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From p ‐Dimethoxybenzene to Crown‐benzenophanes, 4 – Cation‐Complexing Properties of Bis( p ‐phenylene‐34‐crown‐10) – A Structural and Spectrophotometric Study
Author(s) -
Marquis Damien,
Greiving Helmut,
Desvergne JeanPierre,
Lahrahar Nacer,
Marsau Pierre,
Hopf Henning,
BouasLaurent Henri
Publication year - 1996
Publication title -
liebigs annalen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0947-3440
DOI - 10.1002/jlac.199719970115
Subject(s) - chemistry , hypsochromic shift , acetonitrile , titration , crystallography , quenching (fluorescence) , metal , absorption spectroscopy , inorganic chemistry , photochemistry , fluorescence , physics , organic chemistry , chromatography , quantum mechanics
The title compound 2 , an electron‐rich macrocyclic paracyclophane of the coronand type, known to form a charge‐transfer complex with paraquat, was found to encapsulate strontium cations and to bind to magnesium cations. X‐ray analysis revealed that 2 forms a 2:1 (metal/substrate) complex with Sr(ClO 4 ) 2 , in which the two benzene rings weakly overlap, whereas in the single crystals grown from Mg(ClO 4 ) 2 , the metal cation prefers to lie outside the coronand (1:1 stoichiometry). In acetonitrile solution, cations were observed to trigger an hypsochromic shift of the UV absorption spectra, proportional to their size and charge density. The stoichiometries and binding constants were also determined by UV absorption titration in acetonitrile using the LETAGROP‐SPEFO program for several monovalent and divalent cations. For Na + , Ca 2+ , and Sr 2+ , 1:1 and 2:1 complexes were shown to be formed. In the free ligand, a weak interaction between the benzene rings was detected by fluorescence decay kinetic analysis, indicating the presence of two conformer populations within the nanosecond time scale. In solution, metal cations neither induce detectable excimer formation nor seem to have a strong influence on the fluorescence emission spectra, except a heavy atom quenching with Sr 2+ and Ba 2+ , in contrast to the effect observed in absorption. However, Sr 2+ and Mg 2+ induce a clear hypsochromic shift in the single crystal fluorescence spectra. Compound 2 was prepared by a new and efficient route which is compared to the previous procedures.