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Recei ed 00 h Janua y 20xx,
Accep ed 00 h Janua y 20xx
DOI: 10.1039/x0xx00000x
T iphenylene-e hylammonium Te achlo ome alla e sal s:
Mul icolumna Mesophases, The moch omism and Langmui
ilms†
Ma ía Ba cenilla,a Ma ía Jesús Baena,a Be and Donnio,*,b Benoî Hein ich,b Lucía Gu ié ez,c
Sil e io Coco,*,a and Pablo Espine .*,a
This s udy epo s new mesomo phic benzyle hylammonium sal s con aining a 2,3,6,7,10-pen akis(dodecyloxy)-11-
(hexyloxy) iphenylene uni and Cl- o [MCl4]2- (M = Cu, Ni, Co, Mn) as coun e ion. They show a ich columna
polymesomo phism, cha ac e ized by pola ized op ical mic oscopy (POM), di e en ial scanning calo ime y (DSC), and
small- and wide-angle X- ay sca e ing (S/WAXS). All he compounds sel -o ganize in o mul iseg ega ed s uc u es in he
solid s a e and in he mesophases, wi h he al e na ion wi hin la ge supe la ices o iphenylene-con aining columns and
benzylammonium chlo ide o e acho ome alla e agmen s. In e es ingly, he nickel de i a i e displays a con inuous and
e e sible he moch omic beha io in he ange o 50-80 °C. Magne ic measu emen s and UV-Vis da a a di e en
empe a u es, suppo changes in he coo dina ion sphe e o he Ni(II) a om om oc ahed al o e ahed al. Fu he mo e,
hese sys ems o m s able and homogeneous Langmui ilms a he ai -wa e in e ace. These ilms ha e been success ully
ans e ed on o solid subs a es gi ing ise o nanos uc u ed LB ilms wi h a clea ly de ined bilaye s uc u e in which each
laye consis s o molecula columns aligned along he su ace.
In oduc ion
Building low-cos de ices wi h lexible and easily p ocessable
componen s is a s ongly desi ed objec i e in so elec onic
echnology. This equi es new unc ional ma e ials wi h
p ede e mined physical p ope ies. A ep esen a i e case is
ha o unc ional columna liquid c ys als wi h speci ic op ical,
elec ic o magne ic p ope ies ha can be combined wi h he
sup amolecula o ganiza ion and luidi y o he liquid c ys alline
mesophases.
1
-
8
T iphenylene-based mesogens a e pa o a
widely s udied subclass o columna liquid c ys als.
9
,
10
Thei
p ope ies can be modula ed h ough ailo ing o he
iphenylene co e wi h a a ie y o unc ional g oups,
11
-
15
including me al-o ganic complexes.
16
-
21
In his sense,
we ha e
epo ed mesomo phic me al-o ganic complexes con aining
iphenylene moie ies,
22
-
24
whe e he luminescen p ope ies o
he mesophase
25
and he cha ge mobili y along he columna
s acking
26
,
27
a e modula ed by he me al agmen .
The moch omic ma e ials a e also p omising unc ional
ma e ials o mul iple applica ions, such as ene gy-sa ing
windows,
28
,
29
empe a u e indica o s,
30
,
31
display ins umen s
32
o secu i y ma e ials.
33
They can be designed o a a ie y o
ma e ials including liquid c ys als,
34
polyme s,
35
and me al-
con aining complexes.
36
In he liquid c ys als ield, he
he moch omic beha iou p oduced by chi al mesophases is
well known and widely used o he p epa a ion o
he moindica o s. The moch omic liquid c ys als based on non-
chi al sys ems a e ela i ely sca ce and mainly co espond o
columna me allomesogens, in which he colou change is
a ibu ed o he a ia ion o he in e disc dis ance wi h
empe a u e, o o phase ansi ions in he case o calami ic
sys ems.
37
,
38
In non-mesogenic me al complexes, his beha iou
is usually due o a change in ei he he c ys alline phase, he
geome y o he me al cen e, o he numbe o sol en
molecules in he s uc u e.
36
Looking o he moch omic liquid c ys als based on me al
complexes ha can induce me al-cen ed he moch omism
wi hou he need o chi al s uc u es, we ha e chosen o s udy
iphenylene-e hylammonium sal s (TPh-NH
2
E
+
) o po en ially
he moch omic Cu(II), Ni(II), Co(II) and Mn(II)
e achlo ome alla es. Fo ins ance, i is known ha
(NE
2
H
2
)
2
[NiCl
4
] shows a e e sible he moch omic beha io .
40
Fu he mo e, hese designed molecula s uc u es, inspi ed by
o he p e ious s uc u ally epo ed ma e ials,
23,26
made o a
iphenylene uni connec ed o a benzylammonium sal ia an
a. IU CINQUIMA/Química Ino gánica, Facul ad de Ciencias, Uni e sidad de
Valladolid, 47071 Valladolid, Cas illa y León, Spain. E-mail; sil e io.coco@u a.es,
espine @qi.u a.es
b. Ins i u de Physique e Chimie des Ma é iaux de S asbou g (IPCMS), UMR 7504
(CNRS-Uni e si é de S asbou g), F-67034 S asbou g Cedex 2 (F ance). E-mail:
be [email protected] a.
c. Dep . Química Analí ica, Ins i u o de Nanociencia y Ma e iales de A agón (INMA),
CSIC-Uni e sidad de Za agoza and Cibe -BBN, Za agoza 50018, Spain.
