Self-assembly and liquid-crystalline supramolecular organizations of semifluorinated block co-dendritic supermolecules

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PAPER

Self-assembly and liquid-crystalline supramolecular organizations of

semiﬂuorinated block co-dendritic supermoleculeswz

a

b

ˆ

Izabela Bury, Benoıt Heinrich, Cyril Bourgogne, Georg H. Mehl,

Daniel Guillon^aand Bertrand Donnio*^a

Received (in Montpellier, France) 16th June 2011, Accepted 19th September 2011

DOI: 10.1039/c1nj20530g

The synthesis and self-organizing behaviour into liquid-crystalline mesophases of two libraries of

segmented block co-dendrimers are described. The overall structure of the dendritic

supermolecules consists of two chemically incompatible molecular moieties, covalently connected

by combinatory cross-coupling reactions. One block is composed of linear perﬂuorinated

segments (2 generations, deﬁning the two libraries), and the bulky dendritic compartment is

formed by a lipophilic poly(benzyl ether)-based dendron (3 generations). The mesomorphic

properties were studied as a function of the respective generations of both blocks and of the

peripheral alkyl chains’ substitution pattern. The results of these investigations reveal the

formation of unusual and highly segregated supramolecular liquid-crystalline mesophases, whose

arrangements are subtly controlled by the lipophilic/ﬂuorophobic balance and dendritic

connectivity.

systems is at the origin of the development of noncovalent

Introduction

supramolecular chemistry, aiming at the elaboration of

preprogrammed self-assemblies of simple molecules interacting

by noncovalent intermolecular forces and mimicking natural

processes.⁴The dynamic nature, function-integration and

stimuli-responsiveness abilities of these structured assemblies⁵

should oﬀer many new research opportunities in molecular

chemistry with inﬁnite potentialities in the development of

highly complex and functional molecular systems, in addition

render them inevitable for some future technological and

biological applications (molecular machines, host–guest

architectures, sensors, catalysts, switches, signal ampliﬁcation

devices, therapeutic and transfecting agents, . . .). A careful

molecular design and judicious choice of the primary constitutive

building blocks (chemical shape, interaction strength, speciﬁcity

and directionality) makes it possible to partially predict the

nature of such dynamic supramolecular assemblies and a

plethora of supramolecular architectures have been fabricated

by design,⁶including spherical micelles, vesicles, ﬁbers,^1–3,72D

polygons and 3D cages and polyhedra,⁸grids,⁹supramolecular

helices,¹⁰knots,¹¹polymers,¹²networks^13–15and frameworks,¹⁶

nanoribbons,¹⁷and nanotubes,¹⁸etc.. . . However, in mostly all

situations, it appears diﬃcult to anticipate any of their emergent

functions.

Large and complex biological chemical systems are formed

dynamically, i.e. in a reversible manner, via a subtle balance of

weak attractive and repulsive, noncovalent intermolecular

interactions, between small preexisting complementary molecular

components. Their further hierarchical self-assembly, essentially

driven by chemical shape-encoding and by the directionality

and strength of these intermolecular interactions, leads to a

broad and diverse range of complex supramolecular self-organized

structures and objects, eventually responsible for emerging

new functions. See for example, long strands of nucleic acids,

formed from a few building blocks held together by weak

hydrogen bonds, responsible for information retrieval and

processing, or the function triggering of hormone–protein pairs

assembled by molecular recognition, endowed with sensing

abilities once self-organized in speciﬁc association with glyco-

lipids or phospholipids into cell walls, vesicles, ﬁbers and

membranes.^1–3Such high level complexity found in living

a

´

Institut de Physique et Chimie des Materiaux de Strasbourg

(IPCMS), UMR 7504, CNRS-Universite de Strasbourg,

´

23 rue du Loess, BP43, 67034, Strasbourg cedex 2, France.

E-mail: bdonnio@ipcms.u-strasbg.fr; Fax: +33 388107246;

Tel: +33 388107156

^bUniversity of Hull, Department of Chemistry, Cottingham Road,

Hull, HU67RX, UK

Thermotropic (and lyotropic) liquid crystals (LCs), for

which weak intermolecular interactions have long been

exploited, can be envisioned as such basic units and considered

as a prime example of noncovalent supramolecular assemblies

where order coexists with ﬂuidity. In recent decades, various

supramolecular approaches based on molecular recognition

w This article is part of the themed issue Dendrimers II, guest-edited

by Jean-Pierre Majoral.

z Electronic supplementary information (ESI) available: Experimental

section, optical textures (Fig. S1–S6), molecular dynamics (Fig. S7),

diﬀractograms (Fig. S8–S12), tables (Tables S1–S2), model (Fig. S13),

DSC (Fig. S14–S17). See DOI: 10.1039/c1nj20530g

c

452 New J. Chem., 2012, 36, 452–468

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events have been successfully considered for generating novel

LC assemblies integrating new functions.^19–22In particular,

self-organization of functional dendritic supermolecules and

supramolecules, originating from predeﬁned self-assembly

programs, into low-dimensional periodic liquid crystalline

lattices, elicits intense research activity in the ﬁeld of

dendrimers.^23,24Indeed, not only a great diversity of complex

supermolecular architectures may be accessible, a large variety

of functional supramolecular organizations may also

emerge.^23–25Molecular design of dendrimers should provide a

better understanding of the intricate self-assembling processes

involved in the formation of structurally related primary to

high-level structures, mimicking those of biological structures,

and possibly to permit a better control of functions hierarchy

and speciﬁcity. Despite these remarkable assets, the control of

self-assembling and self-organizing processes into predeﬁned

supramolecular structures, essential criteria for their uses in

various applications, still remain a demanding challenge.

In this regard, the supramolecular dendritic concept developed

by Virgil Percec is particularly remarkable.²⁴The idea consists of

the selective self-assembling of structurally perfect, alkyl-chains

terminated, supermolecular dendritic poly(aryl)ethers, designed

with pre-programmed molecular conformations (chemical-shape

encoding), into coins, cones, sheets, cylinders or pseudo-spherical

supramolecular objects, and their subsequent self-organization

into lamellar, columnar and cubic/tetragonal (discontinuous and

bicontinuous) liquid-crystalline mesophases.²⁴The originality

(and strength) of this concept lies essentially in its simplicity

(e.g. straightforward molecular design and synthesis) and

versatility (e.g. facile and multiple modiﬁcations of the intrinsic

dendritic connectivity leading to a wide range of simple-

to-highly complex molecular architectures). The dendritic

arborescence is generated by the multivalent connections of

benzyl (or aryl) junctions through ether links into successive

rows; the generation number (G = 0 - 5), the branching

multiplicity (1 - 3 for 4-, 3,4-, 3,5- and 3,4,5-type branching),

and topology of the arborescence (homogeneous or mixed

arborescence with generation increase, nature of the junctions)

have been systematically varied. The periphery is equipped by

ﬂexible alkyl²⁴and/or semi-ﬂuorinated chains (RQOC_nH_2n+1

vs. O(CH₂)_n(CF₂)_mF),²⁶with diﬀerent positions of grafting

(1 chain in the 4-position, 2 chains in the 3,4- or 3,5-positions,

and 3 chains in the 3,4,5-positions on the terminal phenyl rings),

whilst the apical functional group is usually made hydrophilic

(i.e. CO₂R, with RQH, Me, Et, alkali metals, alkali earth

metals, rare earth metals, CH₂OH, CO₂(CH₂CH₂O)_pR,

with RQH, Me, crown ethers, polyols, peptides, etc.. . .)^23,24

but not always (e.g. polymeric backbone).²⁴Comprehensive

investigations of the self-organizing behavior of this plethora

of dendrons libraries, with rationally designed architectures,

have permitted understanding self-assembling processes as

well as assessing molecular criteria governing growth rates,

shape and size of the dendrimers and supramolecular assem-

blies. In such ramiﬁed molecular systems, self-organization is

governed by time-average conformational changes adopted by

the dendron. Alkylated dendritic wedges of low connectivity can

approach fan, conical, semi-discoid shapes and aggregate into

inﬁnite supramolecular sheets or columns to form lamellar or

columnar phases, respectively. Functionalized at the periphery

by ﬂuorinated segments, they however generate more restricted

cone-like shape which stack on top of each other to yield polar

columns.²⁶As theoretically anticipated, systems of high connec-

tivity rather lead to reduced cooperative molecular rotation

which favors important 3D deformations of the molecules

(pseudo-spherical conformations, via conical and hemi-sphere-like

intermediates) and contribute to the formation of 3D structures

(e.g. micellar cubic or even more complicated 3D phases).²⁷

The resulting nanostructures appear therefore as promising

candidates, prior to the appropriate functionalization of the

dendritic wedges and focal points, to be integrated into

optoelectronic and electronic devices,^24,26or as biomaterials

in which the principles of organization into 3D tertiary

structures of bioinspired supramolecular dipeptidic^24,28and

folic²⁹dendrimers, can help modeling and understanding

biological processes or used in gene and viral therapies.

In the following study, the liquid-crystalline self-organizing

behaviour of two main libraries of segmented block co-dendrimers

is investigated as a function of the two blocks’ generations and

peripheral chains’ substitution pattern (Chart 1). The co-dendritic

supermolecules are constituted of linear perﬂuorinated

segments and of a poly(benzyl ether)-based dendron as the

bulky wedge, whose periphery is functionalized selectively by

lipophilic dodecyl aliphatic fragments to ensure ﬂuidity; as such,

they possess an inverted topology with respect to LC dendrons²⁶

and dendrimers functionalized by end-ﬂuorinated tails.³⁰

As revealed by low-angle X-ray diﬀraction, polarized optical

microscopy and diﬀerential scanning calorimetry, the induction

of liquid-crystalline mesophases is intimately linked to both the

generation of the respective blocks and to end-chains substitution

topology i.e. chemical shape and lipophilic/ﬂuorophilic

balance. Mesomorphism is totally absent in dendrimers with

3,5-chain substitution peripheral patterns, irrespectively of the

Chart 1 Chemical structures and general nomenclature of the semi-

ﬂuorinated block co-dendrimers: (x,y,z)¹(3,5)^jH-Fⁱ(j = 0 - 2, i = 1,

2, ﬁrst and second libraries, respectively); (x,y,z)¹= (3,5)¹: R^x= R^z=

OC₁₂H₂₅, R^y= H; (x,y,z)¹= (3,4)¹: R^x= R^y= OC₁₂H₂₅, R^z= H;

(x,y,z)¹= (3,4,5)¹: R^x= R^y= R^z= OC₁₂H₂₅

.

c

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New J. Chem., 2012, 36, 452–468 453

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para position, the low-G precursory esters of (3,4)¹H-F¹and

generation numbers of both constitutive blocks. In contrast,

co-dendrimers with 3,4- and 3,4,5-chain substitution patterns

and mostly of high generations exhibit rather low-temperatures,

highly segregated lamellar, columnar and/or monoclinic 3D

thermotropic mesophases. The mesomorphic properties (thermal

and thermodynamic stabilities, phase’s symmetries) and supra-

molecular organizations of the corresponding subsets of ﬂuori-

nated co-dendrimers are discussed on the basis of their structural

diﬀerences.

