Twistophane macrocycles with integrated 6,6′-connected-2,2′-bipyridine units: A new lead class of fluorescence sensors for metal ions

Chemistry - A European Journal

Volumn 8, Issue 22, 2002, Pages 5250-5264

  Baxter, Paul N W ^a  

^a UNIVERSITÉ LOUIS PASTEUR   (France)

Author keywords

Alkynes; Cyclooligomerization; Cyclophanes; Macrocyclic ligands; Sensors

Indexed keywords

CONFORMATIONS; ENVIRONMENTAL IMPACT; FLUORESCENCE; POLLUTION; QUENCHING; TRACE ELEMENTS; ULTRAVIOLET SPECTROGRAPHS;

TWISTOPHANE MACROCYCLES;

CHEMICAL SENSORS;

2,2' BIPYRIDINE DERIVATIVE; METAL ION;

ARTICLE; BINDING KINETICS; CALCULATION; CHEMICAL ANALYSIS; CHEMICAL STRUCTURE; FLUORESCENCE; MOLECULAR DYNAMICS; MOLECULAR MECHANICS; PROTON TRANSPORT; STRUCTURE ANALYSIS; SYNTHESIS; ULTRAVIOLET SPECTROSCOPY;

EID: 0037112712     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3765(20021115)8:22<5250::AID-CHEM5250>3.0.CO;2-Q     Document Type: Article