† This wo k is dedica ed o hono P o esso Pe e M Mai lis, who has passed away
a he age o 90 when he e ision o his pape was o be submi ed. Mai lis was an
ou s anding and dedica ed man o science and a human example o all hose who
had he p i ilege o wo k close him. We owe him much mo e han he wo d
“me allomesogens”.
Elec onic Supplemen a y In o ma ion (ESI) a ailable: [de ails o any supplemen a y
in o ma ion a ailable should be included he e]. See DOI: 10.1039/x0xx00000x
Jou nal o Ma e ials Chemis y C, 2022, 10, 9222. DOI: h ps://doi.o g/10.1039/D2TC01100J
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alkyl space , we e expec ed o lead o he o ma ion o
mul icolumna mesophases, as bo h immiscible species should
phase sepa a e and be con ined in di e en egions in he
mesophase. As an addi ional aspec o in e es , hese sys ems
may o m s able Langmui ilms a he ai /wa e in e ace,
which could be ans e ed e y e icien ly o glass subs a es o
gi e Langmui -Blodge ilms wi h well-o de ed bilaye
s uc u es.
Resul s and discussion
Syn hesis and Cha ac e iza ion
The un epo ed iphenylene de i a i e [TPh-NH
2
E ]Cl (
3
) was
p epa ed om he co esponding aldehyde as shown in Scheme
1. The e hylammonium e achlo ome alla e sal s (
4-7
) we e
syn hesized by di ec eac ion o
3
wi h he co esponding
me al chlo ide MCl
2
(Scheme 1) and isola ed as colou ed solids
in 88-98% yield. Fo syn he ic and cha ac e iza ion de ails, see
ESI.
Scheme 1. Syn hesis o he Cl
–
and [MCl
4
]
2–
sal s o [TPhO-C
6
H
4
-CH
2
-NH
2
E ]
+
(3-7).
i: a) E NH
2
, THF; b) NaBH
4
, THF + E OH. ii: HCl, CH
2
Cl
2
. iii: MCl
2
, CH
2
Cl
2
/E OH.
The s uc u es o con en ional (R
2
NH
2
)
2
[MCl
4
] complexes (M =
Cu, Ni, Mn, Co, R = alkyl) epo ed in he li e a u e can be aken
as easonable models o
4
-
7
. In he solid s a e, hese s uc u es
consis o an al e na ion o anionic me al halide laye s
pa i ioned by a ays o ca ions. The ino ganic egions o he
coope ,
39
nickel,
40
and manganese
41
,
42
compounds consis o
dis o ed MCl
6
oc ahed a ea u ing MCl
4
laye s o squa e plana
me al cen es sha ing b idging chlo o ligands, and wo apical
e minal Cl ligands on each me al cen e.
43
A a iance wi h
hose, epo ed e ahed al [CoCl
4
]
2-
g oups we e ound in he
cobal a e sal s.
44
Consis en wi h hese li e a u e da a, he IR spec a o he Cu,
Mn and Ni sal s
4
,
5
, and
7
(Figu e 1) a e ypical o oc ahed al,
polyme ic ma e ials con aining b idging halo-ligands, wi h an
abso p ion a ca. 226 cm
-1
.
40
In con as , he cobal sal
6
displays a single abso p ion a 282 cm
-l
, assigned o
n
(Co–Cl) in
a e ahed al [CoCl
4
]
2-
anion.
44
Figu e 1. Fa -in a ed spec a o TPh-NH
2
E
+
sal s a 298 K (L = Cl
–
sal ; M = [MCl
4
]
2–
sal ).
The elec onic spec a o he
4
-
7
TPh-NH
2
E
+
sal s in he solid
s a e (di use e lec ance) a oom empe a u e display a
spec al pa e n wi h abso p ion bands in he ange 240-400
nm, co esponding o he 2,3,6,7,10,11-hexaalkoxy iphenylene
g oup (Figu e 2).
45
,
46
The cobal a e sal shows, in addi ion, an
in ense abso p ion band a lowe ene gy assigned o an
4
A
2
→
4
T
1
(
4
P) ansi ion in he e ahed al [CoCl
4
]
2-
g oup.
47
In
con as , o he o he e achlo ome alla e de i a i es only
b oad low-in ensi y abso p ion bands in he ange 400-480 nm
a e obse ed, in acco dance wi h hei oc ahed al o dis o ed-
oc ahed al coo dina ion geome ies (Figu e 2).
48
Figu e 2. UV-Vis di use e lec ance spec a o he TPh-NH
2
E
+
sal s in he solid
s a e (di use e lec ance) a 298 K (L = Cl
–
sal ; M = [MCl
4
]
2–
sal ).
The mal beha iou and sel -o ganiza ion p ope ies
The mesomo phic p ope ies o [TPh-NH
2
E ]Cl (
3
) and he ou
e achlo ome alla e sal s (
4
-
7
) ha e been s udied by pola ized
op ical mic oscopy (POM), di e en ial scanning calo ime y
(DSC), and small- and wide-angle X- ay sca e ing (S/WAXS). The
op ical, he mal and he modynamic da a a e ga he ed in Table
1. Rep esen a i e mic opho og aphs a e shown in Figu e 3. The
mesophase assignmen o Table 1 is based on he esul s o he
S/WAXS s udies. Addi ional da a a e p o ided in he Elec onic
Suppo ing In o ma ion.
