Synthesis of (NH)(m)(NMe)(4-m)-bridged calix[4]pyridines and the effect of NH bridge on structure and properties.
The (NH)(m)(NMe)(4-m)-bridged calix[4]pyridines (m = 1-4) 19-23 were synthesized in excellent yields from deprotection of N-allyl groups of (NAllyl)(m)(NMe)(4-m)-bridged calix[4]pyridine derivatives 8 and 15-18, which were prepared in moderate yields by macrocyclic 2+2 and 1+3 coupling reactions between simple diamino- and dibromo-substituted fragments. In the solid state, (NH)(m)(NMe)(4-m)-bridged calix[4]pyridines adopted different 1,3-alternate conformations due to mainly the formation of varied conjugation systems of bridging NH units with their neighboring pyridines. In solution, all (NH)(m)(NMe)(4-m)-bridged calix[4]pyridines were very fluxional and the rates of interconversion of various conformational structures were very rapid relative to the NMR time scale. While (NH)(4)-bridged calix[4]pyridine 23 formed the strongest conjugation system, (NH)(2)(NMe)(2)-bridged calix[4]pyridine 21 acted as a selective fluorescence probe in the recognition of zinc(II) ion in solution with the dramatic enhancement of fluorescence intensity.
Zhang
En-Xuan
EX
Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Wang
De-Xian
DX
Huang
Zhi-Tang
ZT
Wang
Mei-Xiang
MX
D003500:Cyclization; D015394:Molecular Structure; D011725:Pyridines / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D011725:Pyridines