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56. a) P. N. W. Baxter, J. Org. Chem. 2001, 66, 4170; the term "twistophane" is used to describe ethynyl cyclophanes that are completely ortho-conjugated, yet helically twisted and, therefore, nonplanar chiral structures. Such molecules represent a small but slowly emergent subclass of conjugated ethynyl macrocycles of which 1, 2 and 3 are the first reported examples with integrated heterocyclic N-donor sites for metal ion coordination. Examples of this type of molecule include the following: b) M. J. Marsella, Z.-Q. Wang, R. J. Reid, K. Yoon, Org. Lett. 2001, 3, 885; c) S. K. Collins, G. P. A. Yap, A. G. Fallis, Org. Lett. 2000, 2, 3189; d) S. K. Collins, G. P. A. Yap, A. G. Fallis, Angew. Chem. Int. Ed. Engl. 2000, 39, 385; e) M. M. Haley, M. L. Bell, J. J. English, C. A. Johnson, T. J. R. Weakley, J. Am. Chem. Soc. 1997, 119, 2956; f) K. P. Baldwin, R. S. Simons, J. Rose, P. Zimmerman, D. M. Hercules, C. A. Tessier, W. J. Youngs, Chem. Commun. 1994, 1257; g) reference [18c].
57. a) P. N. W. Baxter, J. Org. Chem. 2001, 66, 4170; the term "twistophane" is used to describe ethynyl cyclophanes that are completely ortho-conjugated, yet helically twisted and, therefore, nonplanar chiral structures. Such molecules represent a small but slowly emergent subclass of conjugated ethynyl macrocycles of which 1, 2 and 3 are the first reported examples with integrated heterocyclic N-donor sites for metal ion coordination. Examples of this type of molecule include the following: b) M. J. Marsella, Z.-Q. Wang, R. J. Reid, K. Yoon, Org. Lett. 2001, 3, 885; c) S. K. Collins, G. P. A. Yap, A. G. Fallis, Org. Lett. 2000, 2, 3189; d) S. K. Collins, G. P. A. Yap, A. G. Fallis, Angew. Chem. Int. Ed. Engl. 2000, 39, 385; e) M. M. Haley, M. L. Bell, J. J. English, C. A. Johnson, T. J. R. Weakley, J. Am. Chem. Soc. 1997, 119, 2956; f) K. P. Baldwin, R. S. Simons, J. Rose, P. Zimmerman, D. M. Hercules, C. A. Tessier, W. J. Youngs, Chem. Commun. 1994, 1257; g) reference [18c].
58. a) P. N. W. Baxter, J. Org. Chem. 2001, 66, 4170; the term "twistophane" is used to describe ethynyl cyclophanes that are completely ortho-conjugated, yet helically twisted and, therefore, nonplanar chiral structures. Such molecules represent a small but slowly emergent subclass of conjugated ethynyl macrocycles of which 1, 2 and 3 are the first reported examples with integrated heterocyclic N-donor sites for metal ion coordination. Examples of this type of molecule include the following: b) M. J. Marsella, Z.-Q. Wang, R. J. Reid, K. Yoon, Org. Lett. 2001, 3, 885; c) S. K. Collins, G. P. A. Yap, A. G. Fallis, Org. Lett. 2000, 2, 3189; d) S. K. Collins, G. P. A. Yap, A. G. Fallis, Angew. Chem. Int. Ed. Engl. 2000, 39, 385; e) M. M. Haley, M. L. Bell, J. J. English, C. A. Johnson, T. J. R. Weakley, J. Am. Chem. Soc. 1997, 119, 2956; f) K. P. Baldwin, R. S. Simons, J. Rose, P. Zimmerman, D. M. Hercules, C. A. Tessier, W. J. Youngs, Chem. Commun. 1994, 1257; g) reference [18c].
59. a) P. N. W. Baxter, J. Org. Chem. 2001, 66, 4170; the term "twistophane" is used to describe ethynyl cyclophanes that are completely ortho-conjugated, yet helically twisted and, therefore, nonplanar chiral structures. Such molecules represent a small but slowly emergent subclass of conjugated ethynyl macrocycles of which 1, 2 and 3 are the first reported examples with integrated heterocyclic N-donor sites for metal ion coordination. Examples of this type of molecule include the following: b) M. J. Marsella, Z.-Q. Wang, R. J. Reid, K. Yoon, Org. Lett. 2001, 3, 885; c) S. K. Collins, G. P. A. Yap, A. G. Fallis, Org. Lett. 2000, 2, 3189; d) S. K. Collins, G. P. A. Yap, A. G. Fallis, Angew. Chem. Int. Ed. Engl. 2000, 39, 385; e) M. M. Haley, M. L. Bell, J. J. English, C. A. Johnson, T. J. R. Weakley, J. Am. Chem. Soc. 1997, 119, 2956; f) K. P. Baldwin, R. S. Simons, J. Rose, P. Zimmerman, D. M. Hercules, C. A. Tessier, W. J. Youngs, Chem. Commun. 1994, 1257; g) reference [18c].
