Rotaxane building blocks bearing blocked isocyanate stoppers: Polyrotaxanes through post-assembly chain extension

Angewandte Chemie - International Edition

Volumn 42, Issue 29, 2003, Pages 3379-3383

  Kidd, Timothy J ^a   Loontjens, Ton J A ^a   Leigh, David A ^b   Wong, Jenny K Y ^b  

^a DSM RESEARCH   (Netherlands)

^b UNIVERSITY OF EDINBURGH   (United Kingdom)

Author keywords

Polymers; Polyrotaxanes; Rotaxanes; Template synthesis

Indexed keywords

MONOMERS; POLYMERIZATION; SYNTHESIS (CHEMICAL); TOPOLOGY;

BUILDING BLOCKS;

POLYMERS;

FUNCTIONAL GROUP; ISOCYANATE; MONOMER; POLYMER; POLYROTAXANE; ROTAXANE; UNCLASSIFIED DRUG;

ARTICLE; MOLECULAR SIZE; MOLECULAR STABILITY; POLYMERIZATION; REACTION ANALYSIS; SYNTHESIS;

EID: 0042530480     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200351458     Document Type: Article

References (47)

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23. For other examples of post-assembly elaboration of rotaxanes, see: a) M. P. L. Werts, M. van der Boogaard, G. Hadziioannou, G. M. Tsivgoulis, Chem. Commun. 1999, 623-624; b) S. J. Rowan, S. J. Cantrill, J. F. Stoddart, A. J. P. White, D. J. Williams, Org. Lett. 2000, 2, 759-762; c) S. J. Rowan, J. F. Stoddart, J. Am. Chem. Soc. 2000, 122, 164-165; d) D. W. Zehnder, D. B. Smithrud, Org. Lett. 2001, 3, 2485-2487; e) S.-H. Chiu, S. J. Rowan, S. J. Cantrill, J. F. Stoddart, A. J. P. White, D. J. Williams, Chem. Eur. J. 2002, 8, 5170-5183; f) S.-H. Chiu, S. J. Rowan, S. J. Cantrill, L. Ridvan, P. R. Ashton, R. L. Garrell, J. F. Stoddart, Tetrahedron 2002, 58, 807-814.
24. For other examples of post-assembly elaboration of rotaxanes, see: a) M. P. L. Werts, M. van der Boogaard, G. Hadziioannou, G. M. Tsivgoulis, Chem. Commun. 1999, 623-624; b) S. J. Rowan, S. J. Cantrill, J. F. Stoddart, A. J. P. White, D. J. Williams, Org. Lett. 2000, 2, 759-762; c) S. J. Rowan, J. F. Stoddart, J. Am. Chem. Soc. 2000, 122, 164-165; d) D. W. Zehnder, D. B. Smithrud, Org. Lett. 2001, 3, 2485-2487; e) S.-H. Chiu, S. J. Rowan, S. J. Cantrill, J. F. Stoddart, A. J. P. White, D. J. Williams, Chem. Eur. J. 2002, 8, 5170-5183; f) S.-H. Chiu, S. J. Rowan, S. J. Cantrill, L. Ridvan, P. R. Ashton, R. L. Garrell, J. F. Stoddart, Tetrahedron 2002, 58, 807-814.
25. For other examples of post-assembly elaboration of rotaxanes, see: a) M. P. L. Werts, M. van der Boogaard, G. Hadziioannou, G. M. Tsivgoulis, Chem. Commun. 1999, 623-624; b) S. J. Rowan, S. J. Cantrill, J. F. Stoddart, A. J. P. White, D. J. Williams, Org. Lett. 2000, 2, 759-762; c) S. J. Rowan, J. F. Stoddart, J. Am. Chem. Soc. 2000, 122, 164-165; d) D. W. Zehnder, D. B. Smithrud, Org. Lett. 2001, 3, 2485-2487; e) S.-H. Chiu, S. J. Rowan, S. J. Cantrill, J. F. Stoddart, A. J. P. White, D. J. Williams, Chem. Eur. J. 2002, 8, 5170-5183; f) S.-H. Chiu, S. J. Rowan, S. J. Cantrill, L. Ridvan, P. R. Ashton, R. L. Garrell, J. F. Stoddart, Tetrahedron 2002, 58, 807-814.
