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Transformations in Chemically Responsive Copper‐Calixarene Architectures
Author(s) -
Percástegui Edmundo G.,
ReyesMata Carlos,
FloresAlamo Marcos,
QuirozGarcía Beatriz,
Rivera Ernesto,
Castillo Ivan
Publication year - 2018
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201701741
Subject(s) - thermochromism , chemistry , copper , luminescence , salt (chemistry) , crystallography , calixarene , stereochemistry , photochemistry , combinatorial chemistry , molecule , materials science , organic chemistry , optoelectronics
Self‐assembly of bis‐picolyl‐appended calix[4]arene ( L ) with Cu I or Cu II salts resulted in a collection of multinuclear architectures capable of expressing structural reconfigurations in response to various chemical stimuli: addition of copper salt, solvents, or oxidation. Coordination of L to CuX (X=Br, I) selectively yielded dinuclear macrocycles Cu I 2 L 2 Br 2 ( 1 ) and Cu I 2 L 2 I 2 ( 3 ) that were transformed into tetranuclear assemblies Cu I 4 L 2 Br 4 ( 2 ) and Cu I 4 L 2 I 4 ( 4 ) upon further addition of CuX. These supramolecules persist as robust and discrete entities in solution that display red emission; notably, 4 exhibits luminescence thermochromism. Assembly of L with CuCl 2 produced macrocycle Cu II 2 L 2 Cl 4 ( 5 ), which crystallised as cage [Cu II 2 L 4 (μ‐Cl)] 3+ ( 6 ) in the presence of MeOH. Two chemical signals—introduction of CuCl 2 and addition of CH 3 CN—regenerated macrocycle 5 . Coordination of L to Cu(OTf) yielded macrocycle Cu I 2 L 2 (OTf) 2 ( 7 ) that also crystallised as cage 6 upon oxidation in CHCl 3 .