Spectroscopic study in the UV-Vis, near and mid IR of cationic species formed by interaction of thiophene, dithiophene and terthiophene with the zeolite H-Y

被引:51
作者
Geobaldo, F
Palomino, GT
Bordiga, S
Zecchina, A
Areán, CO
机构
[1] Politecn Torino, Dipartimento Sci Mat & Ingn Chim, I-10129 Turin, Italy
[2] Univ Turin, Dipartimento Chim Inorgan Chim Fis & Chim Mat, I-10125 Turin, Italy
[3] Univ Balearic Isl, Dept Quim, E-07071 Palma de Mallorca, Spain
关键词
D O I
10.1039/a807353h
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The vibrational (in the mid-IR and near-IR) and the UV-Vis spectra of products formed upon interaction of thiophene with H-Y, show the initial formation of neutral hydrogen bonded adducts. In the presence of thiophene excess, protonation slowly occurs with formation of C(4)H(5)S(+) followed by oligomerization leading to C(8)H(7)S(2)(+), C(12)H(9)S(3)(+) and more complex species. This conclusion is fully confirmed by the study of the direct interaction of H-Y with dithiophene and terthiophene, where protonated C(8)H(7)S(2)(+) and C(12)H(9)S(3)(+) are produced in the initial interaction stages. The ascertained occurrence of intramolecular and intermolecular hydrogen transfer points towards a network of complex reactions leading to the final formation of some families of similar isomers. Some of the protonated (oligomeric) species interact via strong hydrogen bonds with the unreacted Bronsted groups of H-Y. The positively charged species can easily react with NH, with the formation of NH(4)(+) and neutral species. At room temperature the process is partially reversible.
引用
收藏
页码:561 / 569
页数:9
相关论文
共 52 条
[31]   SPECTROSCOPIC STUDIES OF PROTONATED AROMATIC SPECIES AND RADICAL CATIONS IN H+-ZEOLITES [J].
LIU, XS ;
IU, KK ;
THOMAS, JK ;
HE, HY ;
KLINOWSKI, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (26) :11811-11818
[32]   POLYANILINE - INTERCONVERSION OF METALLIC AND INSULATING FORMS [J].
MACDIARMID, AG ;
CHIANG, JC ;
HALPERN, M ;
HUANG, WS ;
MU, SL ;
SOMASIRI, NLD ;
WU, WQ ;
YANIGER, SI .
MOLECULAR CRYSTALS AND LIQUID CRYSTALS, 1985, 121 (1-4) :173-180
[33]   NONLINEAR-OPTICAL POLYMERS - DISCOVERY TO MARKET IN 10 YEARS [J].
MARDER, SR ;
FERRY, JW .
SCIENCE, 1994, 263 (5154) :1706-1707
[34]   COMPOSITE POLYMER POSITIVE ELECTRODES IN SOLID-STATE LITHIUM SECONDARY BATTERIES [J].
NOVAK, P ;
INGANAS, O ;
BJORKLUND, R .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1987, 134 (06) :1341-1345
[35]   Spectroscopic characterization of hydroxyl groups in SAPO-40 .1. Study of the template-free samples and their interaction with ammonia [J].
Onida, B ;
Gabelica, Z ;
Lourenco, J ;
Garrone, E .
JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (26) :11072-11079
[36]   IR study of the adsorption of unsaturated hydrocarbons on highly outgassed silica: Spectroscopic and thermodynamic results [J].
Onida, B ;
Allian, M ;
Borello, E ;
Ugliengo, P ;
Garrone, E .
LANGMUIR, 1997, 13 (19) :5107-5113
[37]   NANOCHEMISTRY - SYNTHESIS IN DIMINISHING DIMENSIONS [J].
OZIN, GA .
ADVANCED MATERIALS, 1992, 4 (10) :612-649
[38]   MODIFICATION OF PHOTOCHEMICAL REACTIVITY BY ZEOLITES - GENERATION, ENTRAPMENT, AND SPECTROSCOPIC CHARACTERIZATION OF RADICAL CATIONS OF ALPHA-OMEGA-DIPHENYL POLYENES WITHIN THE CHANNELS OF PENTASIL ZEOLITES [J].
RAMAMURTHY, V ;
CASPAR, JV ;
CORBIN, DR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (02) :594-600
[39]   CONDUCTING POLYMERS INTERCALATED IN LAYERED SOLIDS [J].
RUIZHITZKY, E .
ADVANCED MATERIALS, 1993, 5 (05) :334-340
[40]   NANOCOMPOSITE MATERIALS WITH CONTROLLED ION MOBILITY [J].
RUIZHITZKY, E ;
ARANDA, P ;
CASAL, B ;
GALVAN, JC .
ADVANCED MATERIALS, 1995, 7 (02) :180-184