C
H
O
OC6H12
RO
RO
RO
OR
OR
TPhO
HN
TPhO
H2N
TPhO
MCl4
2-
M = Cu (4, 95 %), Ni (5, 88 %), Co (6, 96 %), Mn (7, 98 %)
ii
+
Cl-
H2N
TPhO
+
2
i
R = C12H25
(1) (2), 89 %
(3), 96 %
iii
= TPh
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Table 1. Op ical, he mal, and he modynamic da a o he TPh-NH2E + sal s.
Cpd
T ansi iona
Tb (°C)
∆Hb (kJ mol-1)
(3)
C
→
M
M
→
Col ec
Col ec
→
I
40.8
80.1
95.7
42.6
2.6
3.2
(4)
C
→
M
M
→
Col ec
Col ec
→
I
43.4
99.7
116.1
102.4
2.7
2.8
(5) c
C
→
M
M
→
Col ec
Col ec
→
I
44.6
99.7
120.4
108.3
2.7
6.0
(6)
C
→
M
M
→
Col ec
Col ec
→
Colhex/Colsqu
Colhex/Colsqu
→
I
43.6
103.7
126.5
139.9
95.7
3.2
1.8
1.8
(7) c
C
→
M
M
→
Col ec
Col ec
→
Colhex/Colsqu
Colhex/Colsqu
→
I
45.4
110.6
124.2
140.1
104.3
2.3
0.3
2.6
a C , c ys al phase; M: unknown mesophase wi h a la ge supe la ice; Col ec,
ec angula columna mesophase; Colhex, hexagonal columna mesophase; Colsqu,
squa e columna mesophase; I, iso opic liquid; mesophase assignmen based on
S/WAXS s udies b Da a collec ed om he second hea ing DSC cycle. The ansi ion
empe a u es a e gi en as peak onse s. c Scanning a e: 5 °C/min.
All he compounds show good s abili y up o empe a u es
abo e 200 °C (Figu es S12–S15), and display enan io opic
mesophases, as deduced om he obse a ion o luid and
bi e ingen op ical ex u es (Figu e 3 and Table 1). Ei he wo
( o
3
,
4
,
5
) o h ee ( o
6
,
7
) mesophases a e de ec ed be ween
he mel ing and he clea ing poin in he DSC cycles, bo h in he
hea ing and in he cooling, con i ming he polymesomo phism
o hese compounds (Figu es S7-S11 in he Suppo ing
In o ma ion). The ex u es obse ed by POM on cooling om
he iso opic liquid, simila o all compounds, a e a p io i
compa ible wi h he occu ence o columna mesophases.
26,34
Howe e , hei unambiguous exac iden i ica ion om he
ex u es obse ed is no possible.
Figu e 3. Op ical pola izing mic oscopy pho og aphs (x100, c ossed pola ize s) on
cooling om he iso opic phase o : a) [TPh-NH
2
E ]Cl (3) a 87 °C; b) [TPh-
NH
2
E ]
2
[CuCl
4
] (4) a 109 °C; c) [TPh-NH
2
E ]
2
[NiCl
4
] (5) a 112 °C.
A mo e p ecise iden i ica ion o he liquid c ys alline
mesophases was achie ed by S/WAXS. The pa e ns eco ded
o all compounds in hei p is ine s a e and a a ious
empe a u es (Figu es S16-S20, Tables 2 and S1 in ESI) con i m
ha he complexes sel -o ganize in o mul iseg ega ed columna
s uc u es, wi h he al e na ion wi hin la ge supe la ices o
TPh-con aining columns and benzylammonium chlo ide o
e acho ome alla e sal s (labelled as BzaS = Benzylamonium-
Sal ) embedded in an alipha ic con inuum. The p is ine s a es
a e cha ac e ized by he p esence o one sha p small-angle
peak, se e al un esol ed di used signals o e he S/WAXS
angula ange, and a sligh ly s uc u ed b oad signal in he wide-
angle ange, co esponding o incomple ely mol en alipha ic
chains, an indica ion o pa ially c ys allized solid s a e wi h s ill
high le el o s uc u al diso de . On u he hea ing, he X- ay
pa e ns a e sys ema ically ans o med, in ag eemen wi h he
induc ion o a mo e long- ange sup amolecula o ganiza ion.
Whils s ill e aining he single sha p small-angle e lec ion, one
could obse e he de elopmen o he mid-angle b oad
sca e ing signal, labelled D, in o a se o se e al no -well
esol ed bu sha p e lec ions (Figu e 4 and S16-S20), and he
spli ing o he b oad la ge-angle sca e ing in o wo di e en
con ibu ions, namely: i) he s ong one a ca. 4.5-4.6 Å,
co esponding o he undi e en ia ed liquid-like la e al
dis ances be ween alipha ic chains and space s and
benzylammonium-sal moie ies, h
ch
+h
BzaS
, espec i ely; and ii)
he one a 3.5-3.6 Å, co esponding o he iphenylene uni s
o hogonally s acked o e sho dis ances, h
p
. A his s age, he
na u e and symme y o his mesophase, M, could
un o una ely no be unambiguously esol ed, as oo many
indexa ion solu ions we e compa ible wi h so ew no -so-well
esol ed e lec ions. I could ne e heless co espond o a long-
ange, likely 3D, p e-o ganized s uc u e o he mesophase
o ming a highe empe a u e.