(3,4,5)¹H-F¹were ﬁrst converted into their corresponding

acid chlorides by thionyl chloride. The second library of

block co-dendrimers (Chart 1) was obtained by Mitsunobu

etheriﬁcation³¹of the isophthalic derivative 4 with the benzyl

ether dendrimers. The low-G precursory esters of (3,4)¹H-F²

and (3,4,5)¹H-F²could not be prepared this way, and the

corresponding benzylic alcohols were transformed into their

chloride derivatives and reacted with 4 according to the

Williamson etheriﬁcation procedure.

The purity and characterization of the precursory dendritic

derivatives and of all intermediate compounds were determined

Results and discussion

by a combination of thin layer chromatography (TLC), ¹H, ¹³

C

Synthesis

and ¹⁹F NMR spectroscopy, and the ﬁnal co-dendrimers by

additional elemental analysis and MALDI-TOF mass spectro-

scopy. In all cases, the results were in good agreement with the

proposed structures.

The 3,5-arborescence based-wedges (3,5-dihydroxybenzyl

building block) of generations j = 0 - 2 and diﬀering in the

peripheral chains substitution patterns were prepared by

the conventional convergent synthetic method.²⁴It involved the

repetition of elementary chemical sequences such as the etheriﬁ-

cation of the peripheral hydroxy groups and the transformation

of the ester derivative into either the acidic (hydrolysis) or

the benzylic (reduction) corresponding compounds (Scheme 2).

Depending on the chemical nature of the ﬁnal dendrimers, both

types of benzylic and acid based monodendrons were needed for

the last stage of the fabrication (Scheme 3).

Thermal and self-organizing behaviours

The thermal and mesomorphic behaviours of the dendrimers

were investigated by three complementary techniques, including

polarized optical microscopy (POM), diﬀerential scanning

calorimetry (DSC), and small angle X-ray diﬀraction

(SA-XRD), and their thermal stability was systematically

controlled by thermogravimetric analyses (TGA). The results

of these investigations are compiled in Tables 1 and 2.

All the co-dendritic compounds possess an excellent thermal

stability, as veriﬁed by TGA, with decomposition starting well

above their clearing temperatures (240 1C o T_dec.o 280 1C,

onset for weight loss of ca. 3%). This good stability was

further conﬁrmed by DSC (perfectly reproducible heat–cool

cycles). Out of the 18 synthesized dendritic compounds, only

ﬁve of them displayed mesomorphism (Table 1). All the

dendrimers of the ﬁrst library, i.e. F¹-systems, but one i.e.

(3,4)¹(3,5)²H-F¹, are deprived of mesomorphic properties.

Mesomorphism is observed in a few of them only upon

connection of the larger F²group (second library). Thus,

ﬁxation of perﬂuorinated fragments at the apexes of Percec-

type dendrons (inverted topology) appears globally deleterious

to mesophase formation/induction as compared to related

amphiphilic^24,32,33and other ﬂuorinated^24,26block co-dendritic

homologues.

The ﬂuorinated F²-block (Chart 1, i = 2, second library),

5-hydroxy-isophthalic

acid

bis-(3,3,4,4,5,5,6,6,7,7,8,8,8-

tridecaﬂuoro-octyl)ester, 4, was obtained from isophthalic

acid and the commercially available 3,3,4,4,5,5,6,6,7,7,8,8,8-

tridecaﬂuoro-1-octanol in four steps (Scheme 1). It succes-

sively consisted in the protection of the hydroxyl and carbonyl

groups of the isophthalic acid by the use of t-butyldimethylsilyl

chloride (TBDMSCl) under slightly basic conditions to form

ﬁrstly the fully silylated derivative 1, immediately followed by

the selective hydrolysis of the two ester functions of 1 with

acetic acid to give the desired diacid 2. 2 was then esteriﬁed

into 3 with tridecaﬂuoro-1-octanol, followed by the cleavage

of the TBDMS protecting group with tetrabutylammonium

ﬂuoride (TBAF), to produce compound 4, in good yields.

The block co-dendrimers were obtained by cross-coupling

reactions of the various generations of poly(benzyl ether) acid

(or acid chloride) and/or benzylic alcohol (or chloride) deri-

vatives (j = 0 - 2) with the ﬁrst (F¹) and second (F²)

generations of perﬂuorinated building blocks, respectively

(Scheme 3). The dendrimers of the ﬁrst library (Chart 1)

having one perﬂuorinated chain were prepared from the

dendritic acid branches according to the typical procedure of

esteriﬁcation, in the presence of DCC and 4-PPy. Because of

the low reaction yields due to the presence of the chain in the

Scrutinizing the thermal behavior of the two diﬀerent series

of dendrimers reveals that the end-chain functionalisation

pattern impacts appreciably on the mesomorphism, evidenced

by radically diﬀerent behaviours. Thus, none of the dendrimers

with the 3,5-chain peripheral substitution pattern exhibit meso-

phases. They melted instead directly into the isotropic liquid at

or near room temperature; on cooling no crystallization was

observed, and samples remained waxy-like until solidiﬁcation

into the glass state. In both sub-series, i.e. (3,5)^j+1H-F¹and

(3,5)^j+1H-F²(j = 0–2), the melting temperature decreases

monotonously with the generation increase of the lipophilic

dendrons, the increase of the number of divergent aliphatic

chains being responsible for this low melting-temperature

behaviour; note that these temperatures are similar in both

subsets, indicating that the ﬂuorinated segments have only

little eﬀect on the thermal behavior, essentially dominated by

the lipophilic dendron.

Scheme 1 Preparation of the ﬂuorinated block dendron, 4.

c

454 New J. Chem., 2012, 36, 452–468

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Table 1 Thermal behaviour and phase sequences of the block co-dendrimers^a

Compounds

Transitions temperatures/1C, enthalpies/kJ mol^ꢀ1, decomposition temperatures/1C

(3,5)¹H-F¹

Cr 61 (58.2) I

Cr 39 (118.1) I

241

278

251

275

270

250

248

252

272

(3,5)²H-F¹

(3,5)³H-F¹

Cr₁ꢀ10 (1.7) Cr₂38 (11.2) I

(3,5)¹H-F²

Cr 66 (72.2) I

Cr 49 (40.7) I

(3,5)²H-F²

(3,5)³H-F²

Cr 32 (4.25) I

Cr 57 (86.0) I

Cr 44 (72.1) I

Cr₁21 (ꢀ) Cr₂30 (54.9) Col_r50 (4.8) I

I 45 (ꢀ) Col_h40 (ꢀ9.7) Col_r9 (34.1) Cr^b

Cr 80 (62.4) I

(3,4)¹H-F¹

(3,4)¹(3,5)¹H-F¹

(3,4)¹(3,5)²H-F¹

(3,4)¹H-F²

254

I 71 (ꢀ6.2) Cr₂68 (ꢀ57.2) Cr₁

Cr₁ꢀ1 (ꢀ) Cr₂88 (56.8) I

Cr 66 (12.7) Col_h185 (1.5) Col_h292 (11.6) I

I 89 (ꢀ18.2) Col_h283 (ꢀ1.4) Col_h1ꢀ5 (ꢀ) G

Cr₁34 (77.1) Cr₂40 (10.5) I

Cr 40 (110.6) I

Cr₁ꢀ1 (ꢀ) Cr₂49 (39.65) I

Cr 41 (67.2) Lam 49 (2.35) I

I 48 (ꢀ2.0) Lam 33 (ꢀ65.0) Cr

Cr 9 (62.3) Col_h168 (9.8) I

I 64 (ꢀ8.55) Col_h16 (ꢀ16.4) Cr

Cr 33 (61.1) Mon 55 (2.4) I

(3,4)¹(3,5)¹H-F²

(3,4)¹(3,5)²H-F²

271

276

(3,4,5)¹H-F¹

260

259

268

263

(3,4,5)¹(3,5)¹H-F¹

(3,4,5)¹(3,5)²H-F¹

(3,4,5)¹H-F²

(3,4,5)¹(3,5)¹H-F²

265

266

(3,4,5)¹(3,5)²H-F²

a

Cr, Cr₁, Cr₂: crystalline and semi-crystalline solid phases, I: isotropic liquid, Lam: lamellar phase, Col_h, Col_h1, Col_h2: hexagonal columnar

phases, Col_r: rectangular columnar phase, Mon: monoclinic phase, G: glassy state. Temperatures have been measured on second cooling and/or

b

third heating cycle. Temperature of the cooling sequence determined by POM (monotropic phase).

Liquid crystalline behavior was induced in two derivatives

of the corresponding constitutional isomeric family, i.e. with the

3,4-chain substitution pattern, probing the importance of chains

substitution pattern and the great sensitivity of the systems to

subtle structural modiﬁcations. The low-generation terms of both

the sub-series, (3,4)¹H-Fⁱand (3,4)¹(3,5)¹H-Fⁱ, i = 1,2), are devoid

of mesomorphic properties, whilst in contrast both compounds of

the third generation ((3,4)¹(3,5)²H-Fⁱ, i = 1, 2) exhibit a columnar

polymorphism as deduced by microscope observations of their

optical textures (Fig. 1, S1 and S2, ESIz): they appeared homo-

geneous and ﬂuid, and contained recognizable and characteristic

defects (e.g. cylindrical and developable domains). Finally, meso-

morphism is observed in all generation members of the

(3,4,5)¹(3,5)^jH-F²series (j = 0 - 2), with the formation of a

lamellar, columnar and 3D phases on increasing the generation

(Fig. S3–S6, ESIz); again, those containing the F¹-block melt at or

near room temperature directly into the isotropic liquid phase.

Identiﬁcation and mesophases assignment were achieved by

small angle X-ray diﬀraction on powder samples. On average, a

good agreement between the transition temperatures determined

by XRD, POM and DSC was found. The liquid crystalline

nature of the supramolecular organizations was unambiguously

conﬁrmed by the presence of several sharp and intense reﬂections

in the small angle region indicative of segregated organizations,

and of a broad scattering halo with a maximum located between

5.3 and 4.6 A, depending on the respective contribution of the

molten aliphatic and ﬂuorinated chains. For molten aliphatic

chains, the maximum should be located at 4.5 A and for the

ﬂuorinated chains at around 5.5 A (h_Hand h_Fare visualized with

arrows on the diﬀractograms, Fig. 2,4–6); the dendritic moiety

gives rise to a diﬀuse scattering coinciding with h_H.

(enantiotropic) symmetries. The X-ray pattern recorded at 30 1C

(on heating, Fig. 2, S8, ESIw) is consistent with columnar

rectangular phase Col_rwhere the columns are packed in accord

with c2mm symmetry (a = 72.2 A, b = 47.95 A, Table 2). The

two intense and sharp small-angle reﬂections were indexed as the

fundamental reﬂections (11) and (20) and the remaining higher

order reﬂections as (31), (22) and (40), respectively. Note that the

ratio a/b o O3 (i.e. a/b E 1.5) is not so commonly observed

within the c2mm symmetry, whilst is more frequent in the p2gg

symmetry. The conditions on the reﬂections, h + k = 2n + 1, for

p2gg have however not been found, and at this stage, one cannot

fully discriminate between the two planar groups (Fig. S13, ESIz).