26. For other examples of post-assembly elaboration of rotaxanes, see: a) M. P. L. Werts, M. van der Boogaard, G. Hadziioannou, G. M. Tsivgoulis, Chem. Commun. 1999, 623-624; b) S. J. Rowan, S. J. Cantrill, J. F. Stoddart, A. J. P. White, D. J. Williams, Org. Lett. 2000, 2, 759-762; c) S. J. Rowan, J. F. Stoddart, J. Am. Chem. Soc. 2000, 122, 164-165; d) D. W. Zehnder, D. B. Smithrud, Org. Lett. 2001, 3, 2485-2487; e) S.-H. Chiu, S. J. Rowan, S. J. Cantrill, J. F. Stoddart, A. J. P. White, D. J. Williams, Chem. Eur. J. 2002, 8, 5170-5183; f) S.-H. Chiu, S. J. Rowan, S. J. Cantrill, L. Ridvan, P. R. Ashton, R. L. Garrell, J. F. Stoddart, Tetrahedron 2002, 58, 807-814.
27. For other examples of post-assembly elaboration of rotaxanes, see: a) M. P. L. Werts, M. van der Boogaard, G. Hadziioannou, G. M. Tsivgoulis, Chem. Commun. 1999, 623-624; b) S. J. Rowan, S. J. Cantrill, J. F. Stoddart, A. J. P. White, D. J. Williams, Org. Lett. 2000, 2, 759-762; c) S. J. Rowan, J. F. Stoddart, J. Am. Chem. Soc. 2000, 122, 164-165; d) D. W. Zehnder, D. B. Smithrud, Org. Lett. 2001, 3, 2485-2487; e) S.-H. Chiu, S. J. Rowan, S. J. Cantrill, J. F. Stoddart, A. J. P. White, D. J. Williams, Chem. Eur. J. 2002, 8, 5170-5183; f) S.-H. Chiu, S. J. Rowan, S. J. Cantrill, L. Ridvan, P. R. Ashton, R. L. Garrell, J. F. Stoddart, Tetrahedron 2002, 58, 807-814.
28. For other examples of post-assembly elaboration of rotaxanes, see: a) M. P. L. Werts, M. van der Boogaard, G. Hadziioannou, G. M. Tsivgoulis, Chem. Commun. 1999, 623-624; b) S. J. Rowan, S. J. Cantrill, J. F. Stoddart, A. J. P. White, D. J. Williams, Org. Lett. 2000, 2, 759-762; c) S. J. Rowan, J. F. Stoddart, J. Am. Chem. Soc. 2000, 122, 164-165; d) D. W. Zehnder, D. B. Smithrud, Org. Lett. 2001, 3, 2485-2487; e) S.-H. Chiu, S. J. Rowan, S. J. Cantrill, J. F. Stoddart, A. J. P. White, D. J. Williams, Chem. Eur. J. 2002, 8, 5170-5183; f) S.-H. Chiu, S. J. Rowan, S. J. Cantrill, L. Ridvan, P. R. Ashton, R. L. Garrell, J. F. Stoddart, Tetrahedron 2002, 58, 807-814.
29. Other approaches for controlling the macrocycle:thread repeat-unit stoichiometry in polyrotaxanes include a) the polymerization of monomer threads containing bulky blocking groups [I. Yamaguchi, K. Osakada, T. Yamamoto, J. Am. Chem. Soc. 1996, 118, 1811-1812; C. Gong, T. E. Glass, H. W. Gibson, Macromolecules 1998, 31, 308-313; C. Gong, H. W. Gibson, Angew. Chem. 1997, 109, 2426-2428; Angew. Chem. Int. Ed. Engl. 1997, 36, 2331-2333; M. B. Steinbrunn, G. Wenz, Angew, Chem. 1996, 108, 2274-2277; Angew. Chem. Int. Ed. Engl. 1996, 35, 2139-2141] and/or initiators [H. W. Gibson, P. T. Engen, S. H. Lee, Polymer 1999, 40, 1823-1832] in the presence of a macrocycle; b) the formation of a pseudorotaxane coordination polymer [D. Whang, Y.-M. Yeon, J. Heo, K. Kim, J. Am. Chem. Soc. 1996, 118, 11333-11334; D. Whang, K. Kim, J. Am. Chem. Soc. 1997, 119, 451-452; E. Lee, J. Heo, K. Kim, Angew. Chem. 2000, 112, 2814-2819; Angew. Chem. Int. Ed. 2000, 39, 2699-2701]; and c) the catalytic polymerization of monomer threads where the threaded macrocycle itself acts as the catalyst to polymer formation [D. Tuncel, J. H. G. Steinke, Chem. Commun. 1999, 1509-1510].
