A Sequential Photoinduced Electron Relay Accelerated by Fullerene in a Porphyrin‐Pyromellitimide‐C60 Triad
A Sequential Photoinduced Electron Relay Accelerated by Fullerene in a Porphyrin‐Pyromellitimide‐C60 Triad
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卟啉-均苯四酰亚胺-C60 三联体中富勒烯加速的顺序光致电子中继
DOI：
10.1002/anie.199726261
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发表时间：
1997
影响因子：
--
通讯作者：
Y. Sakata
中科院分区：
文献类型：
--
作者：
H. Imahori;Koji Yamada;Masato Hasegawa;S. Taniguchi;T. Okada;Y. Sakata
[4]晶体结构分析：1:G， H,， AIF, NOSi， M,= 413.59，单斜空间群PZ，/c, a= 954.7 (2), b= 1324.6 (3), c= 1951.7 (4) pm,@= 90.54(3)”，V= 2.468 (1) nm3, 2= 4, pc,,= 1.113 gcm-3, F (ooO)= 896, 1= 71.073 pm， T= 243 K, p (MoKo)= 0.155 mm-'。晶体尺寸：0.4 x 0.4 x 0.2毫米'。6 5 28 5 44"。在收集到的5216个反射中，3226个是独立的，并在0约束的帮助下用于252个参数的结构细化。R1= 0.0572 (I> Zu (I)), wR2= 0.1722（所有数据），min./max.；剩余电子密度：-332/226 enm-)。2: &， H,, AIF2NOSi， M,= 428.64，三斜空间群Pi， a= 1445.9 (7), b= 1638 (1), c= 2345.7 (9) pm, a= 90.23 (2),/3= 101.83 (2), y= 110.54 (2)‘， V= 5.074 (4) nm’， Z= 8, pralcd= 1.122 gcm-', F (OO0)= 1864， I= 71.073 pm， T= 193 K, p (MoKu)= OX 3 mm-I。晶体尺寸：0.4 x 0.3 x 0.3毫米'。4 5 28 5 52"。在收集到的78028个反射信号中，有20680个是独立的，用于在1204个约束条件下对1225个参数进行结构细化。R l=~ l F,-F, R l~ F = 0。0 5 5 8 (> 2 u (I)), wR2 = [Zw (F, F) 2 i2wf:]”minhax = 0.1244(所有数据)。剩余电子密度：-250/563enm-'。3a: C~ Hll, A1， F,， NIO, Si,， M,= 1487.84，单斜空间群PZ， lc, a= 3180.8 (4), b= 1569.4 (3), C = 2692.2 (4) pm, p= 113.11 (1)‘， V= 12.361 (3) nm3， Z= 6, pC,,,,= 1.261 gcm-’， F (00)= 5004, 1= 71.073 pm， T= 133 K, p (MoKu)= 0.209 mm-'。晶体尺寸：0.4 x 0.4 x 0.2毫米'。4、5、20、5、52”。在收集到的41 945个反射中，22 119个是独立的，并利用664个约束对1525个参数进行了结构优化。R1= 0.0725 (I> 2u (I)), wR2= 0.1702 （all data), rmin ./max. 1= 0.0725 (I)）剩余电子密度：-613/696 enm-'。4a: C68HIZOA16F12-N， O, Si,， M,= 1543.95，单斜空间群P2， lc, a= 1338.7 (3), b= 2468.3 (8), c= 1509.8 (7) pm, 8= 115.82(2)”，Y= 4.491 (3) nm‘， Z= 2, pcalcd= 1.248 gcm-’， F (OO0)= 1804, 1= 71.073 pm， T= 193 K, p (MoKc)= 0.197 mm-'。晶体尺寸：0.7 x 0.6 x 0.6毫米3。6 5 2 8 5 48"。在收集到的8978个反射信号中，7803个是独立的，并利用338个约束对579个参数进行了结构优化。R1= 0.0609 (I> 20 (1)), wR2= 0.1845（所有数据）；minhax。剩余电子密度：-487/360 emr从1和3a的数据是用stoe - siemens - s收集的，除了显示出各种独特的性质，如超导性、生物活性和铁磁性外，[']C在光物理和光化学过程中是一个很好的电子受体和敏化剂。[*，~]我们[3,41]和其他的~ l~-~ 1证明了C，，可以加速供体连接富勒烯的光诱导电荷分离（CS）和减速电荷重组（CR）。在更复杂的分子系统中利用这种构建块似乎有希望构建太阳能转换系统。在光合作用中将光转化为化学势能的基本原理是光驱动的CS和随后在反应中心内排列良好的色素之间的快速电子中继。[*]虽然已经有许多尝试模拟电子的矢量传输