60. a) P. N. W. Baxter, J. Org. Chem. 2001, 66, 4170; the term "twistophane" is used to describe ethynyl cyclophanes that are completely ortho-conjugated, yet helically twisted and, therefore, nonplanar chiral structures. Such molecules represent a small but slowly emergent subclass of conjugated ethynyl macrocycles of which 1, 2 and 3 are the first reported examples with integrated heterocyclic N-donor sites for metal ion coordination. Examples of this type of molecule include the following: b) M. J. Marsella, Z.-Q. Wang, R. J. Reid, K. Yoon, Org. Lett. 2001, 3, 885; c) S. K. Collins, G. P. A. Yap, A. G. Fallis, Org. Lett. 2000, 2, 3189; d) S. K. Collins, G. P. A. Yap, A. G. Fallis, Angew. Chem. Int. Ed. Engl. 2000, 39, 385; e) M. M. Haley, M. L. Bell, J. J. English, C. A. Johnson, T. J. R. Weakley, J. Am. Chem. Soc. 1997, 119, 2956; f) K. P. Baldwin, R. S. Simons, J. Rose, P. Zimmerman, D. M. Hercules, C. A. Tessier, W. J. Youngs, Chem. Commun. 1994, 1257; g) reference [18c].
61. a) P. N. W. Baxter, J. Org. Chem. 2001, 66, 4170; the term "twistophane" is used to describe ethynyl cyclophanes that are completely ortho-conjugated, yet helically twisted and, therefore, nonplanar chiral structures. Such molecules represent a small but slowly emergent subclass of conjugated ethynyl macrocycles of which 1, 2 and 3 are the first reported examples with integrated heterocyclic N-donor sites for metal ion coordination. Examples of this type of molecule include the following: b) M. J. Marsella, Z.-Q. Wang, R. J. Reid, K. Yoon, Org. Lett. 2001, 3, 885; c) S. K. Collins, G. P. A. Yap, A. G. Fallis, Org. Lett. 2000, 2, 3189; d) S. K. Collins, G. P. A. Yap, A. G. Fallis, Angew. Chem. Int. Ed. Engl. 2000, 39, 385; e) M. M. Haley, M. L. Bell, J. J. English, C. A. Johnson, T. J. R. Weakley, J. Am. Chem. Soc. 1997, 119, 2956; f) K. P. Baldwin, R. S. Simons, J. Rose, P. Zimmerman, D. M. Hercules, C. A. Tessier, W. J. Youngs, Chem. Commun. 1994, 1257; g) reference [18c].
62. a) P. N. W. Baxter, J. Org. Chem. 2001, 66, 4170; the term "twistophane" is used to describe ethynyl cyclophanes that are completely ortho-conjugated, yet helically twisted and, therefore, nonplanar chiral structures. Such molecules represent a small but slowly emergent subclass of conjugated ethynyl macrocycles of which 1, 2 and 3 are the first reported examples with integrated heterocyclic N-donor sites for metal ion coordination. Examples of this type of molecule include the following: b) M. J. Marsella, Z.-Q. Wang, R. J. Reid, K. Yoon, Org. Lett. 2001, 3, 885; c) S. K. Collins, G. P. A. Yap, A. G. Fallis, Org. Lett. 2000, 2, 3189; d) S. K. Collins, G. P. A. Yap, A. G. Fallis, Angew. Chem. Int. Ed. Engl. 2000, 39, 385; e) M. M. Haley, M. L. Bell, J. J. English, C. A. Johnson, T. J. R. Weakley, J. Am. Chem. Soc. 1997, 119, 2956; f) K. P. Baldwin, R. S. Simons, J. Rose, P. Zimmerman, D. M. Hercules, C. A. Tessier, W. J. Youngs, Chem. Commun. 1994, 1257; g) reference [18c].
63. The construction of ethynyl macrocycles that incorporate pyridine and pyridine-type units has recently attracted a flurry of interest. For examples of conjugated ethynyl macrocycles incorporating pyridine units, see a) Y. Tobe, H. Nakanishi, M. Sonoda, T. Wakabayashi, Y. Achiba, Chem. Commun. 1999, 1625; b) Y. Tobe, A. Nagano, K. Kawabata, M. Sonoda, K. Naemura, Org. Lett. 2000, 2, 3265; c) S.-S. Sun, A. J. Lees, Organometallics 2001, 20, 2353; d) reference [26a]: For other examples of conjugated ethynyl macrocycles incorporating bipyridine units, see e) O. Henze, D. Lentz, A. D. Schlüter, Chem. Eur. J. 2000, 6, 2362; f) reference [26b]; for an example of a conjugated phenylethynyl macrocycle incorporating phenanthroline units, see g) M. Schmittel, H. Ammon. Synlett 1999, 750.