30. Other approaches for controlling the macrocycle:thread repeat-unit stoichiometry in polyrotaxanes include a) the polymerization of monomer threads containing bulky blocking groups [I. Yamaguchi, K. Osakada, T. Yamamoto, J. Am. Chem. Soc. 1996, 118, 1811-1812; C. Gong, T. E. Glass, H. W. Gibson, Macromolecules 1998, 31, 308-313; C. Gong, H. W. Gibson, Angew. Chem. 1997, 109, 2426-2428; Angew. Chem. Int. Ed. Engl. 1997, 36, 2331-2333; M. B. Steinbrunn, G. Wenz, Angew, Chem. 1996, 108, 2274-2277; Angew. Chem. Int. Ed. Engl. 1996, 35, 2139-2141] and/or initiators [H. W. Gibson, P. T. Engen, S. H. Lee, Polymer 1999, 40, 1823-1832] in the presence of a macrocycle; b) the formation of a pseudorotaxane coordination polymer [D. Whang, Y.-M. Yeon, J. Heo, K. Kim, J. Am. Chem. Soc. 1996, 118, 11333-11334; D. Whang, K. Kim, J. Am. Chem. Soc. 1997, 119, 451-452; E. Lee, J. Heo, K. Kim, Angew. Chem. 2000, 112, 2814-2819; Angew. Chem. Int. Ed. 2000, 39, 2699-2701]; and c) the catalytic polymerization of monomer threads where the threaded macrocycle itself acts as the catalyst to polymer formation [D. Tuncel, J. H. G. Steinke, Chem. Commun. 1999, 1509-1510].
31. Other approaches for controlling the macrocycle:thread repeat-unit stoichiometry in polyrotaxanes include a) the polymerization of monomer threads containing bulky blocking groups [I. Yamaguchi, K. Osakada, T. Yamamoto, J. Am. Chem. Soc. 1996, 118, 1811-1812; C. Gong, T. E. Glass, H. W. Gibson, Macromolecules 1998, 31, 308-313; C. Gong, H. W. Gibson, Angew. Chem. 1997, 109, 2426-2428; Angew. Chem. Int. Ed. Engl. 1997, 36, 2331-2333; M. B. Steinbrunn, G. Wenz, Angew, Chem. 1996, 108, 2274-2277; Angew. Chem. Int. Ed. Engl. 1996, 35, 2139-2141] and/or initiators [H. W. Gibson, P. T. Engen, S. H. Lee, Polymer 1999, 40, 1823-1832] in the presence of a macrocycle; b) the formation of a pseudorotaxane coordination polymer [D. Whang, Y.-M. Yeon, J. Heo, K. Kim, J. Am. Chem. Soc. 1996, 118, 11333-11334; D. Whang, K. Kim, J. Am. Chem. Soc. 1997, 119, 451-452; E. Lee, J. Heo, K. Kim, Angew. Chem. 2000, 112, 2814-2819; Angew. Chem. Int. Ed. 2000, 39, 2699-2701]; and c) the catalytic polymerization of monomer threads where the threaded macrocycle itself acts as the catalyst to polymer formation [D. Tuncel, J. H. G. Steinke, Chem. Commun. 1999, 1509-1510].
