TY - JOUR
T1 - Tetranuclear Uranyl Polyrotaxanes
T2 - Preferred Selectivity toward Uranyl Tetramer for Stabilizing a Flexible Polyrotaxane Chain Exhibiting Weakened Supramolecular Inclusion
AU - Mei, Lei
AU - Wang, Lin
AU - Liu, Cai Ming
AU - Zhao, Yu Liang
AU - Chai, Zhi Fang
AU - Shi, Wei Qun
N1 - Publisher Copyright:
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2015/7/1
Y1 - 2015/7/1
N2 - Introduction of mechanically interlocked components into actinide-based metal-organic materials such as polyrotaxanes will generate an entirely new type of inorganic-organic hybrid materials showing more supramolecular encapsulation-based dynamics. In this work, tetranuclear uranyl-directed polyrotaxanes (UO2)4O2-C5A3-CB6 (1) and (UO2)4O2-C6A3-CB6 (2), which are the first actinide pseudorotaxanes with high-nuclearity uranium centers, were obtained through systematic extension of the string spacer in pseudorotaxane ligands from 1,4-butylene (C4) to 1,5-pentylene (C5) and 1,6-hexylene (C6). Both of the as-synthesized tetranuclear uranyl polyrotaxanes were structurally characterized and analyzed. Considering the structure of UO2-C4A3-CB6 and the 1,4-butylene string spacer, the preference for the uranyl tetramer may be related to the configurational inversion of the pseudorotaxane ligands from trans mode to cis mode on coordination to the uranyl center. Detailed structural analysis suggests that the length of the stretched string molecules for CB6-encapsulated pseudorotaxanes has remarkable effect on the supramolecular inclusion interactions and the configurations of pseudorotaxanes, and should be responsible for the configurational inversion of pseudorotaxane spacers and subsequent distinct changes of the uranyl building units and geometric structures.
AB - Introduction of mechanically interlocked components into actinide-based metal-organic materials such as polyrotaxanes will generate an entirely new type of inorganic-organic hybrid materials showing more supramolecular encapsulation-based dynamics. In this work, tetranuclear uranyl-directed polyrotaxanes (UO2)4O2-C5A3-CB6 (1) and (UO2)4O2-C6A3-CB6 (2), which are the first actinide pseudorotaxanes with high-nuclearity uranium centers, were obtained through systematic extension of the string spacer in pseudorotaxane ligands from 1,4-butylene (C4) to 1,5-pentylene (C5) and 1,6-hexylene (C6). Both of the as-synthesized tetranuclear uranyl polyrotaxanes were structurally characterized and analyzed. Considering the structure of UO2-C4A3-CB6 and the 1,4-butylene string spacer, the preference for the uranyl tetramer may be related to the configurational inversion of the pseudorotaxane ligands from trans mode to cis mode on coordination to the uranyl center. Detailed structural analysis suggests that the length of the stretched string molecules for CB6-encapsulated pseudorotaxanes has remarkable effect on the supramolecular inclusion interactions and the configurations of pseudorotaxanes, and should be responsible for the configurational inversion of pseudorotaxane spacers and subsequent distinct changes of the uranyl building units and geometric structures.
KW - chain structures
KW - organic-inorganic hybrid composites
KW - rotaxanes
KW - supramolecular chemistry
KW - uranium
UR - http://www.scopus.com/inward/record.url?scp=84933498762&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84933498762&partnerID=8YFLogxK
U2 - 10.1002/chem.201500343
DO - 10.1002/chem.201500343
M3 - Article
AN - SCOPUS:84933498762
SN - 0947-6539
VL - 21
SP - 10226
EP - 10235
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 28
ER -