64. The construction of ethynyl macrocycles that incorporate pyridine and pyridine-type units has recently attracted a flurry of interest. For examples of conjugated ethynyl macrocycles incorporating pyridine units, see a) Y. Tobe, H. Nakanishi, M. Sonoda, T. Wakabayashi, Y. Achiba, Chem. Commun. 1999, 1625; b) Y. Tobe, A. Nagano, K. Kawabata, M. Sonoda, K. Naemura, Org. Lett. 2000, 2, 3265; c) S.-S. Sun, A. J. Lees, Organometallics 2001, 20, 2353; d) reference [26a]: For other examples of conjugated ethynyl macrocycles incorporating bipyridine units, see e) O. Henze, D. Lentz, A. D. Schlüter, Chem. Eur. J. 2000, 6, 2362; f) reference [26b]; for an example of a conjugated phenylethynyl macrocycle incorporating phenanthroline units, see g) M. Schmittel, H. Ammon. Synlett 1999, 750.
65. The construction of ethynyl macrocycles that incorporate pyridine and pyridine-type units has recently attracted a flurry of interest. For examples of conjugated ethynyl macrocycles incorporating pyridine units, see a) Y. Tobe, H. Nakanishi, M. Sonoda, T. Wakabayashi, Y. Achiba, Chem. Commun. 1999, 1625; b) Y. Tobe, A. Nagano, K. Kawabata, M. Sonoda, K. Naemura, Org. Lett. 2000, 2, 3265; c) S.-S. Sun, A. J. Lees, Organometallics 2001, 20, 2353; d) reference [26a]: For other examples of conjugated ethynyl macrocycles incorporating bipyridine units, see e) O. Henze, D. Lentz, A. D. Schlüter, Chem. Eur. J. 2000, 6, 2362; f) reference [26b]; for an example of a conjugated phenylethynyl macrocycle incorporating phenanthroline units, see g) M. Schmittel, H. Ammon. Synlett 1999, 750.
66. The construction of ethynyl macrocycles that incorporate pyridine and pyridine-type units has recently attracted a flurry of interest. For examples of conjugated ethynyl macrocycles incorporating pyridine units, see a) Y. Tobe, H. Nakanishi, M. Sonoda, T. Wakabayashi, Y. Achiba, Chem. Commun. 1999, 1625; b) Y. Tobe, A. Nagano, K. Kawabata, M. Sonoda, K. Naemura, Org. Lett. 2000, 2, 3265; c) S.-S. Sun, A. J. Lees, Organometallics 2001, 20, 2353; d) reference [26a]: For other examples of conjugated ethynyl macrocycles incorporating bipyridine units, see e) O. Henze, D. Lentz, A. D. Schlüter, Chem. Eur. J. 2000, 6, 2362; f) reference [26b]; for an example of a conjugated phenylethynyl macrocycle incorporating phenanthroline units, see g) M. Schmittel, H. Ammon. Synlett 1999, 750.
67. The construction of ethynyl macrocycles that incorporate pyridine and pyridine-type units has recently attracted a flurry of interest. For examples of conjugated ethynyl macrocycles incorporating pyridine units, see a) Y. Tobe, H. Nakanishi, M. Sonoda, T. Wakabayashi, Y. Achiba, Chem. Commun. 1999, 1625; b) Y. Tobe, A. Nagano, K. Kawabata, M. Sonoda, K. Naemura, Org. Lett. 2000, 2, 3265; c) S.-S. Sun, A. J. Lees, Organometallics 2001, 20, 2353; d) reference [26a]: For other examples of conjugated ethynyl macrocycles incorporating bipyridine units, see e) O. Henze, D. Lentz, A. D. Schlüter, Chem. Eur. J. 2000, 6, 2362; f) reference [26b]; for an example of a conjugated phenylethynyl macrocycle incorporating phenanthroline units, see g) M. Schmittel, H. Ammon. Synlett 1999, 750.
68. The construction of ethynyl macrocycles that incorporate pyridine and pyridine-type units has recently attracted a flurry of interest. For examples of conjugated ethynyl macrocycles incorporating pyridine units, see a) Y. Tobe, H. Nakanishi, M. Sonoda, T. Wakabayashi, Y. Achiba, Chem. Commun. 1999, 1625; b) Y. Tobe, A. Nagano, K. Kawabata, M. Sonoda, K. Naemura, Org. Lett. 2000, 2, 3265; c) S.-S. Sun, A. J. Lees, Organometallics 2001, 20, 2353; d) reference [26a]: For other examples of conjugated ethynyl macrocycles incorporating bipyridine units, see e) O. Henze, D. Lentz, A. D. Schlüter, Chem. Eur. J. 2000, 6, 2362; f) reference [26b]; for an example of a conjugated phenylethynyl macrocycle incorporating phenanthroline units, see g) M. Schmittel, H. Ammon. Synlett 1999, 750.