32. Other approaches for controlling the macrocycle:thread repeat-unit stoichiometry in polyrotaxanes include a) the polymerization of monomer threads containing bulky blocking groups [I. Yamaguchi, K. Osakada, T. Yamamoto, J. Am. Chem. Soc. 1996, 118, 1811-1812; C. Gong, T. E. Glass, H. W. Gibson, Macromolecules 1998, 31, 308-313; C. Gong, H. W. Gibson, Angew. Chem. 1997, 109, 2426-2428; Angew. Chem. Int. Ed. Engl. 1997, 36, 2331-2333; M. B. Steinbrunn, G. Wenz, Angew, Chem. 1996, 108, 2274-2277; Angew. Chem. Int. Ed. Engl. 1996, 35, 2139-2141] and/or initiators [H. W. Gibson, P. T. Engen, S. H. Lee, Polymer 1999, 40, 1823-1832] in the presence of a macrocycle; b) the formation of a pseudorotaxane coordination polymer [D. Whang, Y.-M. Yeon, J. Heo, K. Kim, J. Am. Chem. Soc. 1996, 118, 11333-11334; D. Whang, K. Kim, J. Am. Chem. Soc. 1997, 119, 451-452; E. Lee, J. Heo, K. Kim, Angew. Chem. 2000, 112, 2814-2819; Angew. Chem. Int. Ed. 2000, 39, 2699-2701]; and c) the catalytic polymerization of monomer threads where the threaded macrocycle itself acts as the catalyst to polymer formation [D. Tuncel, J. H. G. Steinke, Chem. Commun. 1999, 1509-1510].
33. Other approaches for controlling the macrocycle:thread repeat-unit stoichiometry in polyrotaxanes include a) the polymerization of monomer threads containing bulky blocking groups [I. Yamaguchi, K. Osakada, T. Yamamoto, J. Am. Chem. Soc. 1996, 118, 1811-1812; C. Gong, T. E. Glass, H. W. Gibson, Macromolecules 1998, 31, 308-313; C. Gong, H. W. Gibson, Angew. Chem. 1997, 109, 2426-2428; Angew. Chem. Int. Ed. Engl. 1997, 36, 2331-2333; M. B. Steinbrunn, G. Wenz, Angew, Chem. 1996, 108, 2274-2277; Angew. Chem. Int. Ed. Engl. 1996, 35, 2139-2141] and/or initiators [H. W. Gibson, P. T. Engen, S. H. Lee, Polymer 1999, 40, 1823-1832] in the presence of a macrocycle; b) the formation of a pseudorotaxane coordination polymer [D. Whang, Y.-M. Yeon, J. Heo, K. Kim, J. Am. Chem. Soc. 1996, 118, 11333-11334; D. Whang, K. Kim, J. Am. Chem. Soc. 1997, 119, 451-452; E. Lee, J. Heo, K. Kim, Angew. Chem. 2000, 112, 2814-2819; Angew. Chem. Int. Ed. 2000, 39, 2699-2701]; and c) the catalytic polymerization of monomer threads where the threaded macrocycle itself acts as the catalyst to polymer formation [D. Tuncel, J. H. G. Steinke, Chem. Commun. 1999, 1509-1510].
34. Other approaches for controlling the macrocycle:thread repeat-unit stoichiometry in polyrotaxanes include a) the polymerization of monomer threads containing bulky blocking groups [I. Yamaguchi, K. Osakada, T. Yamamoto, J. Am. Chem. Soc. 1996, 118, 1811-1812; C. Gong, T. E. Glass, H. W. Gibson, Macromolecules 1998, 31, 308-313; C. Gong, H. W. Gibson, Angew. Chem. 1997, 109, 2426-2428; Angew. Chem. Int. Ed. Engl. 1997, 36, 2331-2333; M. B. Steinbrunn, G. Wenz, Angew, Chem. 1996, 108, 2274-2277; Angew. Chem. Int. Ed. Engl. 1996, 35, 2139-2141] and/or initiators [H. W. Gibson, P. T. Engen, S. H. Lee, Polymer 1999, 40, 1823-1832] in the presence of a macrocycle; b) the formation of a pseudorotaxane coordination polymer [D. Whang, Y.