The X- ay pa e ns we e sligh ly modi ied on u he hea ing,
and all he sha p and s ong e lec ions could be indexed
acco ding o a 2D ec angula symme y (Table S1). In he wide-
angle pa , he spli signals h
ch
+h
BzaS
/h
p
o he p eceding M
phase was ans o med in o a single b oad and ex ended wide-
angle signal co esponding o he o e all me ging o all he
a ious con ibu ions (h = h
ch
+h
BzaS
+ h
p
) (h
p
, is ha dly isible o
compounds
3
and
7
, and has o ally disappea ed o he o he
compounds, in ag eemen wi h he educ ion o he s acking
dis ance o a ew iphenylene uni s only). As jus men ioned, in
he small-angle ange, hey exhibi a se o se e al sha p small-
angle e lec ions (hk) cha ac e izing he wo-dimensional
a angemen o mesogenic columns sepa a ed in space by a
mol en alipha ic con inuum. The p esence o he unde lying
b oad signal a in e media e angula ange, D, was s ill
de ec ed, as o he mesophase M, which was associa ed o he
de elopmen o some local- ange supe s uc u e.
Finally, as men ioned abo e, o he Co and Mn complexes an
addi ional mesophase could be de ec ed be ween he
ec angula phase and he iso opic liquid. In he wo cases, he
only di e ence wi h he ec angula phase is he collapse o he
mid-angle e lec ions in o he single b oad sca e ing signal, D,
and he p esence o only one sha p small-angle e lec ion. In he
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wide-angle, all signals om he chains, he BzaS and TPh uni s
a e o e lapped in o an undi e en ia ed single b oad signal, h.
On his basis, he mesophase could be assigned ei he as
hexagonal (Col
hex
) o as squa e (Col
squ
) columna mesophase.
In he iso opic liquid phase (Iso), he b oad small-angle signal D
was ound o pe sis , which is due o some eminiscence o he
nanoseg ega ion s ill occu ing a he local- ange le el be ween
he TPh and he BzaS moie ies. The single b oad signal seen in
he wide-angle ange o he Col
hex/squ
phase is associa ed o
undi e en ia ed liquid-like con ibu ions o he chains, BzaS
and TPh moie ies.
Figu e 4. Rep esen a i e S/WAXS pa e ns o he compounds in he mesophase. hk
indexa ion o he small-angle peaks; hch+hBzaS, undi e en ia ed liquid-like la e al
dis ances be ween alipha ic chains and space s, and benzylammonium-sal moie ies,
espec i ely; hp, iphenylene s acking o e sho dis ances; D, sho - ange co ela ed
pe iodici y om he sup amolecula assembly. Fo 6, he signal canno be decon olu ed
since he s acking signal (hp) is oo weak, i no unexis en ; i s heo e ical posi ion (shown
in b acke s) is indica ed by he dashed a ow.
The eme gence o columna mesophases wi h la ge supe la ice
s uc u es, con aining se e al columns pe la ice
(mul icolumna mesophases, see below), was hus con i med
o all compounds by he p esence o se e al sha p, small-angle
e lec ions, e ealing la ices wi h la ge dimensions, along wi h
he modula ion o he e lec ions in ensi y dis ibu ion. These
pa e ns also con i med he e icien seg ega ion be ween he
a ious pa s, namely, he iphenylene discs, he BzaS species
(Cl
–
o [MCl
4–
] anions) and he chains. As expec ed, he
mesomo phism induc ion o his kind o compounds is s ongly
d i en by he endency o he iphenylenes o s ack in o one-
dimensional columns and o nanoseg ega e in space due o
hei pe iphe al alkyl chains. Howe e , he BzaS agmen s a e
also con ined in o sepa a e zones, and hei a angemen mus
espec he a ious geome ical cons ain s and he mesophase
symme y in each case. The e o e, hese sal s sel -assemble in
la ge supe la ices o ec angula and hexagonal/squa e
symme ies wi h he conce ed en anglemen o wo
subne wo ks o se e al iphenylene-based columns and BzaS-
based (me al-based) columns, espec i ely, each ypes being
sepa a ed by he in ini e con inuum o mol en alkyl chains.
As p e iously de eloped,
23,26
mo e in ima e de ails abou he
espec i e o ganiza ion o he wo subse s o columns wi hin
he supe la ices can be e ealed om he a io be ween he
molecula olume (V
mol
) and he la ice a ea (A, wi h Z = 2, o
he ec angula symme y, and Z = 1 o hexagonal/squa e
symme y), scaled by he o al numbe o ligands o complexes
pe la ice, Z
mol
(Table 2). This le us o deduce he numbe o
TPh- and BzaS-based columns pe la ice (Z
col,TPh
= Z
mol
×n
TPh/mol
,
Z
col,BzaS
= Z, espec i ely) by epea ing ial-e o es s and
conside ing he mos logical solu ion in ag eemen wi h he
symme y elemen s o he plana g oup, i.e. ec angula and
hexagonal/squa e plana g oups (Table 2). This calcula ion also
p o ides a alue o h
TPh
, he molecula slice hickness along he
TPh-based columns (h
TPh
= (V
mol
/n
TPh,mol
)/(A/Z
col,TPh
)), which lies
close o he alue o h
p
, consis en wi h a nea ly o hogonal
s acking o he iphenylene discs in he columns.