[4] Crystal structure analyses: 1: G, H,, AIF, NOSi, M,= 413.59, monoclinic space group PZ,/c, a= 954.7 (2), b= 1324.6 (3), c= 1951.7 (4) pm,@= 90.54 (3)", V= 2.468 (1) nm3, 2= 4, pc,,= 1.113 gcm-3, F (ooO)= 896, 1= 71.073 pm, T= 243 K, p (MoKo)= 0.155 mm-'. Crystal dimensions: 0.4 x 0.4 x 0.2 mm'. 6 5 28 5 44". Of the 5216 reflections collected, 3226 were independent and used for the structure refinement of 252 parameters with the aid of 0 restraints. R1= 0.0572 (I> Zu (I)), wR2= 0.1722 (all data), min./max. residual electron density:-332/226 enm-). 2: &, H,, AIF2NOSi, M,= 428.64, triclinic space group Pi, a= 1445.9 (7), b= 1638 (1), c= 2345.7 (9) pm, a= 90.23 (2),/3= 101.83 (2), y= 110.54 (2)', V= 5.074 (4) nm', Z= 8, pralcd= 1.122 gcm-', F (OO0)= 1864, I= 71.073 pm, T= 193 K, p (MoKu)= OX 3 mm-I. Crystal dimensions: 0.4 x 0.3 x 0.3 mm'. 4 5 28 5 52". Of the 78028 reflections collected, 20680 were independent and used for the structure refinement of 1225 parameters with the aid of 1204 restraints. R l=~ l F,-F, lll~ F~= 0. 0 5 5 8 (I> 2u (I)), wR2=[Zw (F;-F:) 2i2wF:]'"= 0.1244 (all data), minhax. residual electron density:-250/563enm-'. 3a: C~ Hll, A1, F,, NIO, Si,, M,= 1487.84, monoclinic space group PZ, lc, a= 3180.8 (4), b= 1569.4 (3), c= 2692.2 (4) pm, p= 113.11 (1)', V= 12.361 (3) nm3, Z= 6, pC,,,,= 1.261 gcm-', F (O00)= 5004, 1= 71.073 pm, T= 133 K, p (MoKu)= 0.209 mm-'. Crystal dimensions: 0.4 x 0.4 x 0.2 mm'. 4 5 20 5 52". Of the 41 945 reflections collected, 22 119 were independent and used for the structure refinement of 1525 parameters with the aid of 664 restraints. R1= 0.0725 (I> 2u (I)), wR2= 0.1702 (all data), rnin./max. residual electron density:-613/696 enm-'. 4a: C68HIZOA16F12-N, O, Si,, M,= 1543.95, monoclinic space group P2, lc, a= 1338.7 (3), b= 2468.3 (8), c= 1509.8 (7) pm, 8= 115.82 (2)", Y= 4.491 (3) nm', Z= 2, pcalcd= 1.248 gcm-', F (OO0)= 1804, 1= 71.073 pm, T= 193 K, p (MoKc)= 0.197 mm-'. Crystal dimensions: 0.7 x 0.6 x 0.6 mm3. 6 5 2 8 5 48". Of the 8978 reflections collected, 7803 were independent and used for the structure refinement of 579 parameters with the aid of 338 restraints. R1= 0.0609 (I> 20 (1)), wR2= 0.1845 (all data); minhax. residual electron density:-487/360 emr 3. The data from 1 and 3a were collected by using a Stoe-Siemens-In addition to displaying a variety of unique properties such as superconductivity, biological activity, and ferromagnetism,['] C, is a good electron acceptor as well as a sensitizer when employed in photophysical and photochemical processe~.[*,~] We [3, 41 and other~ l~-~ l demonstrated that C,, can accelerate photoinduced charge separation (CS) and decelerate charge recombination (CR) in donor-linked fullerenes. Utilization of such a building block in more elaborate molecular systems seems to be promising for the construction of solar energy conversion systems. In photosynthesis the fundamental principle for converting light into chemical potential energy is photodriven CS and subsequent fast electron relay between well-arranged pigments within the reaction center.[*] Although there have been numerous attempts to mimic vectorial electron transport across the