On cooling from the isotropic liquid phase, a mesophase

with p6mm hexagonal symmetry is induced prior to the Col_r

phase. The XRD pattern registered at 40 1C revealed the

presence of three sharp small-angle X-ray reﬂections, with

reciprocal spacing in the ratio 1 : O3 : O4, readily assigned as

the (10), (11) and (20) reﬂections of a hexagonal plane lattice

with a parameter a = 37.8 A (Fig. 2 and S8, ESIz, Table 2).

The related compound of the second generation of ﬂuorinated

segment, (3,4)¹(3,5)²H-F², exhibits a rather unusual mesomorphic

phase sequence (vide infra) involving a ﬁrst order transition

between two columnar phases of same symmetry (Fig. 3). This

thermal behavior is perfectly reproducible on successive heating

and cooling cycles.

The symmetry of the low-temperature phase was deduced

from a set of ﬁve small-angle sharp reﬂections, for which the

reciprocal spacing in the ratio 1 : O3 : O7 : O9 : O12 (Fig. 4 and

S9, ESIz) permitted the peak indexation as the (10), (11), (21),

(30) and (22) reﬂections of the hexagonal lattice (a = 65.05 A,

Table 2). The high intensity of the second reﬂection assigned

as (11) results from a modulation of the electronic density

consequent to a speciﬁc distribution of the various chemical

XRD reveals that (3,4)¹(3,5)²H-F¹exhibits two columnar

mesophases with hexagonal (monotropic) and rectangular

c

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New J. Chem., 2012, 36, 452–468 455

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Table 2 X-Ray characterization of the mesophases of the semiﬂuorinated block co-dendrimers

Compounds

d_meas/A

I

hk/00l/hkl

d_calc/A

Mesophase parameters

(3,4)¹(3,5)²H-F¹

39.95

36.1

21.7

20.0

17.9

4.6

33.75

19.35

16.85

4.6

56.4

32.5

21.3

18.8

16.25

4.8

56.5

32.55

18.8

16.3

4.8

57.55

28.6

19.1

14.35

5.3

4.16

52.95

30.25

19.9

17.75

4.8

70.5

64.7

58.0

53.6

50.5

44.2

41.8

—

VS (sh)

M (sh)

M(sh)

11

20

31

22

40

—

10

11

20

—

10

11

21

30

22

—

d

10

11

20

—

001

002

003

004

—

10

11

21

30

—

39.95

36.1

21.5

19.95

18.05

h_H+ h_F

33.65

19.45

16.8

h_H+ h_F

56.35

32.55

21.3

Col_r-c2mm (T = 30 1C)

a = 72.2 A, b = 47.95 A, S_r= 3462 A²(Z = 2)

V_mol= 4045 A³(r = 1.05)

h = 2.34 A

VS (br)

VS (sh)

M (sh)

VS (br)

VS (sh)

M (sh)

W (sh)

VS (br)

VS (sh)

M (sh)

W (sh)

VS (sh)

M (sh)

S (sh)

W (sh)

S (br)

M (sh)

VS (sh)

S (sh)

W (sh)

VS (br)

W (sh)

M (sh)

S (sh)

Col_h-p6mm (T = 40 1C)

a = 38.85 A, S_h= 1308 A²(Z = 1)

V_mol= 4080 A³(r = 1.05)

h = 3.12 A

(3,4)¹(3,5)²H-F²

Col_h1-p6mm (T = 75 1C)

a = 65.05 A, S_h= 3666 A²(Z = 2)

18.8

V_mol= 4810 A³(r = 1.05)

h = 2.62 A

16.25

h_H+ h_F

56.5

32.55

18.8

16.3

h_H+ h_F

57.35

28.7

Col_h2-p6mm (T = 89 1C)

a = 37.6 A, S_h= 1225 A²(Z = 2/3)

V_mol= 4875 ³(r = 1.04)

h = 2.63 A

A

(3,4,5)¹H-F²

Lam (T = 40 1C)

d = 57.35 A, A_mol= 34.5 A², A_lam= 69.0 A²

19.1

14.35

h_F

h_H

52.8

30.5

V_mol= 1980 A³(r = 1.27)

(3,4,5)¹(3,5)¹H-F²

(3,4,5)¹(3,5)²H-F²

Col_h1-p6mm (T = 40 1C)

a = 61.0 A, S_h= 3220 A²(Z = 2)

19.95

17.6

V_mol= 3320 A³(r = 1.14)

h = 2.06 A

Mon-P2₁/m (T = 45 1C)

a = 78.57₄A, b = 67.68₄A, c = 141.3 A

h_H+ h_F

70.65

65.55

58.30

53.89

50.22

44.97

40.93

39.00

37.60

32.77

32.20

31.93

29.73

27.23

26.95

h_H+ h_F

002

1ꢀ10

100

10ꢀ1/101

W (sh)

S (sh)

W (sh)

a = b = 901, g = 132.11

10

V = 557 568 A³(N = 95)

10ꢀ2/102

01ꢀ2/012

2ꢀ10

A = a ꢁ b ꢁ sin(g) = 3946 A²(Z = 2)

V_mol= 5870 A³(r = 1.08)

h = 2.97 A

37.8

32.7

—

31.9

29.8

27.1

—

M (sh)

W (sh)

2ꢀ1ꢀ1/2ꢀ11

2ꢀ20

1ꢀ20

S (sh)

VW (sh)

2ꢀ2ꢀ1/2ꢀ21

2ꢀ2ꢀ2/2ꢀ22

11ꢀ2/112

20ꢀ2/202

4.8

VS (br)

P

d_measand d_calcare the measured and calculated diﬀraction spacings [d_calcis deduced from the following mathematical expressions: d_00l

=

d_00ll/

P

N_l, where N_lis the number of 00l reﬂections observed for the lamellar phase; a = 2 ( d_hk(h²+ k²+ hk)^1/2/N_hkO3, where N_hkis the number of hk

reﬂections observed for the Col_h, Col_h1, Col_h2phases; 1/d_hk= O(h²/a²+ k²/b²) for the Col_r]; I is the intensity of the sharp reﬂections

(VS: very strong, S: strong, M: medium, W: weak, VW: very weak); sh and br stand for sharp and broad reﬂections; h_H+ h_F, h_Fand h_H: maximum

of the diﬀuse scatering due to lateral distances between molten aliphatic tails, dendrimer and ﬂuorinated chains, mainly between aliphatic tails

(h_H) or mainly between ﬂuorinated chains (h_F); 00l, hk and hkl are the Miller indexations of the reﬂections corresponding to the lamellar, columnar

and monoclinic phases respectively; V_mol, molecular volume, r, the density in g cm^ꢀ3; d is the lamellar periodicity, A_molis the molecular area

(A_mol= V_mol/d) and A_lam, the lamellar cross-section area (A_lam= 2 ꢁ A_mol); a and b are the lattice parameters of the Col_r(a a b) and Col_h, Col_h1

,

Col_h2(a = b) phases; for the Col_h, Col_h1, Col_h2phases, the lattice area is given by S_h= 2a²/O3 and for the Col_rphase, S_ris the lattice area

(S_r= ab); Z is the number of dendrimers per columns or ‘‘micelle’’ strings per lattice; a, b, c, a, b, g, A, V are the parameters of the monoclinic

phase, A = a ꢁ b is the sub-lattice area; N is the number of molecules in the 3D lattice. h = ZV_mol/S, or ZV_mol/A is the height of a single mesogen

in a column or a micelle string.

parts constituting the dendrimers in the hexagonal lattice. The

second phase showed three small-angle reﬂections (spacing

ratio 1 : O3 : O4, indexed as (10), (11), (20) reﬂections, Fig. 4

and S9, ESIz) corresponding again to a hexagonal symmetry

(a = 37.6 A, Table 2). A small-angle but more diﬀuse

scattering, d, was also observed, at the same position of the

fundamental reﬂection of the low-temperature phase pre-

viously analyzed, which suggests that some structural features

reminiscent of low-temperature phase remained in the upper

phase (lattice melting). In the following, Col_h1and Col_h2will

be used to distinguish between the low- and high-temperature

hexagonal phases, respectively.

c

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Fig. 1 Characteristic optical textures of (3,4)¹(3,5)²H-F²photographed

on cooling at T = 89 1C (left, fan texture) in the Col_h2phase and at

T = 75 1C (right, cylindrical domains) of the Col_h1phase (see text).

Fig. 4 X-Ray diﬀractograms of the Col_h1phase (top, at T = 75 1C)

and the Col_h2phase (middle, at T = 89 1C), small-angle region of the

two superimposed patterns of (3,4)¹(3,5)²H-F²(bottom).

Fig. 2 X-Ray diﬀractograms of the monotropic Col_hphase (top) and

the enantiotropic Col_rphase (bottom) of (3,4)¹(3,5)²H-F¹.

Fig. 5 X-Ray diﬀractograms of the lamellar phase of (3,4,5)¹H-F²

(T = 40 1C).

Fig. 3 DSC traces of (3,4)¹(3,5)²H-F²recorded at 1 1C min^ꢀ1, second

(blue) and third cycles (red).

Finally in the (3,4,5)¹(3,5)^jH-Fⁱseries, none of the dendrimers

bearing one ﬂuorinated chain (i = 1) have mesomorphic

properties, while each one bearing two chains (i = 2) exhibit

a diﬀerent liquid crystalline phase (Table 1). The compound

(3,4,5)¹H-F²presents a lamellar phase, whose layer periodicity

of 57.35 A (Table 2) is directly given by the position of four

sharp small-angle reﬂections in the spacing ratio 1 : 2 : 3 : 4

(Fig. 5, S10 and S14, ESIz). The abnormal intensity proﬁle in

the reﬂection series, with a relatively small ﬁrst order (001) and

an exhausted (003) reﬂection reveals the alternation of several

high electronic density sublayers, respectively, associated to

the mesogens and to the ﬂuorinated chains, with low electronic

density sublayers, associated to the aliphatic tails and to the

spacers. Another sharp signal of medium intensity is observed

in the wide-angle range. Its location at 4.16 A is not compatible

with a smectic B type of long range ordered hexagonal packing

c

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New J. Chem., 2012, 36, 452–468 457

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Fig. 6 X-Ray diﬀractograms of the Col_h1phase of (3,4,5)¹(3,5)¹H-F²

(T = 40 1C).

Fig. 7 Small-angle zone of the powder X-ray diﬀraction pattern of

the dendrimer (3,4,5)¹(3,5)²H-F²in the isotropic phase (blue curve

above) and in the monoclinic mesophase (black curve below). Blue

crosses represent the location of the barycentre of the diﬀuse reﬂection

in the isotropic phase. Black bars represent the location of the sharp

reﬂections in the monoclinic mesophase.

of the mesogens, for which an intense ﬁrst order reﬂection located

between 4.4 and 4.6 A would be expected. However this reﬂection

is in good agreement with hexagonally packed crystallized

aliphatic chains, as is in the case of the R_IIrotator phase

described for long chain normal alkanes³⁴(previously counted

among the phases with H sub-lattice).³⁵This sharp peak thus

characterizes the lateral packing of the terminal chains, whilst the

overlapping diﬀuse reﬂection therefore occurs from the lateral

packing of the ﬂuorinated tails, the mesogens and the spacers.

