To improve the
se
lectivity of
sen
sing, the thermodynamic
s of the comp
lex formation of
some ca
lix[4]areneho
st
s with neutra
l pheno
l gue
st
s wa
s studied in carbon tetrach
loride a
s nonpo
lar
so
lvent. The mo
lecu
lar
shapeof ca
lixarene
s wa
s varied by the
se
lective functiona
lization with
tBu and O-CH
2-Ph (O-benzy
l) or OPrgroup
s at the upper and
lower rim, re
spective
ly. To vary the e
lectron den
sity on the gue
st'
s aromatic ring
s,the parent pheno
l wa
s functiona
lized in the para po
sition with e
lectron-withdrawing C
l, a
s we
ll a
s H, ande
lectron-re
lea
sing CH
3 and
tBu group
s. To
study the interaction between ca
lixarene and the gue
st
s, PL andquantum-chemica
l method
s were app
lied. The re
su
lt
s revea
led an overa
ll 1:1 comp
lex
stoichiometry exceptfor the parent dibenzy
loxyca
lix[4]arene, where 1:2 ho
st-gue
st
stoichiometrie
s were ob
served irre
spective ofthe qua
lity of pheno
l. In the
latter ca
se, the comp
lex formation
show
s a
se
lf-
switched character: the fir
stpheno
l mo
lecu
le i
s inc
luded in the ca
lixarene cavity, and on
ly afterward, a
second gue
st mo
lecu
le i
s boundby the two benzy
loxy aromatic
s. A
lthough the entha
lpy change predict
s strong interaction between the ho
stand the gue
st, the Gibb
s free energy change of the comp
lex formation i
s sma
ll, re
su
lting in a re
lative
ly
lowcomp
lex
stabi
lity. The
so
lvent-re
laxation mea
surement
s support that the unexpected entropy change cou
ld bethe con
sequence of the reorientation of
so
lvent mo
lecu
le
s around the ca
lixarene bui
lding b
lock. The reorientationi
s a
ssi
sted by di
sper
sive force
s between
so
lute and
so
lvent mo
lecu
le
s. IR and RAMAN ana
ly
si
s of thecomp
lexe
s exc
lude a con
siderab
le participation of the pheno
lic OH group in the
stabi
lization of the comp
lex.Thi
s re
su
lt i
s in agreement with ear
lier finding
s where determini
stic ro
le of
![](/image<font color=)
s/gifchar
s/pi.gif" BORDER=0 >-
![](/image<font color=)
s/gifchar
s/pi.gif" BORDER=0 > interaction in the comp
lex
stabi
lity wa
s a
ssumed.