Ultrafast energy-electron transfer cascade in a multichromophoric light-harvesting molecular square

被引:179
作者
Sautter, A
Kaletas, BK
Schmid, DG
Dobrawa, R
Zimine, M
Jung, G
van Stokkum, IHM
De Cola, L
Williams, RM
Würthner, F
机构
[1] Univ Amsterdam, Van Hoff Inst Mol Sci, NL-1018 WV Amsterdam, Netherlands
[2] Univ Wurzburg, Inst Organ Chem, D-97094 Wurzburg, Germany
[3] Univ Tubingen, Inst Organ Chem, D-72076 Tubingen, Germany
[4] Vrije Univ Amsterdam, Dept Phys & Astron, NL-1081 HV Amsterdam, Netherlands
关键词
D O I
10.1021/ja0448216
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A molecular square with dimensions of about 4 nm, incorporating sixteen pyrene chromophores attached to four ditopic bay-functionalized perylene bisimide chromophores, has been synthesized by coordination to four Pt(II) phosphine corner units and fully characterized via NMR spectroscopy and ESI-FTICR mass spectrometry. Steady-state and time-resolved emission as well as femtosecond transient absorption studies reveal the presence of a highly efficient (> 90%) and fast photoincluced energy transfer (k(en) approximate to 5.0 x 10(9) s(-1)) from the pyrene to the perylene bisimide chromophores and a very fast and efficient electron transfer (> 94%, k(et) 5 x 10(11) up to 43 x 10(11) s(-1)). Spectrotemporal parametrization indicates upper excited-state electron-transfer processes, various energy and electron-transfer pathways, and chromophoric heterogeneity. Temperature-dependent time-resolved emission spectroscopy has shown that the acceptor emission lifetime increases with decreasing temperature from which an electron-transfer barrier is obtained. The extremely fast electron-transfer processes (substantially faster and more efficient than in the free ligand) that are normally only observed in solid materials, together with the closely packed structure of 20 chromophoric units, indicate that we can consider the molecular square as a monodisperse nanoaggregate: a molecularly defined ensemble of chromophores that partly behaves like a solid material.
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收藏
页码:6719 / 6729
页数:11
相关论文
共 93 条
[1]   Self-assembly of supramolecular light-harvesting arrays from covalent multi-chromophore peryiene-3,4:9,10-bis(dicarboximide) building blocks [J].
Ahrens, MJ ;
Sinks, LE ;
Rybtchinski, B ;
Liu, WH ;
Jones, BA ;
Giaimo, JM ;
Gusev, AV ;
Goshe, AJ ;
Tiede, DM ;
Wasielewski, MR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (26) :8284-8294
[2]   Femtosecond IR study of excited-state relaxation and electron-injection dynamics of Ru(dcbpy)2(NCS)2 in solution and on nanocrystalline TiO2 and Al2O3 thin films [J].
Asbury, JB ;
Ellingson, RJ ;
Ghosh, HN ;
Ferrere, S ;
Nozik, AJ ;
Lian, TQ .
JOURNAL OF PHYSICAL CHEMISTRY B, 1999, 103 (16) :3110-3119
[3]   Photophysics, photochemistry and electrochemistry of mixed-ligand platinum(II) complexes with 2-phenylpyridine and 2-(2'-thienyl) pyridine as cyclometalating ligands [J].
Balashev, KP ;
Puzyk, MV ;
Kotlyar, VS ;
Kulikova, MV .
COORDINATION CHEMISTRY REVIEWS, 1997, 159 :109-120
[4]   Rigid, cross-conjugated macrocycles:: A cyclic alternative to 4,4′-bipyridines in supramolecular chemistry [J].
Campbell, K ;
McDonald, R ;
Branda, NR ;
Tykwinski, RR .
ORGANIC LETTERS, 2001, 3 (07) :1045-1048
[5]  
Campos-Fernández CS, 1999, ANGEW CHEM INT EDIT, V38, P3477, DOI 10.1002/(SICI)1521-3773(19991203)38:23<3477::AID-ANIE3477>3.0.CO
[6]  
2-P
[7]   Quantitative comparison of kinetic stabilities of metallomacrocycle-based rotaxanes [J].
Chang, SY ;
Jang, HY ;
Jeong, KS .
CHEMISTRY-A EUROPEAN JOURNAL, 2003, 9 (07) :1535-1541
[8]   Structure, physical, chemical and photophysical properties of Pt(bph)(CO)(2), where bph is the biphenyl dianion [J].
Chen, YH ;
Merkert, JW ;
Murtaza, Z ;
Woods, C ;
Rillema, DP .
INORGANICA CHIMICA ACTA, 1995, 240 (1-2) :41-47
[9]   Self-assembly of a linear multicomponent porphyrin array through axial coordination [J].
Chichak, K ;
Branda, NR .
CHEMICAL COMMUNICATIONS, 1999, (06) :523-524
[10]   Supramolecular coordination chemistry and functional microporous molecular materials [J].
Dinolfo, PH ;
Hupp, JT .
CHEMISTRY OF MATERIALS, 2001, 13 (10) :3113-3125