Because of the high ﬂuorinated volume fraction in this fragment,

the major contribution to this reﬂection should be that of the

ﬂuorinated parts, in consistency with the small gap between the

experimental maximum (5.3 A) and the expected location for

molten ﬂuorinated chains (5.5 A).^36,37

the wide-angle part of the pattern is unchanged between

mesophase and isotropic phase with developed cybotactic

organization, but the low-angle diﬀuse reﬂections split into

twelve sharp reﬂections while the envelopes of the whole

scattered intensity in the small angle region remain similar

(Fig. 7). Attempted indexations into the highly symmetrical

3D orthorhombic, tetragonal, hexagonal, and cubic crystal

systems obviously failed (recall that a weak but a non-zero

birefringence was observed). However, indexations into the

monoclinic system converged to two primitive lattices with

very similar parameters (Tables S1 and S2, ESIz). These solution

structures involve an oblique sub-lattice a ꢁ b (actually a

slightly deformed hexagonal lattice) with a slightly larger lattice

area than for the di-substituted analogue (for the most likely

solution: a = 78.6 A, b = 67.7 A, g = 1321, A = 3950 A²,

Table 2). Perpendicularly to the sub-lattice plane a periodicity

of about twice the sub-lattice parameters (c = 141 A, V =

558 10³A³) is deduced from the 002 and the hk1 and hk2

reﬂections contained in the pattern. From the presence of the

010 and 100 reﬂections, 5 space groups are compatible with the

proposed indexation, i.e. the groups P2, Pm and P2/m, with

no reﬂection conditions, and the groups P2₁and P2₁/m where

the occurrence of a 2₁screw axis parallel to c sets the condition

l even for the 00l reﬂections. However the groups with the

screw axis are more likely, since the 002 reﬂection is observed in

the pattern while the 001 reﬂection is absent. The mesophase,

referred thereafter to as Mon, is provisionally considered as

discontinuous i.e. made of elongated nanosegregated domains.

The following term of the series, (3,4,5)¹(3,5)¹H-F², exhibits a

hexagonal columnar phase (a = 61 A, Table 2) as shown by POM

(Fig. S4 and S5, ESIz) and also deduced from a set of four small

angle reﬂections for which the reciprocal spacings were in the

ratios 1 : O3:O7:O9, and indexed as the (10), (11), (21) and (30)

reﬂections of the hexagonal lattice (Fig. 6 and S11, ESIz). The

same intensity distribution of the reﬂections (i.e. high intensity for

the reﬂection 11) as observed above for (3,4)¹(3,5)²H-F²in the

Col_h1phase suggests a similar supramolecular organization.

Finally, compound (3,4,5)¹(3,5)²H-F²does not exhibit any

more the Col_h1and Col_h2phases shown by both the lower-

generation term of the same series, i.e. (3,4,5)¹(3,5)¹H-F², and

the 3rd generation analogue of the series with two alkyl chains

per terminal phenyl ring, i.e. (3,4)¹(3,5)²H-F², but a mesophase

with a more complicated structure. The DSC traces and the

slightly birefringent POM texture (Fig. S6, ESIz) indicate the

existence of an intermediate mesophase between the crystal

and the isotropic phase: the isotropization enthalpy is however

small (0.6 J g^ꢀ1), the hysteresis quite modest (only a few 1C at

2 1C min^ꢀ1), and the texture in the mesophase is quite viscous.

In agreement with these observations, the X-ray pattern

evidences a 3-dimensional mesophase structure. Diﬀractogram

recorded at 60 1C, i.e. slightly above the clearing temperature,

reveals a reminiscence of the columnar packing (lattice melting),

as evidenced by the presence of two intense but diﬀuse

reﬂections with centres electron density maxima in spacing

ratio 3^0.5(Fig. 7 and S12, ESIz).

Supramolecular organization within the mesophases

For lamellar systems, such as that shown by (3,4,5)¹H-F², the

molecular area, A_mol, obtained by dividing the molecular

volume, V_mol, with the layer periodicity, d, gives information

about the molecular packing arrangement within the layers

(A_molE 34.5A²). As a matter of fact, the tri-block architecture

of the layers imposes a head-to-tail piling of vicinal molecular

layers because of the amphipathic segregation of ﬂuorinated

and aliphatic chains in diﬀerent sub-layers. The fundamental

lamellar periodicity therefore corresponds to two molecular

layers and to a molecular area A_lam= 2 ꢁ A_mol= 2 ꢁ V_mol/d E

69 A². Beyond this ﬁxed piling sequence several types of

These diﬀuse reﬂections coincide with the (10) and (11)

reﬂections in the Col_h1phase of the analogous dendrimers,

as well from the point of view of the location of the maximum

as from their abnormal intensity ratio. At lower temperature,

c

458 New J. Chem., 2012, 36, 452–468

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structures are possible, depending upon the molecular organization

in the ﬂuorinated and in the aliphatic terminal sub-layers. The

simplest organization is the bilayer structure consisting in the

juxtaposition of the terminal fragments occurring from adjacent

molecular layers: the area covered by the fragment block of

a single molecule is then just identical to the molecular area, i.e.

69 A². Alternative structures involve monolayer organizations

for one or both sub-layers: only the half of the molecular area

is then available for a single fragment block, i.e. 34.5 A².

By analogy with the S_A2, S_A1and S_Adpolymorphism of mono-

catenar compounds,³⁸partial bilayering may also exist, with a

molecular area per fragment block lying in between. The com-

parison with the sections of the molecular fragments can decide

upon the relevant structure. Thus, the section of the two molten

ﬂuorinated chains³⁶is of about 2 ꢁ 32 = 64 A²and the section

of the three hexagonally crystallized aliphatic chains is of 60 A²

(accordingly 4.16²ꢁ 2/3^0.5E 20.0 A²). These transverse sections

are close to the molecular area and the overall layer structure can

therefore be schematized by nearly untilted and approximately

ﬂat bilayers of molten ﬂuorinated tails and of crystallized

aliphatic tails alternating with layers of strongly tilted mesogens

(tilt angle c E 701, estimated from A_lam) and strongly folded

spacers (Fig. 8). Finally, it must be emphasized that the large tilt

of the mesogens has to be random, since the observation of

myelinic textures by POM (Fig. S3, ESIz) conﬁrmed the absence

of azimuthally long range correlated tilt. The mean packing

viewed by X-ray diﬀraction actually emerges from the local

scale molecular packing, determined by interactions between

neighboring molecules, steric constraints molecule conformation

changes and individual molecule motions, which are smoothed

and averaged to empirical partial volume contributions at the

macroscopic scale.

Fig. 9 Representation of the modeled layer induced by the compact

packing of the dendrimer (3,4,5)¹H-F².

onto the molecular area deduced from X-ray data. However,

the simulation was performed with molten aliphatic tails,

avoiding to set additional constraints to conformations and

to limit the energy minimization; the volume diﬀerence between

hexagonally crystallized chains and molten chains had then

to be taken into account and the molecular area constraint to

75 A²(instead of 69 A²). Moreover the c parameter of the

orthorhombic cell needed to be set to 100 A to allow suﬃciently

large molecular motions for an eﬃcient and reproducible

optimizing of the conformations and of the arrangement.

The result of the calculation is displayed in Fig. 9. It can be

seen that, after important oscillations in the beginning of the

simulation, the amplitude of the layer ﬂuctuations reaches a

stable regime with a thickness varying between 45 and 57.5 A

(Fig. S7, ESIz), in acceptable agreement with the lamellar

periodicity measured by XRD. The ﬂuorinated and aliphatic

bilayers are well deﬁned, whilst the sub-layer containing the

spacers has completely merged in the vicinal sub-layers. The

mesogen sub-layer already exists in the local range, but

the segments of the aliphatic tails and spacers ﬁll some space

between them. This penetration logically reduces the tilt of the

mesogens, but the average tilt measured on the snapshot is still

of about 501 to 551.

By increasing the generation number in the same series, the

number and therefore the total section of the mesogen segments

and of aliphatic tails doubles at each step, whilst the number of

ﬂuorinated chains remains unchanged. Consequently, the

crossover from the lamellar phase of (3,4,5)¹H-F²to the

columnar phase of (3,4,5)¹(3,5)¹H-F²involves the expansion

of the areas containing the mesogens and the aliphatic tails

and therefore curves the interface with the ﬂuorinated sub-layer.

Similarly to that described for classical diblock polycatenar

mesogens,³⁹the curvature generates periodic pinching zones in

the sub-layer of smaller area where it ﬁnally disrupts into

ribbons environed by a continuum formed from the expanding

sub-layer. The disruption of the sub-layers is commonly

associated to the loss of orientational long range correlation

between fragments in the ribbons, which are then averaged to

cylindrical columns at the nodes of a Col_h-p6mm lattice. The

columnar lattice area is then directly related to the columnar

segment height of a single molecule, which is determined by

the curvature at the interface and ﬁnally by the mismatching

sections of the fragments inside and outside the columns.

The simple transposition of this description to the interfaces

of the ﬂuorinated ribbons leads to a model of concentric

columns with the mesogens segregating in a shell between

the ﬂuorinated cores and the aliphatic periphery. However,

this model is clearly excluded by the experiments, since it can

neither explain the high intensity of the (11) reﬂection in the

Molecular modeling and molecular dynamics give a mole-

cular and dynamical insight in this local packing and local

counterparts to the empirical macroscopic partial volumes.

The simulation methods used here provide a snapshot of the

conformations and arrangements of a few molecule models in

a minimized energy status. The detailed procedure for mole-

cular dynamics consisted in placing four molecules, formerly

optimized, in an orthorhombic box and setting a constraint

Fig. 8 Sketch of the sub-layer sequence within the lamellar phase of

(3,4,5)¹H-F²: ﬂuorinated bilayers are in green, mesogens are in black,

spacers and bilayers of crystallized aliphatic tails are in grey. d is the

lamellar periodicity.

c

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Col_h1phase of (3,4,5)¹(3,5)¹H-F²and (3,4)¹(3,5)²H-F²nor the

transition to the Col_h2phase of (3,4)¹(3,5)²H-F², which is

associated to a lattice shrinking to exactly the third area.

Due to the triblock architecture the matching of transverse

sections at the other interface (the one between mesogens and

tails) also constrains the packing. The section of two ﬂuorinated

chains is close to the one of three aliphatic chains, whilst the

sections of a single aliphatic chain or of a single mesogen are

similar (vide supra). This implies that the section mismatch is

also similar at both interfaces and that the curvature should be

similar as well, excluding de facto the concentric core model

for which the curvature at the outer shell interface would be

smaller.

