The synthesis, c
omplete characterizati
on, and s
olid state structural and s
oluti
on c
onf
ormati
ondeterminati
on
of calix[
n]arenes (
n = 4, 6, 8) is rep
orted. A c
omplete series
of X-ray structures
of the alkalimetal salts
of calix[4]arene (
HC4) illustrate the great influence
of the alkali metal i
on
on the s
olid statestructure
of calixani
ons (e.g., the Li salt
of m
on
oani
onic
HC4 is a m
on
omer; the Na salt
of m
on
oani
onic
HC4 f
orms a dimer; and the K, Rb, and Cs salts exist in p
olymeric f
orms). S
oluti
on NMR spectra
of alkalimetal salts
of m
on
oani
onic calix[4]arenes indicate that they have the c
one c
onf
ormati
on in s
oluti
on. Variable-temperature NMR spectra
of salts
HC4·M (M = Li, Na, K, Rb, Cs) sh
ow that they p
ossess similarc
oalescence temperatures, all higher than that
of
HC4. Due t
o steric hindrance fr
om
tert-butyl gr
oups inthe
para p
ositi
on
of
p-
tert-butylcalix[4]arene (
ButC4), the alkali metal salts
of m
on
oani
onic
ButC4 exist inm
on
omeric
or dimeric f
orm in the s
olid state. Calix[6]arene (
HC6) and
p-
tert-butylcalix[6]arene (
ButC6)were treated with a 2:1 m
olar rati
o of M
2CO
3 (M = K, Rb, Cs)
or a 1:1 m
olar rati
o of MOC(CH
3)
3 (M = Li,Na) t
o give calix[6]arene m
on
oani
ons, but calix[6]arenes react in a 1:1 m
olar rati
o with M
2CO
3 (M = K, Rb,Cs) t
o aff
ord calix[6]arene diani
ons. Calix[8]arene (
HC8) and
p-
tert-butylcalix[8]arene (
ButC8) have similarreactivity. The alkali metal salts
of m
on
oani
onic calix[6]arenes are m
ore c
onf
ormati
onally flexible than thealkali metal salts
of diani
onic calix[6]arenes, which has been sh
own by their s
oluti
on NMR spectra. X-raycrystal structures
of
HC6·Li and
HC6·Cs indicate that the size
of the alkali metal has s
ome influence
onthe c
onf
ormati
on
of calixani
ons; f
or example,
HC6·Li has a c
one-like c
onf
ormati
on, and
HC6·Cs has a1,2,3-alternate c
onf
ormati
on. The calix[6]arene diani
ons sh
ow r
oughly the same structural architecture,and the salts tend t
o f
orm p
olymeric chains. F
or m
ost calixarene salts cati
on-
arene interacti
ons were
observed.