Fo he ec angula phases, a alue o 8 ( o he p ecu so
3
) and
4 ( o he complexes
4-7)
is deduced o Z
mol
, espec i ely, which
gi es columna ec angula supe la ices con aining 8 TPh- and
2 BzaS-based columns. A plausible sup amolecula a angemen
o he columns in he ec angula mesophase (Figu e 5) would
consis o a s ack o ammonium/me al agmen s loca ed a he
nodes o he ec angula la ice (co ne s and cen e, Z
col,BzaS
= 2),
in e wined by a ne wo k o 8 discoidal columns (Z
col,TPh
), hus
espec ing he iphenylene-me al agmen s oichiome y,
bo h sepa a ed by he alipha ic con inuum, in comple e
ag eemen wi h he cen ed symme y and dimensions o he
ec angula la ice, and he modula ed dis ibu ion o he
in ensi ies o he highe o de e lec ions.
As o he Col
hex/squ
phase o compounds
6
and
7
, hese
calcula ions gi e 2 complexes, wha e e he symme y
conside ed, ha indica es a sel -assembly made o 4 TPh- and 1
BzaS-based columns (Table 2). F om he S/WAXS pa e ns, i
was no possible o disc imina e be ween a columna
mesophase wi h hexagonal o squa e symme y (only he
undamen al e lec ion is seen), so bo h mesophases a e
equip obable. Thus, a possibili y o a anging he columns in
he mesophase (Figu e 4) would consis o a s ack o me al
agmen s loca ed a he co ne s o he hexagonal/squa e
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la ice (Z
col,BzaS
= 1), in e wined by a ne wo k o 4 discoidal
columns (Z
col,TPh
) wi hin he la ice, also espec ing he
iphenylene-me al agmen s oichiome y, bo h ypes o
columns being sepa a ed by he alipha ic con inuum. The only
di e ence, and his would be mo e in he a ou o he squa e
la ice, is he es ima ion o h
TPh
, which gi es a alue o ca. 4.2-
4.3Å close o h (4.3Å, Table 2), conside ing he squa e
symme y, whe eas his calcula ion gi es a alue o ca. 3.7Å o
he hexagonal case.
Table 2: S uc u al pa ame e s.
Cpdsa
T (°C)
Phaseb
(Z)
2D la ice
pa ame e sc
Vmold
nBzaS/mole
nTPh/mol
hp [x]/h
Zmol
Zcol,BzaSg
Zcol,TPh
hTPhh
3
90
Col ec
c2mm
(Z = 2)
a = 89.6(9);
b = 65.6(7);
g = 90°;
A = 5890 Å2;
a/b = 1.37
2541
0.94
1
1
3.6 [2]/4.5
8
2
8
3.45
4
110
Col ec
c2mm
(Z = 2)
a = 91.0(8);
b = 65.0(8);
g = 90°;
A = 5927 Å2;
a/b = 1.40
5269
0.95
1
2
3.6 [2]/4.5
4
2
8
3.56
5
110
Col ec
c2mm
(Z = 2)
a = 90.4(7);
b = 65.7(3);
g = 90°;
A = 5947 Å2;
a/b = 1.38
5268
0.95
1
2
3.6 [2]/4.5
4
2
8
3.54
6
115
Col ec
c2mm
(Z = 2)
a = 91.3(0);
b = 66.2(5);
g = 90°;
A = 6049 Å2;
a/b = 1.38
5285
0.94
1
2
3.5 [2]/4.5
4
2
8
3.50
6
135
Colhex
p6mm
(Z = 1)
a = b = 57.6;
g = 120°
A = 2871 Å2
5352
0.93
1
2
-/4.3
2
1
4
3.73
Colsqu
p4mm
(Z = 1)
a = b = 49.9;
g = 90°
A = 2490 Å2
5352
0.93
1
2
-/4.3
2
1
4
4.3
7
115
Col ec
c2mm
(Z = 2)
a = 92.2(5);
b = 65.5(5);
g = 90°;
A = 6047 Å2;
a/b = 1.41
5310
0.94
1
2
3.6 [2]/4.5
4
2
8
3.51
7
135
Colhex
p6mm
(Z = 1)
a = b = 58.0;
g = 120°;
A = 2917 Å2
5360
0.93
1
2
-/4.3
2
1
4
3.68
Colsqu
p4mm
(Z = 1)
a = b = 50.3;
g = 90°
A = 2530 Å2
5360
0.93
1
2
-/4.3
2
1
4
4.2
aT: empe a u e o he measu emen ; bCol ec, Colhex/squ: ec angula and hexagonal/squa e columna mesophases and highes possible symme y, Z: numbe o mo i s
(molecula agg ega es) pe la ice; ca, b, g, A = a×b×sing, Z, a/b: la ice pa ame e s, la ice a ea and la ice pa ame e a io; dVmol (Å3), (g/cm3): calcula ed molecula
olume and densi y; enBzaS/mol, nTPh/mol: numbe o benzylammonium/anion uni s and numbe o TPh uni s pe molecule (s oichiome y); hp, [x]: a e age p-s acking
dis ance (Å) and associa ed co ela ion leng h om wide-angle sca e ing analysis (nm) calcula ed using he Sche e equa ion wi h shape ac o K = 0.9;
49
h:
undi e en ia ed liquid-like con ibu ions o he chains, BzaS and TPh moie ies; Zmol: numbe o molecules pe la ice; gZcol,BzaS = Z: numbe o benzylammonium/anion
columns pe la ice; Zcol,Tph = Zmol×nTPh/mol: numbe o TPh columns pe la ice; hhTPh = (Vmol/nTPh,mol)/(A/Zcol,TPh): molecula slice hickness along TPh columns (Å).