The exclusion of a core shell double-segregation process

implies that the mesogens and the ﬂuorinated chains segregate

in separated columns. The simplest hexagonal lattice with two

diﬀerent types of columns actually contains three of them: two

identical at the nodes of a honeycomb lattice (Fig. 11, black)

and the third diﬀerent one inside the honeycomb cells (Fig. 11,

green). This type of lattice including two columns of mesogens

and one of ﬂuorinated chains would respect the ratio of the

overall sections of both types of tails (6 aliphatic for 2

ﬂuorinated) and would also be compatible with the repartition

of the tails around the mesogens. Indeed, this organization is

very likely the one of the Col_h1phase (Fig. 10 and 11) and

highlights the intensity anomalies in the small-angle reﬂections

series: ﬂuorinated chains and mesogens in the columns exhibit

close electronic density which are about twice the one of the

aliphatic continuum, in consistency with the reduced (10) and

exhausted (11) reﬂection intensities.

Fig. 11 Model of the transition between Col_h1(top) and Col_h2

(bottom) phases of (3,4)¹(3,5)²H-F²by columns permutation (view

of the symmetry plane). x: in-plane correlation length.

lattice have nearly the same size and it is therefore possible to

exchange columns between the 3 interpenetrated primitive

lattices forming the Col_h1lattice without distorting it. This

explains the transition to the Col_h2phase occurring for

(3,4)¹(3,5)²H-F²(Fig. 11): while in the low temperature

phase the three sub-lattices are long-range correlated, the

mean distance between two lattice permutations in the high-

temperature phase limits the residual Col_h1correlations, which

are revealed by the diﬀuse scattering at the location of the (10)

reﬂection in the low-temperature Col_h1phase (Fig. 4, the

correlation distance is estimated to be B130 A from the signal

width, by using the Scherrer formula). Because of the similar

size of the columns, the permutations occur without distortion

of the lattice geometry and a small lattice containing a single

undiﬀerentiated column remains long range correlated (black

and green columns indiﬀerently positioned on the honeycomb

lattice, Fig. 11).

Besides the ratio of the interface areas determined by the

number of tails connected to the mesogens, both dendrimers

exhibit a partial volume ratio close to two for the mesogen’s

and the ﬂuorinated moieties (the calculation gives 1.8 and 2.7,

respectively). Consequently all columns included in the Col_h1

The sole liquid crystal in the dendrimer series bearing one

ﬂuorinated chain, (3,4)¹(3,5)²H-F¹, also exhibits a columnar

phase with hexagonal symmetry, which is diﬀerent from the

other systems: in this case, the ﬂuorinated volume fraction is

not suﬃcient to form separated columns as in the (3,4)¹(3,5)²H-F²

and (3,4,5)¹(3,5)¹H-F¹dendritic cases. In addition, the reﬂection

intensity ratios in the Col_hphase are classical, suggesting that

the segregating ﬂuorinated chains decorate the column of the

mesogens. This decoration may either consist in a cylindrical shell

or more realistically form a ‘‘Kagome’’ type of decoration.⁴⁰

Nevertheless, the hexagonal symmetry results from an averaging

process as shown by the transition to the Col_rphase. In this

phase, the rectangular lattice is shrunk along the a-axis (with

respect to a hexagonal lattice) and the absence of the (02)

reﬂection in the (02)/(31) series might express a reduced

contrast along the b-axis. These remarks may indicate that

the segregating ﬂuorinated chains mainly intercalate between

columns along the b-axis, as schematically represented in

Fig. 12.

Fig. 10 Schematic representation of the formation of the Col_h1phase

of (3,4)¹(3,5)²H-F²by segregation of the ﬂuorinated tails in columns

(green) distinct from the columns ﬁlled by the dendritic part (black).

Local and macroscopic views after averaging in all directions (view of

the symmetry plane).

Reconsidering the dendritic F²-systems, the vanishing of the

columnar polymorphism in (3,4,5)¹(3,5)²H-F²on going from the

low-generation term of the same series, i.e. (3,4,5)¹(3,5)¹H-F²,

c

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Fig. 12 Model for the Col_rphase of (3,4)¹(3,5)²H-F¹. Black columns

are ﬁlled by the dendritic part, and the green and blue columns by the

ﬂuorinated segments (the blue and green colours indicate F-segments

of diﬀerent molecules).

Fig. 13 Packing model for the monoclinic mesophase of the dendrimer

(3,4,5)¹(3,5)²H-F²with strings of micelles along c. Big black discs

represent the maximum section of the micelles; small black discs

represent the disruption zones between the micelles; green discs repre-

sent the columns of ﬂuorinated parts connecting the strings. The 2₁axis

lies parallel to c onto the green column axes (for the displayed sketch the

symmetry would be P2₁/m).

and to the 3rd generation analogue of the series with two

alkyl chains per terminal phenyl ring, i.e. (3,4)¹(3,5)²H-F², is

concomitant with the increase of the interface area between the

stacked cores and the aliphatic periphery imposed by the

expansion of this periphery. However, the reminiscence of

the columnar organization is preserved in the local packing in

the isotropic phase. Thus, by assuming a strict hexagonal local

packing, the lattice parameters are unchanged with respect to the

di-substituted analogue (Col_h1lattice: a E 65 A, S E 3600 A²;

Col_h2lattice: a E 37 A, S E 1200 A²). This indicates that the

tri-substitution does not stretch signiﬁcantly the columnar

cores despite the larger interface areas, which then necessarily

involve deviations from the cylindrical interface shape. These

deviations would be consistent with the loss of long-range

correlation of the hexagonal lattice and most probably consist

in pinching zones where the overcrowded periphery folds in

between the columnar cores. These pinching zones may develop

up to the disruption of the columnar cores generating micellar

cubic phases, as it was already reported in the literature.⁴¹

The 3-dimensional organization of the mesophase is very likely

the sign of the disruption of the columnar cores at pinching

zones as in the cases reported in the literature, but here the

3-dimensional lattice turned out to be of low symmetry. In the

phase of compound (3,4,5)¹(3,5)²H-F², the presence of a screw

axis (see above) is consistent with the models for the Col_h1and

Col_h2phases of the analogue dendrimers. Thus, the a ꢁ b

oblique sub-lattice is close to the Col_h1lattice which was

shown to contain 3 columnar cores surrounded by aliphatic

tails: two of them are formed by the piled mesogens and

the third one, by the segregated ﬂuorinated chains (Table 2).

Here the columns of stacked mesogens are very likely replaced

by strings of ‘‘micelles’’ formed by the disruption of the

columnar cores. Moreover, for a sterically optimized packing,

both strings should be, respectively, shifted along the c-axis in

such a manner that the maximum section of the micelles of

one string faces the disruption zone of the vicinal string. In

this model, a two-fold screw axis then naturally lies onto the

third column containing the segregated ﬂuorinated segments

(Fig. 13).

length of the discontinuous domains could vary between 100

and 140 A for a diameter of typically 30 A. The eﬀect of the

pinching and disruption process can be best appreciated from

the average molecular height h occupied by a single mesogen

within a columnar core or a string of micelles. For instance,

the 3.0 A found for this mesophase can be compared to the

2.6 A found in the Col_h1and Col_h2phases of the di-substituted

analogue. The discrepancy between a height increase of only

15% for an area interface increase of 50% reveals the deviation

from the cylindricality involved by the tri-substitution. The

comparison with the 2nd generation dendrimer (3,4,5)¹(3,5)¹H-F²

results in the same conclusion: h is increased by 50% but the

interface area by nearly 100%.

The preparation of compounds of the next generation

(j = 3) could not be performed but it is very tempting to

extrapolate the described evolution of the polymorphism.

Thus, if the same type of mesomorphism would have been

maintained, the discrepancy between the variations of the

molecular height and the interface area would have continued

increasing. Consequently the micelles would have become

more spherical with a shrinking of the lattice along c and an

expansion in the a ꢁ b plane.

Conclusions

Two libraries of block dendrimers have been synthesized and

their thermal behaviour analyzed as a function of both the size

of the constitutive blocks and the end-chain substitution

pattern. The thermal properties of classical lipophilic-based

polybenzyl ether wedges are drastically modiﬁed upon the

insertion of rather small ﬂuorinated segments at the focal

point. In most cases, the LC behaviour is absent. However,

when adequate conditions are found, e.g. volume fraction of

the various constitutive parts, chain-pattern, generations,

mesomorphism is observed. The mesophases formed exhibit

rather unusual and highly segregated phase structures, with

the formation of ‘‘three-columns’’ network phases and a 3D

phase with a monoclinic space group made of elongated

nano-segregated strings. In particular, within one subset of

the F²-system, the evolution from a 1D lamellar to a 3D

monoclinic phase via a 2D columnar phase, observed in three

Going on this model of strings of nano-segregated domains

(discontinuous), an average number of mesogens per ‘‘micelle’’

of about 50 is deduced from the ratio of the experimental

lattice volume and of the calculated molecular volume. Partial

volume calculations show that the micelles are elongated:

depending upon the extension of the disruption zones, the

c

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New J. Chem., 2012, 36, 452–468 461

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consecutive terms as a function of the generation number,

(3,4,5)¹(3,5)^jH-F², j = 0 - 2, or the reversible transition between

two mesophases of same symmetry by lattice permutation,

(3,4)¹(3,5)²H-F², are quite remarkable and unique. These

various supramolecular organizations have been comprehensively

and eﬃciently described by the help of classical concepts, such

as partial molecular volumes, and transverse cross-sections of

molecular segments applied at both interfaces generated by

this speciﬁc multiblock architecture.

precipitate was ﬁltrated oﬀ, and the organic solution was

washed with water (2 ꢁ 200 mL) and brine (2 ꢁ 200 mL),

dried over MgSO₄and ﬁltered. The solvent was evaporated

and the residue was dried under vacuum to yield a white solid

(C₂₆H₄₈O₅Si₃, 524.91 g mol^ꢀ1, 19.2 g, 87.6%). ¹H NMR

(CDCl₃): d 8.27 (1 H, t, ³J = 1.5 Hz), 7.70 (2 H, d, ³J =

1.5 Hz), 1.03 (18 H, s), 0.99 (9 H, s), 0.30 (12 H, s), 0.23 (6 H, s).

2. To a solution of 1 (19 g, 36.19 mmol) in THF (100 mL),

glacial acetic acid (300 mL) and distilled water (100 mL) were

added sequentially. The reaction mixture was stirred for 3 h

and diluted with cold water (100 mL) and cooled to 0 1C in an

ice bath. The white solid was precipitated which was ﬁltered

and dried under vacuum (C₁₄H₂₀O₅Si, 296.39 g mol^ꢀ1, 9.48 g,

88%). ¹H NMR (DMSO-d₆): d 8.09 (1 H, t, ³J = 1.5 Hz), 7.54

It would be at this stage precocious and presumptuous to

draw precise relationships between molecular structures and

mesophase structures, but it appears quite clear that such types

of multiblock co-dendritic supermolecules with inverted topology

should provide a plethora of yet unknown and fascinating

multicompartmental self-assemblies, whose complex lattices

may be tuned by the dendritic connectivity.