69. The construction of ethynyl macrocycles that incorporate pyridine and pyridine-type units has recently attracted a flurry of interest. For examples of conjugated ethynyl macrocycles incorporating pyridine units, see a) Y. Tobe, H. Nakanishi, M. Sonoda, T. Wakabayashi, Y. Achiba, Chem. Commun. 1999, 1625; b) Y. Tobe, A. Nagano, K. Kawabata, M. Sonoda, K. Naemura, Org. Lett. 2000, 2, 3265; c) S.-S. Sun, A. J. Lees, Organometallics 2001, 20, 2353; d) reference [26a]: For other examples of conjugated ethynyl macrocycles incorporating bipyridine units, see e) O. Henze, D. Lentz, A. D. Schlüter, Chem. Eur. J. 2000, 6, 2362; f) reference [26b]; for an example of a conjugated phenylethynyl macrocycle incorporating phenanthroline units, see g) M. Schmittel, H. Ammon. Synlett 1999, 750.
70. For the employment of analyte-binding-induced mechanical distortions in linear conjugated polymers as a principle for sensing, see for example: a) D. H. Charych, J. O. Nagy, W. Spevak, M. D. Bednarski, Science 1993, 261, 585; b) R. D. McCullough, P. C. Ewbank, R. S. Loewe, J. Am. Chem. Soc. 1997, 119, 633; c) T. M. Swager, Acc. Chem. Res. 1998, 31, 201; d) S. Okada, S. Peng, W. Spevak, D. Charych, Acc. Chem. Res. 1998, 31, 229; recent investigations have shown that the twisted and coplanar forms of 1, 4-bis(phenylethynyl)benzene are spectroscopically distinct species, see; e) M. Levitus, K. Schmieder, H. Ricks, K. D. Shimizu, U. H. F. Bunz, M. A. Garcia-Garibay, J. Am. Chem. Soc. 2001, 123, 4259; the difference originates from the excited state which can exist as energetically different structures the allplanar one of which has a delocalised cumulene-type bonding pattern This also supports the expectation that mechanical variations in 2 may be accompanied by spectroscopic changes.
71. For the employment of analyte-binding-induced mechanical distortions in linear conjugated polymers as a principle for sensing, see for example: a) D. H. Charych, J. O. Nagy, W. Spevak, M. D. Bednarski, Science 1993, 261, 585; b) R. D. McCullough, P. C. Ewbank, R. S. Loewe, J. Am. Chem. Soc. 1997, 119, 633; c) T. M. Swager, Acc. Chem. Res. 1998, 31, 201; d) S. Okada, S. Peng, W. Spevak, D. Charych, Acc. Chem. Res. 1998, 31, 229; recent investigations have shown that the twisted and coplanar forms of 1, 4-bis(phenylethynyl)benzene are spectroscopically distinct species, see; e) M. Levitus, K. Schmieder, H. Ricks, K. D. Shimizu, U. H. F. Bunz, M. A. Garcia-Garibay, J. Am. Chem. Soc. 2001, 123, 4259; the difference originates from the excited state which can exist as energetically different structures the allplanar one of which has a delocalised cumulene-type bonding pattern This also supports the expectation that mechanical variations in 2 may be accompanied by spectroscopic changes.
72. For the employment of analyte-binding-induced mechanical distortions in linear conjugated polymers as a principle for sensing, see for example: a) D. H. Charych, J. O. Nagy, W. Spevak, M. D. Bednarski, Science 1993, 261, 585; b) R. D. McCullough, P. C. Ewbank, R. S. Loewe, J. Am. Chem. Soc. 1997, 119, 633; c) T. M. Swager, Acc. Chem. Res. 1998, 31, 201; d) S. Okada, S. Peng, W. Spevak, D. Charych, Acc. Chem. Res. 1998, 31, 229; recent investigations have shown that the twisted and coplanar forms of 1, 4-bis(phenylethynyl)benzene are spectroscopically distinct species, see; e) M. Levitus, K. Schmieder, H. Ricks, K. D. Shimizu, U. H. F. Bunz, M. A. Garcia-Garibay, J. Am. Chem. Soc. 2001, 123, 4259; the difference originates from the excited state which can exist as energetically different structures the allplanar one of which has a delocalised cumulene-type bonding pattern This also supports the expectation that mechanical variations in 2 may be accompanied by spectroscopic changes.
