A MOLECULAR MERRY-GO-ROUND - MOTION OF THE LARGE MACROCYCLIC MOLECULE 18-CROWN-6 IN ITS SOLID COMPLEXES STUDIED BY H-2 NMR

被引:45
作者
RATCLIFFE, CI [1 ]
RIPMEESTER, JA [1 ]
BUCHANAN, GW [1 ]
DENIKE, JK [1 ]
机构
[1] CARLETON UNIV,OTTAWA CARLETON CHEM INST,OTTAWA K1S 5B6,ONTARIO,CANADA
关键词
D O I
10.1021/ja00035a021
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
H-2 NMR line shape measurements were used to confirm and refine a model to account for large-amplitude motions in solid 18-crown-6 complexes previously identified from C-13 and H-1 NMR results. Reminiscent of the motion of a merry-go-round, the motion is a combined rotation and conformational adjustment of the macrocycle, in which individual -OCH2CH2- units jump to adjacent sites in the crystal. Specifically, for the malononitrile complex, 18-crown-6.2CH2(CN)2, jump rates were obtained by modeling the intermediate-rate line shapes, yielding an activation energy of 47.6 +/- 0.8 kJ/mol. Because the motion does not introduce disorder, it is diffraction invisible.
引用
收藏
页码:3294 / 3299
页数:6
相关论文
共 31 条
[1]   A NEW TECHNIQUE TO CALCULATE LOW-ENERGY CONFORMATIONS OF CYCLIC MOLECULES UTILIZING THE ELLIPSOID ALGORITHM AND MOLECULAR-DYNAMICS - APPLICATION TO 18-CROWN-6 [J].
BILLETER, M ;
HOWARD, AE ;
KUNTZ, ID ;
KOLLMAN, PA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (25) :8385-8391
[2]   SOLID-PHASE STEREOCHEMICAL DYNAMICS OF 18-CROWN-6 ETHER AND ITS KNCS COMPLEX AS STUDIED BY LOW-TEMPERATURE C-13 NUCLEAR-MAGNETIC-RESONANCE [J].
BUCHANAN, GW ;
KIRBY, RA ;
RIPMEESTER, JA ;
RATCLIFFE, CI .
TETRAHEDRON LETTERS, 1987, 28 (41) :4783-4786
[3]   MACROCYCLE REORIENTATION IN SOLID 18-CROWN-6 COMPLEXES DETECTED BY H-1 AND C-13 NMR-SPECTROSCOPY [J].
BUCHANAN, GW ;
MORAT, C ;
RATCLIFFE, CI ;
RIPMEESTER, JA .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (18) :1306-1308
[4]   CYCLIC OLIGO-ETHERS RELATED TO ETHYLENE OXIDE [J].
DALE, J ;
KRISTIANSEN, PO .
JOURNAL OF THE CHEMICAL SOCIETY D-CHEMICAL COMMUNICATIONS, 1971, (13) :670-+
[5]   QUADRUPOLAR ECHO DEUTERON MAGNETIC-RESONANCE SPECTROSCOPY IN ORDERED HYDROCARBON CHAINS [J].
DAVIS, JH ;
JEFFREY, KR ;
BLOOM, M ;
VALIC, MI ;
HIGGS, TP .
CHEMICAL PHYSICS LETTERS, 1976, 42 (02) :390-394
[6]   MESOMORPHIC STATE OF CYCLOTETRADECANE [J].
DROTLOFF, H ;
ROTTER, H ;
EMEIS, D ;
MOLLER, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (25) :7797-7803
[7]   CHAIN FOLDING AND MESOMORPHIC STATES OF CYCLOALKANES [J].
DROTLOFF, H ;
EMEIS, D ;
WALDRON, RF ;
MOLLER, M .
POLYMER, 1987, 28 (07) :1200-1206
[8]  
DUNITZ JD, 1974, ACTA CRYSTALLOGR B, V30, P2739, DOI 10.1107/S0567740874007928
[9]   CONCERNING THE CRYSTAL-STRUCTURE OF PORPHINE - A PROTON PULSED AND C-13 CPMAS NMR-STUDY [J].
FRYDMAN, L ;
OLIVIERI, AC ;
DIAZ, LE ;
FRYDMAN, B ;
KUSTANOVICH, I ;
VEGA, S .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (18) :7001-7005
[10]   NUCLEAR MAGNETIC RESONANCE INVESTIGATION OF POSSIBLE MOLECULAR MOTION IN CORONENE, PERYLENE, AND TRIPHENYLENE IN SOLID STATE [J].
FYFE, CA ;
DUNELL, BA ;
RIPMEESTER, J .
CANADIAN JOURNAL OF CHEMISTRY-BACK YEAR, 1971, 49 (20) :3332-+