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Figu e 5. Illus a ion o he p oposed 2D packing o he Col ec mesophase (c2mm
symme y, and o he Colsqu mesophase (p4mm symme y), and o he Colhex
mesophase (p6mm symme y). The pink disks co espond o TP-based columns, and he
g een pe als o BzaS–based agg ega es; he alipha ic chains, occupying he whi e a eas,
a e no shown o cla i y.
The moch omic beha iou
The nickel complex
5
is g een a oom empe a u e and
swi ches o a bluish colou upon hea ing a abou 60 °C (Figu e
6). The compound shows e e sible he moch omic beha iou
and, upon cooling o oom empe a u e, i e u ns g adually o
i s o iginal g een colou .
Figu e 6. Pho og aphs o he moch omic complex [TPh-NH2E ]2[NiCl4] (5) a di e en
empe a u es.
In o de o unde s and his colou change, he elec onic
spec a o a d op-cas ilm o
5
we e eco ded a di e en
empe a u es (Figu e 7).
Figu e 7. Elec onic spec um o [TPh-NH2E ]2[NiCl4] (5) a 35 °C. Inse : spec al changes
p oduced upon a ying he empe a u e.
As discussed in he syn hesis and cha ac e iza ion sec ion,
be o e hea ing he elec onic spec um o
5
is domina ed by
abso p ion bands in he ange 240-400 nm, co esponding o
he 2,3,6,7,10,11-hexaalkoxy iphenylene g oup, which
p ac ically o e lap he weak abso p ion band (
3
A
2g(F)
→
3
T
1g(P)
ansi ion) co esponding o oc ahed ally coo dina ed nickel.
When he sample is hea ed abo e 45 °C, a double abso p ion
band appea s, wi h maxima a 658 nm and 711 nm, which is
ypical o he blue e ahed al [NiC1
4
]
2-
complex anion (
3
T
1(F)
→
3
T
1(P)
ansi ion).
40,48
The e o e, he he moch omic phase
ansi ion o he complex is assigned o he coo dina ion change
o Ni(II) om oc ahed al o dis o ed-oc ahed al o e ahed al,
as epo ed o ela ed non-mesogenic complexes in he solid
s a e.
48,
50
Acco ding o he plo o abso bance s empe a u e
(Figu e 8), he ansi ion occu s be ween 50 and 80 °C. Thus, he
he moch omic ansi ion s a s and de elops along he mel ing
p ocess.
Figu e 8. Abso bance change a
𝜆
= 650 nm and
𝜆
= 700 nm as a unc ion o empe a u e.
Magne iza ion measu emen s o he nickel compound a
di e en empe a u es we e pe o med o assess he changes
in magne ic p ope ies associa ed o he he moch omic
ans o ma ion. The esul ing ield dependen magne iza ion
cu es a e shown in Figu e 9.
Figu e 9. Field dependen magne iza ion cu e o he nickel compound (5) a di e en
empe a u es.
All he magne iza ion cu es (Figu e 8) show an o e all simila
pa e n, in which wo di e en magne ic con ibu ions a e
obse ed. In e es ingly, when looking in o de ail, he ield
dependen magne iza ion cu es a empe a u es below he
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he moch omic ans o ma ion (3 and 27 ºC) a e di e en om
hose eco ded a highe empe a u es (77 and 100 ºC), in
ag eemen wi h he phase ansi ion occu ing be ween 50 and
80 °C.
In all cases, in he low- ield egime obse ed in he inse o
Figu e 8, a hys e esis loop wi h non-negligible coe ci i y was
eco ded, indica ing e o- o e imagne ic in e ac ion be ween
he Ni(II) a oms. In addi ion o his magne ic con ibu ion, a
clea pa amagne ic beha iou is obse ed a highe ields,
e ealed by he inc ease o he magne iza ion as he magne ic
ield inc eased, wi hou any sign o sa u a ion. These esul s
indica ed he co-exis ence o wo ypes o en i onmen s o he
Ni a oms wi hin he ma e ial s uc u e. This ac is in acco dance
wi h he X- ay da a discussed abo e: i) he pa ially c ys alline
na u e o he solid phase and i s high le el o s uc u al diso de ;
and ii) he pe sis ence in he mesophases o some local- ange
supe s uc u e de ec ed in he solid s a e.
Consequen ly, he e o- o e imagne ic con ibu ion can be
assigned o he c ys al s uc u e o his ype o compound,
whe e dis o ed Ni
II
Cl
6
oc ahed a a e sha ing b idging chlo o
ligands. Howe e , he species con ibu ing o he pa amagne ic
beha iou would be di e en depending on he empe a u e.
A empe a u es abo e he mo opic ansi ion, he o ma ion
o e ahed al e achlo onickela e anions explains he
p esence o a pa amagne ic signal. Howe e , a lowe
empe a u es, whe e his anion was no spec oscopically
obse ed, he pa amagne ic con ibu ion should be associa ed
wi h he non-c ys alline solid ac ion, in which long- ange
o de ing will no occu as in he c ys alline ac ion.
Langmui ilms
Conside ing he amphiphilic na u e o he mesomo phic TPh-
NH
2
E
+
sal s, we decided o s udy hei abili y o o m 2D
nanos uc u es a he ai -wa e in e ace (Langmui ilms).