73. For the employment of analyte-binding-induced mechanical distortions in linear conjugated polymers as a principle for sensing, see for example: a) D. H. Charych, J. O. Nagy, W. Spevak, M. D. Bednarski, Science 1993, 261, 585; b) R. D. McCullough, P. C. Ewbank, R. S. Loewe, J. Am. Chem. Soc. 1997, 119, 633; c) T. M. Swager, Acc. Chem. Res. 1998, 31, 201; d) S. Okada, S. Peng, W. Spevak, D. Charych, Acc. Chem. Res. 1998, 31, 229; recent investigations have shown that the twisted and coplanar forms of 1, 4-bis(phenylethynyl)benzene are spectroscopically distinct species, see; e) M. Levitus, K. Schmieder, H. Ricks, K. D. Shimizu, U. H. F. Bunz, M. A. Garcia-Garibay, J. Am. Chem. Soc. 2001, 123, 4259; the difference originates from the excited state which can exist as energetically different structures the allplanar one of which has a delocalised cumulene-type bonding pattern This also supports the expectation that mechanical variations in 2 may be accompanied by spectroscopic changes.
74. For the employment of analyte-binding-induced mechanical distortions in linear conjugated polymers as a principle for sensing, see for example: a) D. H. Charych, J. O. Nagy, W. Spevak, M. D. Bednarski, Science 1993, 261, 585; b) R. D. McCullough, P. C. Ewbank, R. S. Loewe, J. Am. Chem. Soc. 1997, 119, 633; c) T. M. Swager, Acc. Chem. Res. 1998, 31, 201; d) S. Okada, S. Peng, W. Spevak, D. Charych, Acc. Chem. Res. 1998, 31, 229; recent investigations have shown that the twisted and coplanar forms of 1, 4-bis(phenylethynyl)benzene are spectroscopically distinct species, see; e) M. Levitus, K. Schmieder, H. Ricks, K. D. Shimizu, U. H. F. Bunz, M. A. Garcia-Garibay, J. Am. Chem. Soc. 2001, 123, 4259; the difference originates from the excited state which can exist as energetically different structures the allplanar one of which has a delocalised cumulene-type bonding pattern This also supports the expectation that mechanical variations in 2 may be accompanied by spectroscopic changes.
75. Reports on the use of pyridine-type ligands connected to/or within electronically delocalised organic scaffolds for the sensing of metal ions are sparse. See for example: a) B. Wang, M. R. Wasielewski, J. Am. Chem. Soc. 1997, 119, 12; b) M. Kimura, T. Horai, K. Hanabusa, H. Shirai, Adv. Mater. 1998, 10, 459; c) P. N. W. Baxter, J. Org. Chem. 2000, 65, 1257; d) D. T. McQuade, A. E. Pullen, T. M. Swager, Chem. Rev. 2000, 100, 2537; e) C.-S. Choi, T. Mutai, S. Arita, K. Araki, J. Chem. Soc. Perkin Trans. 2, 2000, 243; f) reference [27a].
76. Reports on the use of pyridine-type ligands connected to/or within electronically delocalised organic scaffolds for the sensing of metal ions are sparse. See for example: a) B. Wang, M. R. Wasielewski, J. Am. Chem. Soc. 1997, 119, 12; b) M. Kimura, T. Horai, K. Hanabusa, H. Shirai, Adv. Mater. 1998, 10, 459; c) P. N. W. Baxter, J. Org. Chem. 2000, 65, 1257; d) D. T. McQuade, A. E. Pullen, T. M. Swager, Chem. Rev. 2000, 100, 2537; e) C.-S. Choi, T. Mutai, S. Arita, K. Araki, J. Chem. Soc. Perkin Trans. 2, 2000, 243; f) reference [27a].
77. Reports on the use of pyridine-type ligands connected to/or within electronically delocalised organic scaffolds for the sensing of metal ions are sparse. See for example: a) B. Wang, M. R. Wasielewski, J. Am. Chem. Soc. 1997, 119, 12; b) M. Kimura, T. Horai, K. Hanabusa, H. Shirai, Adv. Mater. 1998, 10, 459; c) P. N. W. Baxter, J. Org. Chem. 2000, 65, 1257; d) D. T. McQuade, A. E. Pullen, T. M. Swager, Chem. Rev. 2000, 100, 2537; e) C.-S. Choi, T. Mutai, S. Arita, K. Araki, J. Chem. Soc. Perkin Trans. 2, 2000, 243; f) reference [27a].
78. Reports on the use of pyridine-type ligands connected to/or within electronically delocalised organic scaffolds for the sensing of metal ions are sparse. See for example: a) B. Wang, M. R. Wasielewski, J. Am. Chem. Soc. 1997, 119, 12; b) M. Kimura, T. Horai, K. Hanabusa, H. Shirai, Adv. Mater. 1998, 10, 459; c) P. N. W. Baxter, J. Org. Chem. 2000, 65, 1257; d) D. T. McQuade, A. E. Pullen, T. M. Swager, Chem. Rev. 2000, 100, 2537; e) C.-S. Choi, T. Mutai, S. Arita, K. Araki, J. Chem. Soc. Perkin Trans. 2, 2000, 243; f) reference [27a].