-M. Yeon, J. Heo, K. Kim, J. Am. Chem. Soc. 1996, 118, 11333-11334; D. Whang, K. Kim, J. Am. Chem. Soc. 1997, 119, 451-452; E. Lee, J. Heo, K. Kim, Angew. Chem. 2000, 112, 2814-2819; Angew. Chem. Int. Ed. 2000, 39, 2699-2701]; and c) the catalytic polymerization of monomer threads where the threaded macrocycle itself acts as the catalyst to polymer formation [D. Tuncel, J. H. G. Steinke, Chem. Commun. 1999, 1509-1510].
35. Other approaches for controlling the macrocycle:thread repeat-unit stoichiometry in polyrotaxanes include a) the polymerization of monomer threads containing bulky blocking groups [I. Yamaguchi, K. Osakada, T. Yamamoto, J. Am. Chem. Soc. 1996, 118, 1811-1812; C. Gong, T. E. Glass, H. W. Gibson, Macromolecules 1998, 31, 308-313; C. Gong, H. W. Gibson, Angew. Chem. 1997, 109, 2426-2428; Angew. Chem. Int. Ed. Engl. 1997, 36, 2331-2333; M. B. Steinbrunn, G. Wenz, Angew, Chem. 1996, 108, 2274-2277; Angew. Chem. Int. Ed. Engl. 1996, 35, 2139-2141] and/or initiators [H. W. Gibson, P. T. Engen, S. H. Lee, Polymer 1999, 40, 1823-1832] in the presence of a macrocycle; b) the formation of a pseudorotaxane coordination polymer [D. Whang, Y.-M. Yeon, J. Heo, K. Kim, J. Am. Chem. Soc. 1996, 118, 11333-11334; D. Whang, K. Kim, J. Am. Chem. Soc. 1997, 119, 451-452; E. Lee, J. Heo, K. Kim, Angew. Chem. 2000, 112, 2814-2819; Angew. Chem. Int. Ed. 2000, 39, 2699-2701]; and c) the catalytic polymerization of monomer threads where the threaded macrocycle itself acts as the catalyst to polymer formation [D. Tuncel, J. H. G. Steinke, Chem. Commun. 1999, 1509-1510].
36. Other approaches for controlling the macrocycle:thread repeat-unit stoichiometry in polyrotaxanes include a) the polymerization of monomer threads containing bulky blocking groups [I. Yamaguchi, K. Osakada, T. Yamamoto, J. Am. Chem. Soc. 1996, 118, 1811-1812; C. Gong, T. E. Glass, H. W. Gibson, Macromolecules 1998, 31, 308-313; C. Gong, H. W. Gibson, Angew. Chem. 1997, 109, 2426-2428; Angew. Chem. Int. Ed. Engl. 1997, 36, 2331-2333; M. B. Steinbrunn, G. Wenz, Angew, Chem. 1996, 108, 2274-2277; Angew. Chem. Int. Ed. Engl. 1996, 35, 2139-2141] and/or initiators [H. W. Gibson, P. T. Engen, S. H. Lee, Polymer 1999, 40, 1823-1832] in the presence of a macrocycle; b) the formation of a pseudorotaxane coordination polymer [D. Whang, Y.-M. Yeon, J. Heo, K. Kim, J. Am. Chem. Soc. 1996, 118, 11333-11334; D. Whang, K. Kim, J. Am. Chem. Soc. 1997, 119, 451-452; E. Lee, J. Heo, K. Kim, Angew. Chem. 2000, 112, 2814-2819; Angew. Chem. Int. Ed. 2000, 39, 2699-2701]; and c) the catalytic polymerization of monomer threads where the threaded macrocycle itself acts as the catalyst to polymer formation [D. Tuncel, J. H. G. Steinke, Chem. Commun. 1999, 1509-1510].
