From Monomers to p Stacks, from Nonconductive to Conductive: Syntheses, Characterization, and Crystal Structures of Benzidine Radical Cations

被引:37
作者
Chen, Xiaoyu [1 ]
Ma, Binbin [1 ]
Wang, Xingyong
Yao, Shengxin [1 ]
Ni, Lichen [1 ]
Zhou, Zhaoyi [1 ]
Li, Yizhi [1 ]
Huang, Wei [1 ]
Ma, Jing [2 ]
Zuo, Jinglin [1 ]
Wang, Xinping
机构
[1] Nanjing Univ, Sch Chem & Chem Engn, Nanjing Natl Lab Microstruct, State Key Lab Coordinat Chem, Nanjing 210093, Jiangsu, Peoples R China
[2] Nanjing Univ, Key Lab Mesoscop Chem, Sch Chem & Chem Engn, Theoret & Computat Chem Inst,MOE, Nanjing 210093, Jiangsu, Peoples R China
基金
中国国家自然科学基金;
关键词
benzidine; conducting materials; pi interactions; radical ions; X-ray diffraction; POLARIZABLE CONTINUUM MODEL; CHARGE-TRANSFER; POTENTIAL INVERSION; WURSTERS BLUE; OXIDATION; POLYMERS; 3,3',5,5'-TETRAMETHYLBENZIDINE; PHENYLENEDIAMINE; 3,4-DIBUTYL-2,5-DIPHENYL-2,25,2-TERTHIOPHENE; DIMERIZATION;
D O I
10.1002/chem.201103972
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Salts that contain radical cations of benzidine (BZ), 3,3',5,5'-tetramethylbenzidine (TMB), 2,2',6,6'-tetraisopropylbenzidine (TPB), and 4,4'-terphenyldiamine (DATP) have been isolated with weakly coordinating anions [Al(ORF)4]- (ORF=OC(CF3)3) or SbF6-. They were prepared by reaction of the respective silver(I) salts with stoichiometric amounts of benzidine or its alkyl-substituted derivatives in CH2Cl2. The salts were characterized by UV absorption and EPR spectroscopy as well as by their single-crystal X-ray structures. Variable-temperature UV/Vis absorption spectra of BZ.+[Al(ORF)4]- and TMB.+[Al(ORF)4]- in acetonitrile indicate an equilibrium between monomeric free radical cations and a radical-cation dimer. In contrast, the absorption spectrum of TPB.+SbF6- in acetonitrile indicates that the oxidation of TPB only resulted in a monomeric radical cation. Single-crystal X-ray diffraction studies show that in the solid state BZ and its methylation derivative (TMB) form radical-cation p dimers upon oxidation, whereas that modified with isopropyl groups (TPB) becomes a monomeric free radical cation. By increasing the chain length, p stacks of p dimers are obtained for the radical cation of DATP. The single-crystal conductivity measurements show that monomerized or p-dimerized radicals (BZ.+, TMB.+, and TPB.+) are nonconductive, whereas the p-stacked radical (DATP.+) is conductive. A conduction mechanism between chains through p stacks is proposed.
引用
收藏
页码:11828 / 11836
页数:9
相关论文
共 68 条
[31]   Accurate Simulation of Optical Properties in Dyes [J].
Jacquemin, Denis ;
Perpete, Eric A. ;
Ciofini, Ilaria ;
Adamo, Carlo .
ACCOUNTS OF CHEMICAL RESEARCH, 2009, 42 (02) :326-334
[32]  
Jalilov A. S., 2011, ANGEW CHEM, V123, P6992
[33]   Intramolecular π-Stacking Interactions of Bridged Bis-p-Phenylenediamine Radical Cations and Diradical Dications: Charge-Transfer versus Spin-Coupling [J].
Jalilov, Almaz S. ;
Nelsen, Stephen F. ;
Guzei, Ilia A. ;
Wu, Qin .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (30) :6860-6863
[34]   Solution and Solid-State Studies of Doubly Trimethylene-Bridged Tetraalkyl p-Phenylenediamine Diradical Dication Conformations [J].
Jalilov, Almaz S. ;
Li, Gaoquan ;
Nelsen, Stephen F. ;
Guzei, Ilia A. ;
Wu, Qin .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (17) :6176-6182
[35]   Balancing Redox Activity Allowing Spectrophotometric Detection of Au(I) Using Tetramethylbenzidine Dihydrochloride [J].
Jang, Gyoung-Gug ;
Roper, D. Keith .
ANALYTICAL CHEMISTRY, 2011, 83 (05) :1836-1842
[36]  
JOSEPHY PD, 1982, J BIOL CHEM, V257, P3669
[37]  
JOSEPHY PD, 1983, MOL PHARMACOL, V23, P766
[38]  
JOSEPHY PD, 1982, CANCER RES, V42, P2567
[39]  
Kallmayer H. J., 2003, SCI PHARM, V71, P263
[40]   BENZIDINE AND DIPHENYLAMINE RADICAL FORMATION ON THE SURFACE OF NAY-ZEOLITE AND GAMMA-ALUMINA WITH AND WITHOUT V2O5 [J].
KHULBE, KC ;
MANN, RS .
REACTION KINETICS AND CATALYSIS LETTERS, 1995, 56 (01) :63-68