79. Reports on the use of pyridine-type ligands connected to/or within electronically delocalised organic scaffolds for the sensing of metal ions are sparse. See for example: a) B. Wang, M. R. Wasielewski, J. Am. Chem. Soc. 1997, 119, 12; b) M. Kimura, T. Horai, K. Hanabusa, H. Shirai, Adv. Mater. 1998, 10, 459; c) P. N. W. Baxter, J. Org. Chem. 2000, 65, 1257; d) D. T. McQuade, A. E. Pullen, T. M. Swager, Chem. Rev. 2000, 100, 2537; e) C.-S. Choi, T. Mutai, S. Arita, K. Araki, J. Chem. Soc. Perkin Trans. 2, 2000, 243; f) reference [27a].
80. Reports on the use of pyridine-type ligands connected to/or within electronically delocalised organic scaffolds for the sensing of metal ions are sparse. See for example: a) B. Wang, M. R. Wasielewski, J. Am. Chem. Soc. 1997, 119, 12; b) M. Kimura, T. Horai, K. Hanabusa, H. Shirai, Adv. Mater. 1998, 10, 459; c) P. N. W. Baxter, J. Org. Chem. 2000, 65, 1257; d) D. T. McQuade, A. E. Pullen, T. M. Swager, Chem. Rev. 2000, 100, 2537; e) C.-S. Choi, T. Mutai, S. Arita, K. Araki, J. Chem. Soc. Perkin Trans. 2, 2000, 243; f) reference [27a].
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91. Further studies on, for example, chirally functionalised derivatives may thus be necessary in order to clarify the solution dynamics of 2.
92. Interestingly, a somewhat higher energy conformational minimum accessible to 3 is that of a triangular tube-type structure. In this conformation, the three bipyridine units are transoid and planar, and define the walls of a tubular void. Cyclophane 3 may therefore also be capable of forming inclusion complexes with guests of complementary size and shape to the triangular cavity.
93. II triflates used were 99.9% purity.
94. I exists at low [3].
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101. Within the context of the above work, the qualitative parameters used to describe the metal-ion binding and sensing properties of ligands 2, 3 and 9, are defined as follows: Complexation selectivity, that is, the number of different types of metal ions that a given ligand is able to complex; the greater the number, the lower the selectivity. Complexation discrimination, that is, the number of strongest coordinating metal ions that equally bind to a given ligand: the higher the number, the less the discrimination. Sensory selectivity, the number of coordinating metal ions that produce similar fluorescence responses; the higher the number, the less the fluorescence selectivity. Output signal intensity, the estimated fluorescence detection limit for a given metal ion, which may be signalled both visually and instrumentally.
102. 3/MeOH. The fluorescence responses of 2 and 3 appear to be generally slightly more sensitive to the presence of metal ions than that of 1. However, if complexation-induced mechano-structural changes are occurring in 2 and 3, the resulting influence upon fluorescence signal amplification must be small. The above results suggest that increasing the conjugation and electronic delocalisation of the sensors may be a more effective future approach to optimising the fluorescence emission sensitivity and thus lowering the sensory detection limit for particular metal ions.
103. Molecules 2, 3 and 9 may be regarded as members of a lead class of metal sensors, as they are structurally significantly different from systems normally employed for this purpose. In particular, 2 and 3 are among the first examples of the utilisation of conjugated cyclic ethynyl scaffolds for metal-ion sensory applications. The majority of traditional ion sensors are constructed from nonaromatic cyclic and acyclic binding sites connected to or incorporated into classical fluorophores such as fluorescein. See for example, K. R. Gee, Z.-L. Zhou, W.-J. Qian, R. Kennedy, J. Am. Chem. Soc. 2002, 124, 776.
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