37. Other approaches for controlling the macrocycle:thread repeat-unit stoichiometry in polyrotaxanes include a) the polymerization of monomer threads containing bulky blocking groups [I. Yamaguchi, K. Osakada, T. Yamamoto, J. Am. Chem. Soc. 1996, 118, 1811-1812; C. Gong, T. E. Glass, H. W. Gibson, Macromolecules 1998, 31, 308-313; C. Gong, H. W. Gibson, Angew. Chem. 1997, 109, 2426-2428; Angew. Chem. Int. Ed. Engl. 1997, 36, 2331-2333; M. B. Steinbrunn, G. Wenz, Angew, Chem. 1996, 108, 2274-2277; Angew. Chem. Int. Ed. Engl. 1996, 35, 2139-2141] and/or initiators [H. W. Gibson, P. T. Engen, S. H. Lee, Polymer 1999, 40, 1823-1832] in the presence of a macrocycle; b) the formation of a pseudorotaxane coordination polymer [D. Whang, Y.-M. Yeon, J. Heo, K. Kim, J. Am. Chem. Soc. 1996, 118, 11333-11334; D. Whang, K. Kim, J. Am. Chem. Soc. 1997, 119, 451-452; E. Lee, J. Heo, K. Kim, Angew. Chem. 2000, 112, 2814-2819; Angew. Chem. Int. Ed. 2000, 39, 2699-2701]; and c) the catalytic polymerization of monomer threads where the threaded macrocycle itself acts as the catalyst to polymer formation [D. Tuncel, J. H. G. Steinke, Chem. Commun. 1999, 1509-1510].
38. Other approaches for controlling the macrocycle:thread repeat-unit stoichiometry in polyrotaxanes include a) the polymerization of monomer threads containing bulky blocking groups [I. Yamaguchi, K. Osakada, T. Yamamoto, J. Am. Chem. Soc. 1996, 118, 1811-1812; C. Gong, T. E. Glass, H. W. Gibson, Macromolecules 1998, 31, 308-313; C. Gong, H. W. Gibson, Angew. Chem. 1997, 109, 2426-2428; Angew. Chem. Int. Ed. Engl. 1997, 36, 2331-2333; M. B. Steinbrunn, G. Wenz, Angew, Chem. 1996, 108, 2274-2277; Angew. Chem. Int. Ed. Engl. 1996, 35, 2139-2141] and/or initiators [H. W. Gibson, P. T. Engen, S. H. Lee, Polymer 1999, 40, 1823-1832] in the presence of a macrocycle; b) the formation of a pseudorotaxane coordination polymer [D. Whang, Y.-M. Yeon, J. Heo, K. Kim, J. Am. Chem. Soc. 1996, 118, 11333-11334; D. Whang, K. Kim, J. Am. Chem. Soc. 1997, 119, 451-452; E. Lee, J. Heo, K. Kim, Angew. Chem. 2000, 112, 2814-2819; Angew. Chem. Int. Ed. 2000, 39, 2699-2701]; and c) the catalytic polymerization of monomer threads where the threaded macrocycle itself acts as the catalyst to polymer formation [D. Tuncel, J. H. G. Steinke, Chem. Commun. 1999, 1509-1510].
39. Other approaches for controlling the macrocycle:thread repeat-unit stoichiometry in polyrotaxanes include a) the polymerization of monomer threads containing bulky blocking groups [I. Yamaguchi, K. Osakada, T. Yamamoto, J. Am. Chem. Soc. 1996, 118, 1811-1812; C. Gong, T. E. Glass, H. W. Gibson, Macromolecules 1998, 31, 308-313; C. Gong, H. W. Gibson, Angew. Chem. 1997, 109, 2426-2428; Angew. Chem. Int. Ed. Engl. 1997, 36, 2331-2333; M. B. Steinbrunn, G. Wenz, Angew, Chem. 1996, 108, 2274-2277; Angew. Chem. Int. Ed. Engl. 1996, 35, 2139-2141] and/or initiators [H. W. Gibson, P. T. Engen, S. H. Lee, Polymer 1999, 40, 1823-1832] in the presence of a macrocycle; b) the formation of a pseudorotaxane coordination polymer [D. Whang, Y.