Compounds [TPh-NH
2
E ]Cl (
3
) and [TPh-NH
2
E ]
2
[NiCl
4
] (
5
) we e
chosen as ep esen a i e sal s o his s udy. Bo h compounds
o m monolaye ilms unde comp ession. Figu e 10 shows he
su ace p essu e s. mean molecula a ea (SP-A) ob ained a 20
± 1 °C, as well as he a ia ion o he ecip ocal o he
comp essibili y (1/
𝛽
).
51
,
52
Figu e 10. SP–A iso he ms and 1/
𝛽
–A plo o compounds 3 and 5. Table: Molecula
occupied a eas a di e en phases and collapse p essu e o he Langmui ilms. LC =
liquid condensed phase.
Bo h monolaye ilms unde go a phase ansi ion be ween wo
liquid condensed (LC) phases, deno ed by a minimum in 1/
𝛽
which coincides wi h he sligh in lec ion obse ed in he
iso he m a 20–30 mN/m. The collapse is eached a high
su ace p essu es (
≈
50 mN/m), e ealing a good ancho ing o
he ionic heads o he subphase. In addi ion, he pla eau ha
appea s jus a e he collapse deno es he esis ance o he
monolaye espec o he ans o ma ion in o a 3D phase.
53
In
good ag eemen wi h i s double con en in TPh moie ies, he
o mula uni o
5
occupies wice he a ea o ha o
3
. Howe e ,
he molecula a ea pe iphenylene g oup is la ge o
3
han
o
5
despi e he bigge olume o he [NiCl
4
]
2−
anion. This is
mos likely due o he inc ease in he ionic cha ge in [NiCl
4
]
2−
wi h espec o Cl
−
which enhances he anion-ca ion a ac ions,
inc easing he ilm cohesion.
The ilms s a o be o med wi h molecula a eas pe
iphenylene o 127 ± 5 Å
2
(A
onse
) and each ex apola ed o ze o
mean molecula a eas (A
e
) o 117 ± 4 Å
2
in he i s s ep o he
iso he m. These molecula a eas oge he wi h he 1/
𝛽
alues
indica e ha he loa ing ilms o
3
and
5
a e in a liquid
condensed phase LC1 whe e he TPh moie ies lay edge-on
espec o he subphase.
54
,
55
,
56
On u he comp ession, he LC1
phase e ol es o ano he condensed bu less igid phase LC2,
whe e he ex apola ed a eas a e equal o sligh ly smalle han
hose in LC1, (see Figu e 10).
This beha iou is unlike ha epo ed o he TPh-imidazolium
o py idinium sal s,
55
whe e he monolaye i s ly shows a liquid
expanded (LE) phase, wi h he iphenylenes lying la on he
subphase, and hen eaches a mo e igid phase, bu no LC, wi h
he iphenylenes s acked edge-on. This di e en beha iou
may be ela ed wi h he ac ha he longe chain leng h and
he smalle size o he ca ionic heads in ou compounds
enhance he magni ude o he a ac i e in e ac ions o e he
disagg ega ion powe o he wa e .
Moni o ing o he comp ession p ocess by B ews e 's angle
mic oscopy (BAM) (Figu es S21 and S22 in ESI) shows ha
be o e comp ession,
3
and
5
exhibi i egula pa ches o
condensed monolaye s, in acco dance wi h he high endency
o iphenylene g oups o sel -assembling h ough
𝜋
-
'𝜋
in e molecula in e ac ions. Thus, he comp ession p ocess
should s a wi h agg ega es whose s uc u e mos likely
consis s o columns o ca ions sandwiching a cen al egion o
anions.
As he p essu e inc eases (1 <
𝜋
< 20 mN/m), he app oxima ion
o he agg ega es leads o he o ma ion o a condensed
monolaye (LC1) whe e he molecula a angemen
is, as
p e iously discussed, edge-on ype wi h he iphenylene
g oups a anged in columns pa allel o he subphase (Scheme
2). A highe p essu es (20 <
𝜋
< 50 mN/m), he compac ion o
he monolaye and he consequen inc ease o he epulsion
be ween ions p oduces he phase ansi ion om LC1 o LC2.
BAM images o bo h phases show ha he monolaye is
cons i u ed by di e en domains, which should be due o
di e en domain o ien a ions.
53
No di e ences could be
app ecia ed a he phase ansi ion bu an inc ease in
b igh ness, which is usually ela ed o a mo e dense packing as
well as o an inc ease in he monolaye hickness. These
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obse a ions along wi h he ac ha he ex apola ed a eas in
bo h phases do no display signi ican di e ences, sugges ha
LC1 and LC2 mainly di e in he molecula o ien a ion o he
TPh g oup wi h espec o he aqueous subphase. We p opose
ha he TPh agmen s o a e and only he ionic g oups a e
ancho ed o he subphase in LC2, leading o columna molecula
a angemen s as depic ed in Scheme 2b.
Scheme 2. P oposed columna a angemen a he ai -wa e in e ace co esponding o
LC1 phase (a) and LC2 phase (b) adap ed o compound 5.
Finally, o ma ion o 3D s uc u es (b igh e ical lines) was no
obse ed un il o e aking he p essu e o collapse, hus
co obo a ing he abo e-men ioned esis ance o he
monolaye o ha ans o ma ion.
Langmui -Blodge ilms
Langmui ilms o
3
and
5
we e ans e ed o glass subs a es
a wo di e en p essu es co esponding o LC2 (SP = 35 mN/m)
and LC1 (SP = 15 mN/m) phases o build up Langmui Blodge
(LB) ilms.