3

(2 H, d, J = 1.5 Hz), 0.95 (9 H, s), 0.20 (6 H, s).

3. To a mixture of CH₂Cl₂(50 mL) and THF (30 mL),

2 (9 g, 30.36 mmol) and tridecaﬂuoro-1-octanol (24.32 g,

66.80 mmol) were added and the reaction was cooled to

0 1C for 30 min. Then, DCC (17.52 g, 85.02 mmol) and

4-PPy (catalytic) were added and the reaction was stirred for

48 h at 25 1C. The solvents were removed and the residue

dissolved in CH₂Cl₂(150 mL). A white precipitate was ﬁltered,

and the solution was washed with water (2 ꢁ 200 mL) and

brine (2 ꢁ 200 mL), dried over MgSO₄and ﬁltered. The crude

product was puriﬁed by CC (SiO₂, CH₂Cl₂) to give a white

Experimental section

Materials

Chemicals were used as purchased, without further puriﬁcation.

Methyl 3,5-di-hydroxybenzoate (98%), 3,3,4,4,5,5,6,6,7,7,8,8-

tridecaﬂuoro-1-octanol (97%) and imidazole (99%) were

purchased from Alfa-Aesar. Triphenylphosphine (PPh₃, 99%),

5-hydroxyisophthalic acid (99%), diisopropyl azodicarboxylate

(DIAD, 94%), SOCl₂(99.5%) were obtained from Acros. DCC

(N,N-dicyclohexylcarbodiimide) (99%) was obtained from

Lancaster. 4-PPy (98%) was purchased from Fluka. Tetrabutyl-

ammonium ﬂuoride (TBAF), tert-butyldimethylsilyl chloride

(TBDMSCl, 97%), 2,6-di-tert-butyl-4-methylpyridine (DTBMP,

97%) and LiAlH₄(1 M THF) were purchased from Aldrich.

AcOH (100%) and K₂CO₃were obtained from Prolabo. MgSO₄

solid (C₃₀H₂₆F₂₆O₅Si, 988.57

g

mol^ꢀ1

,

22.51 g, 75%).

¹H NMR (CDCl₃): d 8.27 (1 H, t, J = 1.5 Hz), 7.70 (2 H,

d, ³J = 1.5 Hz), 4.65 (4 H, t, ³J = 6.4 Hz), 2.64 (4 H, m), 1.00

(9 H, s), 0.23 (6 H, s).

3

4. To the solution of 3 (22.4 g, 22.66 mmol) in THF (50 mL),

27.19 mL of a 1 M solution of TBAF in THF was added at

0 1C; the reaction was stirred at room temperature for 12 h.

The solvent was removed by evaporation and the crude

product was crystallised twice from methanol to give a white

solid (C₂₄H₁₂F₂₆O₅, 874.31 g mol^ꢀ1, 15.45 g, 78%). ¹H NMR

was purchased from Ridel-de-Haen. Et N (99.5%), KOH (85%)

¨

3

and NH₄Cl were bought from Carlo-Erba-SDS. All solvents

were distilled before use. Dimethylformamide (DMF) was

obtained from Normapur (99.8% pure). Hexane was obtained

from Carlo-Erba (499.9% pure). Methanol (MeOH), obtained

from Carlo Erba (499.9% pure), was dried over magnesium

turnings and iodine before distillation. Dichloromethane

(CH₂Cl₂), obtained from Carlo Erba (stabilized with amylene,

99.8% pure), was distilled over calcium chloride prior to chemical

reactions and N₂-chromatography columns. Tetrahydrofuran

3

(acetone-d₆): d 9.23 (1 H, s), 8.15 (1 H, t, J = 1.5 Hz), 7.71

(2 H, d, ³J = 1.5 Hz), 4.69 (4 H, t, ³J = 6.0 Hz), 2.88 (4 H, m).

¹³C NMR (acetone-d₆): d 165.51, 158.69, 132.56, 122.31,

121.46, 58.00, 29.99, 29.80, 29.60. ¹⁹F NMR (acetone-d₆):

3

d ꢀ81.63 (6F, t, J = 9.25 Hz), ꢀ113.88 (4F, t, J = 15.0 Hz),

ꢀ122.35 (4F, s), ꢀ123.38 (4F, s), ꢀ124.04 (4F, m), ꢀ126.75

(4F, m).

(THF), obtained from Ridel-de-Haen (499% pure), was dried

¨

over potassium hydroxide, and distilled over sodium wire before

use. HCl was obtained from Normapur (37% pure). All other

chemicals were used without puriﬁcation. Drying under vacuum

was done at 10^ꢀ2Torr. Products were isolated by column

chromatography, CC, (silica gel 60, particle size 40–63 mm,

230–400 mesh, Merck). Thin layer chromatography, TLC:

pre-coated glass sheets with silica gel 60 F254, Merck.

Preparation of the precursor polyarylether dendrons, 6–13

(Scheme 2)

The detailed preparation of 5a (C₃₂H₅₆O₄, 504.78 g mol^ꢀ1), 5b

(C₃₂H₅₆O4, 504.78 g mol^ꢀ1), 5c (C₄₄H₈₀O₅, 689.10 g mol^ꢀ1), 6a

(C₃₁H₅₄O₄, 490.76 g mol^ꢀ1), 6b (C₃₁H₅₄O₄, 490.76 g mol^ꢀ1), 6c

(C₄₃H₇₈O₅, 675.08 g mol^ꢀ1), 7a (C₃₁H₅₆O₃, 476.77 g mol^ꢀ1), 7c

(C₄₃H₈₀O₄, 661.09 g mol^ꢀ1), 7c⁰(C₄₃H₇₉ClO₃, 679.54 g mol^ꢀ1),

8a (C₇₀H₁₁₆O₈, 1085.67 g mol^ꢀ1), 8c (C₉₄H₁₆₄O₁₀, 1454.30 g mol^ꢀ1),

9a (C₆₉H₁₁₄O₈, 1071.64 g mol^ꢀ1), 9c (C₉₃H₁₆₂O₁₀, 1440.28 g mol^ꢀ1),

Preparation of the precursor ﬂuorinated dendron 4 (Scheme 1)

1. To a DMF solution (80 mL) of 5-hydroxyisopthalic acid

(7 g, 38.43 mmol), under an argon atmosphere, imidazole

(9.39 g, 137.92 mmol) and TBDMSCl (20.8 g, 138.32 mmol)

were added. The reaction mixture was warmed to 57 1C and

stirred for 12 h. The solvent was removed by evaporation

and the residue was dissolved in CH₂Cl₂(100 mL). The white

10a (C₆₉H₁₁₆O₇, 1057.66

1426.29 g mol^ꢀ1), 11a (C₁₄₆H₂₃₆O₁₆, 2247.43 g mol^ꢀ1), 11c

(C₁₉₄H₃₃₂O₂₀, 2984.70

mol^ꢀ1), 12a (C₁₄₅H₂₃₄O₁₆,

2233.40

mol^ꢀ1), 12c (C₁₉₃H₃₃₀O₂₀, 2970.67 mol^ꢀ1),

g

mol^ꢀ1), 10c (C₉₃H₁₆₄O₉,

g

c

462 New J. Chem., 2012, 36, 452–468

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3

(4 H, m), 1.77 (4 H, m), 1.27 (36 H, m), 0.89 (6 H, t, J =

6.7 Hz). ¹³C NMR (CDCl₃): d 149.28, 148.64, 133.75, 119.52,

113.83, 112.95, 69.39, 69.18, 65.23, 31.90, 29.68, 29.42, 29.35,

26.02, 22.66, 14.08.

7b⁰. To a CH₂Cl₂solution (100 mL) containing 7b (20 g,

41.95 mmol), DTBMP (17.23 g, 83.89 mmol) in CH₂Cl₂

(100 mL), a solution of SOCl₂(4.99 g, 41.95 mmol) in

50 mL of CH₂Cl₂was added dropwise at room temperature,

and the mixture was stirred for 3 h. The product was dissolved in

hot hexane and ﬁltered. The residue was evaporated to yield a pale

yellow solid chloride compound (C₃₁H₅₅ClO₂, 495.22 g mol^ꢀ1).

8b. A solution of methyl 3,5-dihydroxybenzoate (3.2 g,

19.06 mmol), K₂CO₃(31.62 g, 228.80 mmol) in DMF

(100 mL) were stirred under an inert atmosphere for 1 h at

70 1C and 7b⁰(21.36 g, 43.13 mmol) was added. After 6 h, the

reaction was completed. K₂CO₃was ﬁltered through celite and

DMF was evaporated on a rotary evaporator. The residue was

partitioned between CH₂Cl₂(150 mL) and water (200 mL) and

the organic extract was washed with NH₄Cl (2 ꢁ 250 mL),

dried over MgSO₄, ﬁltered, and the solvent was evaporated to

dryness. The crude product was puriﬁed by CC (SiO₂, 7 : 3

CH₂Cl₂/hexane) and gave a white solid (17.32 g, 84%).

3

¹H NMR (CDCl₃): d 7.21 (2 H, d, J = 2.4 Hz), 6.87 (2 H,

3

dd, J = 2.0 Hz, J = 8.25 Hz), 6.84 (2 H, d, J = 2.0 Hz),

3

6.79 (2 H, d, J = 8.25 Hz), 6.72 (1 H, t, J = 2.4 Hz), 4.86

3

(4 H, s), 3.91 (8 H, m), 3.82 (3 H, s), 1.72 (8 H, m), 1.18

3

(72 H, m), 0.80 (12 H, t, J = 6.9 Hz). ¹³C NMR (CDCl₃):

d 166.78, 159.77, 149.26, 149.09, 131.88, 128.84, 120.50,

113.63, 113.51, 108.24, 107.19, 70.36, 69.26; 69.20, 52.21,

31.09, 29.68, 29.62, 29.41, 29.34, 22.66, 14.09.

9b. The preparation of 9b followed the same procedure used

for the preparation of acidic compounds 6. 8b (3 g, 2.76 mmol),

KOH (1.55 g, 27.63 mmol), MeOH/water (15 mL : 15 mL),

HCl (6 M, drops). White solid (C₆₉H₁₁₄O₈, 1071.64 g mol^ꢀ1

,

1

2.84 g, 96%). H NMR (THF-d₈): d 7.22 (2 H, s), 6.78–6.68

(6 H, m), 6.36 (1 H, s), 4.65 (4 H, s), 3.76 (8 H, m), 2.61

(1 H, large), 1.64 (8 H, m), 1.21 (72 H, m), 0.80 (12 H, t,

³J = 6.8 Hz).

10b. The preparation of 10b followed the same procedure

used for the preparation of 7. 8b (12.5 g, 11.51 mmol), LiAlH₄

(8.64 mL, 1 M in THF). CC (SiO₂, CH₂Cl₂). White glassy solid

(C₆₉H₁₁₆O₇, 1057.66 g mol^ꢀ1, 11.6 g, 95%). ¹H NMR

Scheme 2 Synthesis of the polybenzyl ether dendrons, 5–13 (a: R^x=

R^z= OC₁₂H₂₅, R^y= H; b: R^x= R^y= OC₁₂H₂₅, R^z= H; c: R^x

=

3

(CDCl₃): d 6.96 (2 H, dd, J = 1.8 Hz, J = 8.25 Hz), 6.92

R^y= R^z= OC₁₂H₂₅).

