From Hetero- to Homochiral Bis(metallahelicene)s Based on a PtIII-PtIII Bonded Scaffold: Isomerization, Structure, and Chiroptical Properties

被引:71
作者
Anger, Emmanuel [2 ]
Rudolph, Mark [1 ]
Shen, Chengshuo [2 ]
Vanthuyne, Nicolas [3 ]
Toupet, Loic [2 ]
Roussel, Christian [3 ]
Autschbach, Jochen [1 ]
Crassous, Jeanne [2 ]
Reau, Regis [2 ]
机构
[1] SUNY Buffalo, Dept Chem, Buffalo, NY 14260 USA
[2] Univ Rennes 1, CNRS, Inst Phys Rennes, UMR 6226,UMR 6251, F-35042 Rennes, France
[3] Univ Paul Cezanne, ISM2, Chirosci UMR 6263, F-13397 Marseille 20, France
基金
美国国家科学基金会;
关键词
ASYMMETRIC-SYNTHESIS; COMPLEXES; HELICENES; MOLECULES; ROUTE; PLATINUM(III); DERIVATIVES; RESOLUTION; OXIDATION; LIGANDS;
D O I
10.1021/ja200129y
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Hetero- and homochiral diastereomeric bis(metallahelicene)s have been synthesized. They possess a rare Pt-III-Pt-III scaffold bridged by benzoato ligands. It is shown that heterochiral (P,M)-bis(Pt-III-[6]helicene) can isomerize into the homochiral (P,P)- and (M,M)-bis-(Pt-III-[6]helicene). A theoretical study shows a unique sigma-pi conjugation between the two pi-helices and the sigma-Pt-III-Pt-III scaffold that impacts the strong chiroptical properties.
引用
收藏
页码:3800 / 3803
页数:4
相关论文
共 41 条
[1]   Helquats: A Facile, Modular, Scalable Route to Novel Helical Dications [J].
Adriaenssens, Louis ;
Severa, Lukas ;
Salova, Tereza ;
Cisarova, Ivana ;
Pohl, Radek ;
Saman, David ;
Rocha, Shvia V. ;
Finney, Nathaniel S. ;
Pospisil, Lubomir ;
Slavicek, Petr ;
Teply, Filip .
CHEMISTRY-A EUROPEAN JOURNAL, 2009, 15 (05) :1072-1076
[2]   Distinction between homochiral and heterochiral dimers of 1-aza[n]helicenes (n=1-7) with alkaline cations [J].
Alkorta, Ibon ;
Blanco, Fernando ;
Elguero, Jose ;
Schroeder, Detlef .
TETRAHEDRON-ASYMMETRY, 2010, 21 (08) :962-968
[3]   Chiral recognition in noncovalent bonding interactions between helicenes: right-handed helix favors right-handed helix over left-handed helix [J].
Amemiya, Ryo ;
Yamaguchi, Masahiko .
ORGANIC & BIOMOLECULAR CHEMISTRY, 2008, 6 (01) :26-35
[4]   Two-Component Gel Formation by Pseudoenantiomeric Ethynylhelicene Oligomers [J].
Amemiya, Ryo ;
Mizutani, Marie ;
Yamaguchi, Masahiko .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (11) :1995-1999
[5]   Computing Chiroptical Properties with First-Principles Theoretical Methods: Background and Illustrative Examples [J].
Autschbach, Jochen .
CHIRALITY, 2009, 21 (1E) :E116-E152
[6]   TETRAMETHYLDIPLATINUM(III) (PT-PT) COMPLEXES WITH 2-HYDROXYPYRIDINATO BRIDGING LIGANDS .3. COMPOUNDS WITH DIETHYL SULFIDE AS THE AXIAL LIGAND [J].
BANCROFT, DP ;
COTTON, FA .
INORGANIC CHEMISTRY, 1988, 27 (22) :4022-4025
[7]   Unprecedented Near-Infrared (NIR) Emission in Diplatinum(III) (d7-d7) Complexes at Room Temperature [J].
Bennett, Martin A. ;
Bhargava, Suresh K. ;
Cheng, Eddie Chung-Chin ;
Lam, Wai Han ;
Lee, Terence Kwok-Ming ;
Priver, Steven H. ;
Wagler, Joerg ;
Willis, Anthony C. ;
Yam, Vivian Wing-Wah .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (20) :7094-7103
[8]   Electronic Structures of PdII Dimers [J].
Bercaw, John E. ;
Durrell, Alec C. ;
Gray, Harry B. ;
Green, Jennifer C. ;
Hazari, Nilay ;
Labinger, Jay A. ;
Winkler, Jay R. .
INORGANIC CHEMISTRY, 2010, 49 (04) :1801-1810
[9]   BINUCLEAR PLATINUM(III) COMPLEXES - PREPARATION, STRUCTURE, AND D-SIGMA-]D-SIGMA-STAR SPECTRUM OF [BU4N]2[PT2(P2O5H2)4(CH3CN)2] [J].
CHE, CM ;
MAK, TCW ;
MISKOWSKI, VM ;
GRAY, HB .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (24) :7840-7841
[10]   Synthesis and Structures of Multifunctionalized Helicenes and Dehydrohelicenes: An Efficient Route to Construct Cyan Fluorescent Molecules [J].
Chen, Jun-Dao ;
Lu, Hai-Yan ;
Chen, Chuan-Feng .
CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (39) :11843-11846