Good Y- and Z- ype deposi ions we e achie ed, wi h ans e
a es nea o he uni y, using hyd ophobic and hyd ophilic
glasses espec i ely. To he bes o ou knowledge, he e a e no
examples epo ed o Z- ype LB ilms om disco ic
amphiphiles.
51,52,56,
57
,
58
,
59
.
The ans e sal s uc u e o Z and Y- ype mul ilaye LB ilms was
s udied by means o low-angle X- ay di ac ion. The
di ac og ams co esponding o bo h ype o LB ilms buil a a
cons an comp ession o 35 mN/m a e depic ed in Figu e 11. All
o hem show h ee di ac ion peaks co esponding o (00l)
planes, as well as se e al se s o Kiessig inges. This means ha
he LB ilms ha e a pe iodic laye ed s uc u e wi h a small
ugosi y.
60
A 15 mN/m, simila bilaye ed s uc u es ha e been
ob ained, bu wi h smalle laye hickness (di ac og ams in
ESI), con i ming ha he hickness o he monolaye inc eases
on passing om LC1 o LC2 phase, as abo e sugges ed. Table 3
collec s he expe imen al plana dis ances and he mean laye
hickness o each ilm.
Figu e 11. Low-angle X- ay di ac og ams o he LB ilms o 3 and 5.
Table 3. Low-angle XRD da a o he LB ilms o 3 and 5. All alues in Å.
3
5
Y- ype deposi ion a LC2 a
d(00l) c
61.2
63.5
Laye hickness d
32.9
34.3
Z- ype deposi ion a LC2 b
d(00l)
57.6
59.1
Laye hickness
53.5
53.5
Z- ype deposi ion a LC1 b
d(00l)
53.1
54.4
Laye hickness
45.3
45.9
(a) Subs a e = hyd ophobized glass. (b) Subs a e = hyd ophilic glass. (c) Plana
dis ances d(00l) ha e been calcula ed by a e aging he co esponding alues o
each di ac ion peak. (d) The ilm hickness, , was calcula ed om he pe iodici y
o he Kiessig inges subs i u ing he slope a o he g aph senθn/n in he o mula
= λ/2a.60 The mean single laye hickness was calcula ed om he a e /numbe
o ans e ed monolaye s.
I is wo h no ing ha , independen o he deposi ion ype, all
he di ac og ams display a simila pa e n, which is consis en
wi h analogous bilaye s uc u es. A bilaye s uc u e upon Y-
deposi ion is he expec ed esul . Howe e , upon Z-deposi ion,
he o ma ion o a bilaye should equi e a eo ganiza ion o he
deposi ed monolaye , as has been epo ed o LB ilms o a y
acids
61
,
62
,
63
o phospholipids.
64
Thus, i is plausible ha he
ups oke- ans e ed monolaye unde goes o e u ning du ing
he subsequen imme sion, acqui ing a mo e s able bilaye ed
s uc u e wi h a new hyd ophilic su ace p one o adhe e he
ollowing monolaye a ups oke.
Conclusions
This s udy shows he ma ked endency o hese iphenylene-
benzyle hylamonium de i a i es o sel -o ganize in o
mul iseg ega ed s uc u es. S uc u al s udies suppo he
nanoseg ega ion o iphenylene columns and
benzylammonium chlo ide o e acho ome alla e sal
moie ies, leading o mul icolumna sys ems, bo h in he solid
s a e and in he mesophases. The he mal, op ical and magne ic
p ope ies o hese ma e ials a e easily modula ed by he
na u e o he anion. The in oduc ion o he
e achlo onickela e g oup leads o he combina ion o
mesomo phism and he moch omism in he sys em. This
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compound shows isually a e e sible he moch omic
beha iou , ligh -g een a oom empe a u e and blue a 70 °C,
which was s udied wi h spec oscopical and magne iza ion
measu emen s. The he moch omism in his compound implies
a coo dina ion change o he nickel(II) cen e, om oc ahed al
o e ahed al, which is no simple. The magne iza ion
measu emen s a di e en empe a u es e eal he co-
exis ence, in he condi ions o he measu emen s, o wo ypes
o con ibu ions o he Ni(II) a oms in he ma e ial, one
co esponding o e o- o e imagne ic in e ac ions oge he
wi h a pa amagne ic beha iou ha changes abo e
he mo opic ansi ion. In addi ion, hese compounds sel -
assemble in o nanos uc u ed LB ilms wi h a well-de ined
bilaye ed s uc u e whe e each laye is cons i u ed by he
alignmen o molecula columns along he su ace.
These esul s a e in e es ing o u u e ailo ing o me al-
o ganic liquid c ys als combining he moch omic and magne ic
esponse.
Au ho Con ibu ions
The au ho s ha e con ibu ed equally o he pape .
Con lic s o in e es
The e a e no con lic s o decla e.
Suppo ing in o ma ion
Ma e ials and me hods, ull de ails o syn he ic me hods,
spec oscopic and analy ical da a o he new compounds, DSC
he mog ams and X- ay di ac ion pa e ns no included in he
ex .
Acknowledgmen s
This wo k was sponso ed by he Minis e io de Ciencia e
Inno ación (P ojec PID2020-118547GB-I00) and he Jun a de
Cas illa y León (P ojec VA224P20). M. B. hanks he Jun a de
Cas illa y León o a PhD g an . BD and BH hank CNRS and he
Uni e si y o S asbou g o suppo .