(2 H, d, ³J = 1.8 Hz), 6.87 (2 H, d, ³J = 8.25 Hz), 7.63 (2 H, d,

3

³J = 2.2 Hz), 6.55 (1 H, t, J = 2.2 Hz), 4.94 (4 H, s), 4.64

13a (C₁₄₅H₂₃₆O₁₅, 2219.42

2956.69 g mol^ꢀ1) has been already reported.³²

g

mol^ꢀ1), 13c (C₁₉₃H₃₃₂O₁₉,

(2 H, d, ³J = 5.3 Hz), 4.00 (8 H, m), 1.80 (8 H, m), 1.66 (1 H, t,

3

³J = 5.3 Hz), 1.27 (72 H, m), 0.89 (12 H, t, J = 6.8 Hz).

¹³C NMR (CDCl₃): d 160.19, 149.26, 149.03, 143.28, 129.24,

120.46, 113.69, 113.53, 105.63, 101.21, 70.17, 69.22, 65.35,

53.40, 31.91, 29.68, 29.62, 29.42, 29.35, 22.67, 14.10.

7b. To a solution of 5b (25 g, 49.52 mmol) in dry THF

(120 mL), a solution of LiAlH₄(37.12 mL, 1 M in THF) was

added dropwise at 0 1C and the reaction was stirred at room

temperature for 12 h. The excess of LiAlH₄was neutralized by

10 mL of MeOH, and then 20 mL of water was added. THF

was evaporated and the residue was puriﬁed by ﬂash CC

(SiO₂, 7 : 3 CH₂Cl₂/hexane) and obtained as a white solid

(C₃₁H₅₆O₃, 476.77 g mol^ꢀ1, 22.85 g, 97%). ¹H NMR (CDCl₃):

11b. The preparation of 11b followed the same procedure

used for the preparation of 8a. 10b (8.5 g, 8.04 mmol), methyl

3,5-dihydroxybenzoate (0.64 g, 3.83 mmol), PPh₃(2.11 g,

8.04 mmol), THF (70 mL), DIAD (1.58 mL, 8.04 mmol).

CC (SiO₂, 1 : 1 CH₂Cl₂/hexane) to yield a white solid

(C₁₄₆H₂₃₆O₁₆, 2247.43 g mol^ꢀ1, 7.44 g, 87%). ¹H NMR

3

d 6.93 (1 H, s), 6.86 (2 H, d, J = 0.9 Hz), 4.60 (2 H, s), 3.99

c

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New J. Chem., 2012, 36, 452–468 463

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3

(CDCl₃): d 7.30 (2 H, d, J = 2.4 Hz), 6.94 (4 H, dd, J =

1.8 Hz, ³J = 8.25 Hz), 6.92 (4 H, d, ³J = 1.8 Hz), 6.87 (4 H, d,

³J = 8.25 Hz), 6.80 (1 H, t, ³J = 2.2 Hz), 6.69 (4 H, d,

the reaction completeness being checked by TLC. The reaction

mixture was ﬁltered through celite and the resulting organic

solution was washed with NH₄Cl (2 ꢁ 200 mL), dried over

MgSO₄and concentrated under vacuum. The crude product

was puriﬁed by CC (SiO₂, CH₂Cl₂) to give a white solid

³J = 2.2 Hz), 6.58 (2 H, t, J = 2.2 Hz), 5.01 (4 H, s), 4.91

3

(8 H, s), 4.00 (16 H, m), 3.91 (3 H, s), 1.81 (16 H, m), 1.27 (144

H, m), 0.89 (24 H, t, ³J = 6.8 Hz). ¹³C NMR (CDCl₃): d

166.83, 160.21, 159.69, 149.27, 149.06, 138.68, 132.16, 129.12,

120.53, 113.66, 113.56, 108.52, 107.06, 106.28, 101.35, 70.23,

69.29, 69.20, 52.08, 31.91, 29.69, 29.63, 29.44, 29.36, 22.68, 14.11.

1

3

(0.83 g, 73%). H NMR (CDCl₃): d 7.15 (2 H, d, J = 2.2 Hz),

3

6.66 (1 H, t, J = 2.2 Hz), 4.61 (2 H, t, J = 6.6 Hz), 3.97

(4 H, t, ³J = 6.5 Hz), 2.61 (2 H, m), 1.78 (4 H, m), 1.26 (36 H, m),

0.88 (6 H, t, ³J = 6.7 Hz). ¹³C NMR (CDCl₃): d 166.02,

160.23, 131.10, 107.71, 106.81, 68.32, 56.87, 31.92, 30.38, 29.64,

29.36, 26.00, 22.69, 14.09. ¹⁹F NMR (CDCl₃): d ꢀ80.66 (3F, t,

12b. Prepared using the same procedure as that used for 6.

11b (2.3 g, 1.023 mmol), KOH (0.57 g, 10.23 mmol), MeOH/

water (8 mL : 8 mL), HCl (6 M, drops). White glassy solid

(C₁₄₅H₂₃₄O₁₆, 2233.40 g mol^ꢀ1, 2.03 g, 89%). ¹H NMR

(CDCl₃): d 6.89–6.49 (21 H, m), 4.99 (4 H, s), 4.87 (8 H, s),

3.92 (16 H, m), 1.76 (16 H, m), 1.24 (144 H, m), 0.86 (24 H, t,

³J = 6.8 Hz). ¹³C NMR (CDCl₃): d 160.07, 149.11, 148.87,

138.85, 129.22, 120.49, 113.56, 113.40, 105.96, 70.09, 69.25,

69.16, 31.91, 29.71, 29.66, 29.48, 29.36, 22.67, 14.10.

3

³J = 9.25 Hz), ꢀ113.36 (2F, t, J = 15.0 Hz), ꢀ121.76 (2F, s),

ꢀ122.76 (2F, s), ꢀ123.49 (2F, m), ꢀ126.05 (2F, m). Elemental

analysis calcd for C₃₉H₅₇F₁₃O₄(MW = 836.85 g mol^ꢀ1): C 55.97,

H 6.86; found: C 56.25, H 7.17%. MALDI-TOF (M + Na⁺)

calcd for m/z 836.40(100%), 837.41(44.4%), 838.41(10.4%); found

815.71 g mol^ꢀ1

.

(3,4)¹H-F¹. To the suspension of 6b (0.6 g, 1.22 mmol) in

CH₂Cl₂(6 mL) a solution of thionyl chloride (0.99 g,

8.35 mmol) in CH₂Cl₂(10 mL) was added dropwise at room

temperature; the solution was then reﬂuxed for 6 h. After the

solvent and excess of thionyl chloride were removed by

evaporation, the crude product was dried under vacuum for

1 h and dissolved in CH₂Cl₂(10 mL) with Et₃N (0.97 g,

9.54 mmol). The solution was stirred for 15 min at room

temperature and the solution of tridecaﬂuoro-1-octanol

(0.48 g, 1.31 mmol) in CH₂Cl₂(5 mL) was added drop by

drop. The reaction was reﬂuxed for 12 h. The solvent was

removed by evaporation and the residue was partitioned

between CH₂Cl₂(50 mL) and water (100 mL), the organic

extract was washed with NH₄Cl (25 mL) and brine (25 mL),

dried over MgSO₄and ﬁltered, and the solvent was evaporated

to dryness. The crude product was puriﬁed by CC (SiO₂, 7 : 3

CH₂Cl₂/hexane) to give a white solid (0.75 g, 74%). ¹H NMR

13b. The preparation of 13b followed the same procedure

used for the preparation of 7. 11b (4.85 g, 2.16 mmol), THF

(10 mL), LiAlH₄(1.62 mL, 1 M in THF). CC (SiO₂, CH₂Cl₂).

White glassy solid (C₁₄₅H₂₃₆O₁₅, 2219.42 g mol^ꢀ1, 3.97 g,

83%). ¹H NMR (CDCl₃): d 6.95 (4 H, dd, ³J = 1.65 Hz,

³J = 8.25 Hz), 6.93 (4 H, d, ³J = 1.65 Hz), 6.87 (4 H, d,

³J = 8.25 Hz), 7.68 (4 H, d, ³J = 2.2 Hz), 6.59 (3 H, m), 6.52

(2 H, t, ³J = 2.2 Hz), 4.98 (4 H, s), 4.94 (8 H, s), 4.63 (2 H, d,

³J = 5.7 Hz), 4.00 (16 H, m), 1.88 (1 H, t, ³J = 5.7 Hz),

3

1.80 (16 H, m), 1.27 (144 H, m), 0.89 (24 H, t, J = 6.8 Hz).

¹³C NMR (CDCl₃): d 160.14, 159.96, 149.22, 148.99, 143.49,

139.14, 129.16, 120.46, 115.80, 113.64, 113.49, 106.12, 105.60,

101.46, 101.07, 70.17, 69.89, 69.28, 69.19, 65.04, 31.89, 29.68,

29.62, 29.42, 29.35, 22.66, 14.09.

Preparation of the semi-ﬂuorinated block dendrimers (Scheme 3)

3

(CDCl₃): d 7.55 (1 H, dd, J = 2.0 Hz, J = 8.4 Hz), 7.44

(1 H, d, ³J = 2.0 Hz), 6.79 (1 H, d, ³J = 8.4 Hz), 4.51 (2 H, t,

³J = 6.4 Hz), 3.95 (4 H, m), 2.51 (2 H, m), 1.75 (4 H, m), 1.18

(36 H, m), 0.80 (6 H, t, ³J = 6.9 Hz). ¹³C NMR (CDCl₃):

d 166.00, 153.53, 148.52, 123.70, 121.56, 114.13, 111.82, 69.22,

(3,5)¹H-F¹. DCC (0.392 g, 1.901 mmol) and 4-PPy (catalytic

quantity) were added in one portion to a solution of 6a (0.8 g,

1.63 mmol) and tridecaﬂuoro-1-octanol (0.494 g, 1.36 mmol)

in a mixture of CH₂Cl₂(5 mL) and THF (10 mL) at 0 1C. The

resulting solution was stirred for 18 h at ambient temperature,

68.98, 56.54, 31.92, 29.68, 29.62, 29.36, 26.00, 22.68, 14.09. ¹⁹

F

NMR (CDCl₃): d ꢀ80.66 (3F, t, ³J = 9.25 Hz), ꢀ113.37

(2F, t, ³J = 15.0 Hz), ꢀ121.77 (2F, s), ꢀ122.77 (2F, s),

ꢀ123.44 (2F, m), ꢀ126.06 (2F, m). Elemental analysis calcd

for C₃₉H₅₇F₁₃O₄(MW = 836.85 g mol^ꢀ1): C 55.97, H 6.86;

found: C 56.05, H 6.80%. MALDI-TOF (M + Na⁺) calcd for

m/z 836.40(100%), 837.41(44.4%), 838.41(10.4%); found

831.88 g mol^ꢀ1

.

