TY - JOUR
T1 - A Calix[4]arene Carceplex with Four Rh24+ Fasteners
AU - Cotton, F. Albert
AU - Lei, Peng
AU - Lin, Chun
AU - Murillo, Carlos A.
AU - Wang, Xiaoping
AU - Yu, Shu Yan
AU - Zhang, Zhong Xing
PY - 2004/2/11
Y1 - 2004/2/11
N2 - It is shown that a spheroidal carceplex can be assembled by linking two bowl-shaped calix[4]-arenes via four dimetal units, (DAniF)2Rh 2 (DAniF = N, N′-di-p-anisylformamidinate), with a molecule (diethyl ether) or a cation (tetraethylammonium ion) trapped inside. The tetraethylammonium carceplex, 1b, has been characterized by X-ray crystallography, 1H NMR, IR, and mass spectrometry. The tetraethylammonium ion fits snugly in the interior of the spheroidal carceplex. A two-fold axis of the tetrahedral cation coincides with the idealized four-fold axis of the cage, and the cation is disordered over two rotational orientations. Only one axial position on each dirhodium unit is occupied by a ligand, CH3CN or H2O. The carceplex is very stable, and the axial ligands can be exchanged in single crystals without disrupting the crystallinity of the samples. In this way, a red crystal of the complex with all axial positions occupied by acetonitrile can be transformed to a green crystal of the complex with two axial positions having acetonitrile and the other two having water by simply putting the crystal in contact with distilled water. The calix[4]arene used to make the carciplex structure is 25,26,27,28-tetra-n-propoxycalix[4]arene-5,11,17,23-tetracarboxylic acid. By employing 25,26,27,28-tetrapropoxy-5,17-dibromo-calix[4]arene-11, 23-dicarboxylic acid, two 1:1 dimetal: calixarene compounds have also been made and characterized: 2, cis-Rh2(DAniF)2(calix)(CH 3OH), and 3, cis-Mo2(DAniF)2(calix). The Rh-Rh distances in lb are in the range of 2.410(2)-2.428(2) Å, that in 2 is 2.4383(4) Å, and the Mo-Mo distance in 3 is 2.0931(4) Å.
AB - It is shown that a spheroidal carceplex can be assembled by linking two bowl-shaped calix[4]-arenes via four dimetal units, (DAniF)2Rh 2 (DAniF = N, N′-di-p-anisylformamidinate), with a molecule (diethyl ether) or a cation (tetraethylammonium ion) trapped inside. The tetraethylammonium carceplex, 1b, has been characterized by X-ray crystallography, 1H NMR, IR, and mass spectrometry. The tetraethylammonium ion fits snugly in the interior of the spheroidal carceplex. A two-fold axis of the tetrahedral cation coincides with the idealized four-fold axis of the cage, and the cation is disordered over two rotational orientations. Only one axial position on each dirhodium unit is occupied by a ligand, CH3CN or H2O. The carceplex is very stable, and the axial ligands can be exchanged in single crystals without disrupting the crystallinity of the samples. In this way, a red crystal of the complex with all axial positions occupied by acetonitrile can be transformed to a green crystal of the complex with two axial positions having acetonitrile and the other two having water by simply putting the crystal in contact with distilled water. The calix[4]arene used to make the carciplex structure is 25,26,27,28-tetra-n-propoxycalix[4]arene-5,11,17,23-tetracarboxylic acid. By employing 25,26,27,28-tetrapropoxy-5,17-dibromo-calix[4]arene-11, 23-dicarboxylic acid, two 1:1 dimetal: calixarene compounds have also been made and characterized: 2, cis-Rh2(DAniF)2(calix)(CH 3OH), and 3, cis-Mo2(DAniF)2(calix). The Rh-Rh distances in lb are in the range of 2.410(2)-2.428(2) Å, that in 2 is 2.4383(4) Å, and the Mo-Mo distance in 3 is 2.0931(4) Å.
UR - http://www.scopus.com/inward/record.url?scp=1042288170&partnerID=8YFLogxK
U2 - 10.1021/ja0396899
DO - 10.1021/ja0396899
M3 - Article
AN - SCOPUS:1042288170
SN - 0002-7863
VL - 126
SP - 1518
EP - 1525
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 5
ER -