)】〕【(ClO-4)-4】(X=Cl,Br,I;M=Pt,Pd)の単結晶を作成し格子定数の温度変化、DSCの測定を行った。この結果、I架橋を除く混合原子価錯体において、一次元鎖方向の負の熱膨脹を伴う一次相転移が-5℃〜30℃の温度範囲で観測された。これらの結晶は同型であるため、〔Pt【(en-2)】〕-〔Pt【Br_2】【(en-2)】〕【(ClO-4)-4】について相転移前後のX線結晶解析を行い構造変化を詳細に検討した。この結果、一次元方向の【Pt^(IV)】-BKおよび【Pt^(II)】…Br結合距離は、低温相で、2.487(1)、3.006(1)【A!°】、高温相で2.473(1)、2.997(1)【A!°】であり、両者とも負の熱膨脹を示すことが明らかとなった。この結果は、一次元方向の負の熱膨脹が【Pt^(II)】…【Pt^(IV)】間の電荷移動相互作用の変化だけでは説明しきれないことを示している。相転移に伴う結晶構造変化を詳しく検討した結果、Pt【(en-2)】部分のエチレンジアミンキレート環のコンホメーションが高温相でδδ(λλ)、低温相でδλ(λδ)と変化すること、さらにこの変化に伴い一次元鎖状構造を保持しているCl【O(^-4)】とPt【(en-2)】間の水素結合系が大きく変化していることが判明した。【Pt^(IV)】-Brおよび【Pt^#】…Br距離の変化は、水素結合系の変化に伴う配位子場の変化によるものとして説明できる。これらの実験事実から、一次元方向の負の熱膨脹は、電子格子相を作用に起因するものではなく、水素結合系の変化に由来するものであり、またこの種の化合物では水素結合系が一次元鎖状構造の保持だけではなく、その構造パラメータの決定に重要な役割を果していることが結論された。

The structure of the primary element [M ^ (II)]-[M ^ (IV)] is mixed with the atomic error body, and the lattice is used to display the photophysical properties of the primary compound. We have mixed atoms (Pt [(NH-3)-4]) ([PtX_2] [(NH-3)-4]) [(HSO-4)-4] (XMLR) in the direction of primary data. For example, the reason for this effect is that the temperature is changed, the lattice interaction mechanism is analyzed, and the lattice temperature is determined by the lattice temperature curve, and the lattice temperature is determined by the lattice temperature curve, and the lattice temperature is determined by DSC. The results show that the lattice temperature is changed, and the lattice temperature is determined by DSC. (M [(en-2)]) ([MX_2] [(en-2)]) [(ClO-4)-4] [(ClO-4)-4]. The results of the experiment show that the errors of the mixed atoms are eliminated, and the primary phase shift is accompanied by a phase shift in the temperature range of-5 ℃ ~ 30 ℃. The results of X-ray diffraction show that Pt [(en-2)])-(PT [Br _ 2] [(en-2)]) [(ClO-4)-4] X-ray crystal analysis before and after the phase shift of X-ray diffraction. The result of the simulation, the direction of the first dimension [PT ^ (IV)]-BK equation [PT ^ (II)]... Br combined with distance, low temperature phase, 2.487 (1), 3.006 (1) [A! °], high temperature phase 2.473 (1), 2.997 (1) [A! °] temperature. The result of the experiment shows that the one-dimensional direction is related to the expansion [PT ^ (II)]. [PT ^ (IV)] the interaction between charge transfer and electronic charge transfer shows the performance of the system. Phase shift coupled with crystal analysis, Pt [(en-2)] partial temperature response, environmental temperature response, high temperature phase δ (λ λ), low temperature phase δ (λ δ), low temperature phase δ (λ δ) The combination of water and water in the Pt [O (^-4)]] is a key factor in determining the performance of the system. [PT ^ (IV)]-Br benchmark [PT ^ #]... The separation of Br and the combination of water and water are characterized by the combination of ligands and ligands. The cause of the chemical reaction is the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical system, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of the chemical compound, the chemical composition of

项目成果

鳥海幸四郎: Solid State Communications.

鸟海幸四郎：固态通信。