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| In addition to the trans isomer, photoexcitation of cis-stilbene generates the cyclic product 4a,4b-dihydrophenanthrene in 10% yield. The yields of the three processes add up to ~1, suggesting that only one pathway may be available for the deactivation excited stilbene. Trans-stilbene is thermodynamically more stable; however, the barrier to thermal isomerization is significantly larger than that of AB, and the rate of thermal isomerization at room temperature is very slow.Dynamic simulations and ab initio lculations predict isomerization of stilbene to be dominated by rotation, with some contribution from skeletal deformations. A crossover point between S1 and S0 states has been located near a torsional angle of 90. Both trans and cis-stilbene must acquire the same conformation prior to S0 ←S1 intersystem crossing; however a small barrier exists on the side of the trans isomer. As a result, the S1 state of trans-stilbene has a considerably longer lifetime than that of the cis isomer. Ultrafast timeresolved spectroscopy has revealed S0←S1 relaxation of stilbene to be unimodal. |
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商家已經(jīng)主動(dòng)聲明此回帖可能含有宣傳內(nèi)容| 關(guān)于以上引用資料中提到的，以銅為催化劑的PhEt氧化反應(yīng)，有幾篇文章研究?jī)?nèi)容就涉及到了將復(fù)合物固定到某個(gè)支撐點(diǎn)，即，利用Y型沸石，封裝9-, 12-, 14-，16- 三態(tài)水磨石大環(huán)配體復(fù)合物，具體方法首先將CuII Salen復(fù)合物固定在改良的碳納米管上，然后將層狀雙氫氧化物，插入2,20- 二吡啶-5,50-二元羧酸鹽 CuII 復(fù)合物的夾層，最后利用聚合物固定2-(a- 羥甲基)苯并咪唑 CuII 復(fù)合物。 |
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3樓2015-04-21 10:08:21
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wskk: 金幣+10, 翻譯EPI+1, ★★★★★最佳答案, 謝謝你了 2015-04-21 11:16:28
wskk: 金幣+10, 翻譯EPI+1, ★★★★★最佳答案, 謝謝你了 2015-04-21 11:16:28
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In addition to the trans isomer, photoexcitation of cis-stilbene generates the cyclic product 4a,4b-ihydrophenanthrene in 10% yield. 除了反式異構(gòu)體，順勢(shì)光激勵(lì)也能生成環(huán)狀產(chǎn)物4a,4b-二氫菲（產(chǎn)率為10%）。 The yields of the three processes add up to ~1, suggesting that only one pathway may be available for the deactivation excited stilbene. 三個(gè)步驟的產(chǎn)率增加到了 ~1，這就標(biāo)明，其中只有一個(gè)方法能夠鈍化刺激的對(duì)稱二苯代乙烯。 Trans-stilbene is thermodynamically more stable; however, the barrier to thermal isomerization is significantly larger than that of AB, and the rate of thermal isomerization at room temperature is very slow. 雖然二苯乙烯的熱力學(xué)穩(wěn)定性更高，然而，其熱異構(gòu)化的困難比實(shí)現(xiàn)AB異構(gòu)化的困難要大得多，而且在室溫環(huán)境中，熱異構(gòu)化速率非常慢。 Dynamic simulations and ab initio calculations predict isomerization of stilbene to be dominated by rotation, with some contribution from skeletal deformations. 受骨骼形變的啟發(fā)，動(dòng)態(tài)仿真和從頭計(jì)算法預(yù)測(cè)，對(duì)稱二苯代乙烯異構(gòu)將由分子旋轉(zhuǎn)完成。 A crossover point between S1 and S0 states has been located near a torsional angle of 90. Both trans and cis-stilbene must acquire the same conformation prior to S0 ←S1 intersystem crossing; however a small barrier exists on the side of the trans isomer. 經(jīng)過定位，S1和S0質(zhì)檢的交叉點(diǎn)接近于90度的扭轉(zhuǎn)角。在系統(tǒng)由S1穿越到S0之前，無論順式和反式異構(gòu)都必須有同樣的構(gòu)象；其中對(duì)于反式異構(gòu)體，這存在一點(diǎn)小小的困難。 As a result, the S1 state of trans-stilbene has a considerably longer lifetime than that of the cis isomer. Ultrafast timeresolved spectroscopy has revealed S0←S1 relaxation of stilbene to be unimodal. 因此，比起順式異構(gòu)體，反式-二苯乙烯的S1狀態(tài)相當(dāng)?shù)拈L(zhǎng)。 極速時(shí)間分辨光譜法標(biāo)明，對(duì)稱二苯代乙烯又S1狀態(tài)緩沖到S0狀態(tài)是單向的。 |
4樓2015-04-21 10:33:08
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