-M. Yeon, J. Heo, K. Kim, J. Am. Chem. Soc. 1996, 118, 11333-11334; D. Whang, K. Kim, J. Am. Chem. Soc. 1997, 119, 451-452; E. Lee, J. Heo, K. Kim, Angew. Chem. 2000, 112, 2814-2819; Angew. Chem. Int. Ed. 2000, 39, 2699-2701]; and c) the catalytic polymerization of monomer threads where the threaded macrocycle itself acts as the catalyst to polymer formation [D. Tuncel, J. H. G. Steinke, Chem. Commun. 1999, 1509-1510].
40. Other approaches for controlling the macrocycle:thread repeat-unit stoichiometry in polyrotaxanes include a) the polymerization of monomer threads containing bulky blocking groups [I. Yamaguchi, K. Osakada, T. Yamamoto, J. Am. Chem. Soc. 1996, 118, 1811-1812; C. Gong, T. E. Glass, H. W. Gibson, Macromolecules 1998, 31, 308-313; C. Gong, H. W. Gibson, Angew. Chem. 1997, 109, 2426-2428; Angew. Chem. Int. Ed. Engl. 1997, 36, 2331-2333; M. B. Steinbrunn, G. Wenz, Angew, Chem. 1996, 108, 2274-2277; Angew. Chem. Int. Ed. Engl. 1996, 35, 2139-2141] and/or initiators [H. W. Gibson, P. T. Engen, S. H. Lee, Polymer 1999, 40, 1823-1832] in the presence of a macrocycle; b) the formation of a pseudorotaxane coordination polymer [D. Whang, Y.-M. Yeon, J. Heo, K. Kim, J. Am. Chem. Soc. 1996, 118, 11333-11334; D. Whang, K. Kim, J. Am. Chem. Soc. 1997, 119, 451-452; E. Lee, J. Heo, K. Kim, Angew. Chem. 2000, 112, 2814-2819; Angew. Chem. Int. Ed. 2000, 39, 2699-2701]; and c) the catalytic polymerization of monomer threads where the threaded macrocycle itself acts as the catalyst to polymer formation [D. Tuncel, J. H. G. Steinke, Chem. Commun. 1999, 1509-1510].
41. J. A. Loontjens, B. J. M. Plum (DSM), WO patent 00/17169, 2000.
42. a) F. G. Gatti, D. A. Leigh, S. A. Nepogodiev, A. M. Z. Slawin, S. J. Teat, J. K. Y. Wong, J. Am. Chem. Soc. 2001, 123, 5983-5989;
43. b) F. G. Gatti, S. Leòn, J. K. Y. Wong, G. Bottari, A. Altieri, M. A. Farran Morales, S. J. Teat, C. Frochot, D. A. Leigh, A. M. Brouwer, F. Zerbetto, Proc. Natl. Acad. Sci. USA 2003, 100, 10-14.
44. Full details of the experimental procedures can be found in the Supporting Information.
45. Detailed crystallographic data for these compounds is reported in the Supporting Information.
46. A rotaxane similar to 5 but without the extra phenylalanine residues (Figure 1 c) was synthesized through condensation of two equivalents of stopper 1 with fumaroyl chloride. Subsequent polymerization of this rotaxane monomer resulted in the dethreading of the macrocycle from the polymer as a result of the loss of the bulky caprolactam blocking group during chain extension.
47. The calculated degree of polymerization was based on the SEC-determined average molecular weights of Jeffamine D400 and rotaxane monomers.