(3,4,5)¹H-F¹. As (3,4)¹H-F¹. 6c (0.6 g, 0.889 mmol), SOCl₂

(0.74 g, 6.22 mmol), HO(CH₂)₂(CF₂)₆F (0.39 g, 1.07 mmol),

Et₃N (0.72 g, 7.11 mmol), CH₂Cl₂(15 mL). CC (SiO₂,

CH₂Cl₂). White solid (0.48 g, 53%). ¹H NMR (CDCl₃):

d 7.17 (2 H, s), 4.52 (2 H, t, ³J = 6.4 Hz), 3.92 (6 H, m),

3.52 (2 H, m), 1.73 (6 H, m), 1.18 (54 H, m), 0.80 (9 H, t,

³J = 6.8 Hz). ¹³C NMR (CDCl₃): d 165.95, 152.85, 142.70,

123.86, 107.99, 73.50, 69.11, 56.76, 31.92, 29.69, 29.62, 29.38,

26.05, 22.61, 14.09. ¹⁹F NMR (CDCl₃): d ꢀ80.66 (3F, t,

³J = 9.25 Hz), ꢀ113.38 (2F, t, ³J = 15.0 Hz), ꢀ121.77

Scheme 3 Synthesis of the semiﬂuorinated diblock Janus co-dendrimers,

(x,y,z)¹= (3,5)¹: R^x= R^z= OC₁₂H₂₅, R^y= H; (x,y,z)¹= (3,4)¹: R^x=

R^y= OC₁₂H₂₅, R^z= H; (x,y,z)¹= (3,4,5)¹: R^x= R^y= R^z= OC₁₂H₂₅.

c

464 New J. Chem., 2012, 36, 452–468

This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientiﬁque 2012

View Online

(2F, s), ꢀ122.77 (2F, s), ꢀ123.41 (2F, m), ꢀ126.05

(2F, m). Elemental analysis calcd for C₅₁H₈₁F₁₃O₅(MW =

1021.17 g mol^ꢀ1): C 59.98, H 8.00; found: C 60.20, H 8.16%.

MALDI-TOF (M + Na⁺) calcd for m/z 1020.59(100%),

found: C 68.17, H 9.57%. MALDI-TOF (M + Na⁺) calcd for

m/z 1786.22(100%), 1785.22(88.7%), 1787.23(58.3%); found

1810.29 g mol^ꢀ1

.

(3,5)³H-F¹. 12a (0.8 g, 0.358 mmol), HO(CH₂)₂(CF₂)₆F

(0.16 g, 0.429 mmol), DCC (0.103 g, 0.501 mmol), 4-PPy

(catalytic), CH₂Cl₂(10 mL). CC (SiO₂, 7 : 3 CH₂Cl₂/hexane).

Glassy transparent solid (0.5 g, 54%). ¹H NMR (CDCl₃):

1021.59(58.1%), 838.41(16.8%); found 1044.96 g mol^ꢀ1

.

The preparation of the second (x, y, z)¹(3,5)¹H-F¹and third

(x, y, z)¹(3,5)²H-F¹generation followed the procedure used for

the preparation of (3,5)¹H-F¹.

3

d 7.28 (2 H, d, J = 2.2 Hz), 6.82 (1 H, t, J = 2.2 Hz), 6.68

(4 H, d, ³J = 2.0 Hz), 6.58 (2 H, t, ³J = 2.0 Hz), 6.55 (8 H, d,

³J = 2.2 Hz), 6.40 (4 H, t, J = 2.2 Hz), 5.00 (4 H, s), 4.95

(3,5)²H-F¹. 9a (0.8 g, 0.746 mmol), HO(CH₂)₂(CF₂)₆F

(0.33 g, 0.896 mmol), DCC (0.26 g, 1.25 mmol), 4-PPy

(catalytic), CH₂Cl₂(10 mL). CC (SiO₂, CH₂Cl₂). White solid

(0.88 g, 83%). ¹H NMR (CDCl₃): d 7.27 (2 H, s), 6.81 (1 H, t,

3

(8 H, s), 4.62 (2 H, t, ³J = 6.6 Hz), 3.93 (16 H, t, ³J = 6.5 Hz),

2.62 (2 H, m), 1.76 (16 H, m), 1.26 (144 H, m), 0.88 (24 H, t,

³J = 6.7 Hz). ¹³C NMR (CDCl₃): d 165.69, 160.49, 159.75,

138.80, 138.59, 131.20, 108.26, 107.25, 106.40, 105.70, 101.62,

100.75, 70.26, 70.15, 68.03, 57.03, 31.90, 29.65, 29.60, 29.34,

26.04, 22.67, 14.11. ¹⁹F NMR (CDCl₃): d ꢀ80.60 (3F, t, ³J =

9.25 Hz), ꢀ113.35 (2F, t, ³J = 15.0 Hz), ꢀ121.71 (2F, s),

ꢀ122.71 (2F, s), ꢀ123.44 (2F, M); ꢀ126.00 (2F, m). Elemental

analysis calcd for C₁₅₃H₂₃₇F₁₃O₁₆(MW = 2579.49 g mol^ꢀ1):

C 71.24, H 9.26; found: C 71.46, H 9.63%. MALDI-TOF (M +

Na⁺) calcd for m/z 2578.76(100%), 2579.76(88.5%),

3

³J = 2.3 Hz), 6.55 (4 H, d, J = 2.2 Hz), 6.41 (2 H, t, J =

2.2 Hz), 4.98 (4 H, s), 4.61 (2 H, t, ³J = 6.5 Hz), 3.94 (8 H, t,

³J = 6.5 Hz), 2.61 (2 H, m), 1.77 (8 H, m), 1.27 (72 H, m), 0.88

(12 H, t, J = 6.7 Hz). ¹³C NMR (CDCl₃): d 165.78, 160.55,

3

159.81, 138.45, 131.25, 108.47, 107.41, 105.72, 100.87, 70.32,

68.05, 56.95, 31.91, 29.66, 29.63, 29.60, 26.04, 22.67, 14.09.

3

¹⁹F NMR (CDCl₃): d ꢀ80.63 (3F, t, J = 9.25 Hz), ꢀ113.39

(2F, t, ³J = 15.0 Hz), ꢀ121.71 (2F, s), ꢀ122.71 (2F, s),

ꢀ123.44 (2F, m), ꢀ126.06 (2F, m). Elemental analysis calcd

for C₇₇H₁₁₇F₁₃O₈(MW = 1417.73 g mol^ꢀ1): C 65.23, H 8.32;

found: C 65.24, H 8.50%. MALDI-TOF (M + Na⁺) calcd for

m/z 1416.85(100%), 1417.86(87.7%), 1418.86(39.6%); found

2577.75(57.3%); found 2602.62 g mol^ꢀ1

.

(3,4)¹(3,5)²H-F¹.

12b

(0.9

g,

0.403

mmol),

HO(CH₂)₂(CF₂)₆F (0.176 g, 0.483 mmol), DCC (0.116 g,

0.564 mmol), 4-PPy (catalytic), CH₂Cl₂(15 mL). CC (SiO₂,

7 : 3 CH₂Cl₂/hexane). Glassy transparent solid (0.43 g, 41%).

¹H NMR (CDCl₃): d 7.20 (2 H, d, ³J = 2.4 Hz), 6.87 (4 H, dd,

1440.69 g mol^ꢀ1

.

(3,4)¹(3,5)¹H-F¹. 9b (0.6 g, 0.559 mmol), HO(CH₂)₂(CF₂)₆F

(0.25 g, 0.686 mmol), DCC (0.14 g, 0.686 mmol), 4-PPy

(catalytic), CH₂Cl₂(15 mL). CC (SiO₂, CH₂Cl₂). White solid

(0.16 g, 20%). ¹H NMR (CDCl₃): d 7.28 (2 H, d, ³J = 2.2 Hz),

3

³J = 1.8 Hz, J = 8.25 Hz), 6.84 (4 H, d, J = 1.8 Hz), 6.79

(4 H, d, ³J = 8.25 Hz), 6.73 (1 H, t, ³J = 2.4 Hz), 6.60 (4 H, d,

³J = 2.2 Hz), 6.50 (2 H, t, J = 2.4 Hz), 4.92 (4 H, s), 4.85

3

(8 H, s), 4.54 (2 H, t, ³J = 6.6 Hz), 3.91 (16 H, m), 2.53

(2 H, m), 1.73 (16 H, m), 1.18 (144 H, m), 0.80 (24 H, t,

³J = 6.8 Hz). ¹³C NMR (CDCl₃): d 165.37, 160.23, 159.75,

149.28, 149.07, 138.56, 129.10, 120.53, 113.66, 113.57, 108.37,

107.16, 106.33, 101.41, 70.23, 69.29, 69.22, 68.80, 56.53, 31.91,

29.69, 29.63, 29.36, 26.04, 22.67, 14.10. ¹⁹F NMR (CDCl₃):

d ꢀ80.59 (3F, t, ³J = 9.25 Hz), ꢀ113.34 (2F, t, ³J = 15.0 Hz),

ꢀ121.66 (2F, s), ꢀ122.67 (2F, s), ꢀ123.44 (2F, m), ꢀ126.06

(2F, m). Elemental analysis calcd for C₁₅₃H₂₃₇F₁₃O₁₆(MW =

2579.49 g mol^ꢀ1): C 71.24, H 9.26; found: C 71.37, H 9.53%.

MALDI-TOF (M + Na⁺) calcd for m/z 2578.76(100%),

6.95–6.86 (6 H, m), 6.81 (1 H, t, J = 2.2 Hz), 4.97 (4 H, s),

4.61 (2 H, t, ³J = 6.6 Hz), 4.00 (8 H, m), 2.61 (2 H, m),

3

1.79 (8 H, m), 1.27 (144 H, m), 0.88 (12 H, t, J = 6.8 Hz).

¹³C NMR (CDCl₃): d 165.81, 160.59, 159.79, 149.15, 138.57,

131.32, 120.60, 108.45, 107.24, 105.92, 101.15, 70.28, 69.25,

68.85, 56.51, 31.92, 29.69, 29.64, 29.36, 26.05, 22.67, 14.10.

3

¹⁹F NMR (CDCl₃): d ꢀ80.65 (3F, t, J = 9.25 Hz), ꢀ113.37

(2F, t, ³J = 15.0 Hz), ꢀ121.75 (2F, s), ꢀ122.75 (2F, s),

ꢀ123.46 (2F, m), ꢀ126.09 (2F, m). Elemental analysis calcd

for C₇₇H₁₁₇F₁₃O₈(MW = 1417.73 g mol^ꢀ1): C 65.23, H 8.32;

found: C 65.33, H 8.76%. MALDI-TOF (M + Na⁺) calcd for

m/z 1416.85(100%), 1417.86(87.7%), 1418.86(39.6%); found

2579.76(88.5%), 2577.75(57.3%); found 2601.44 g mol^ꢀ1

.

1441.34 g mol^ꢀ1

.

(3,4,5)¹(3,5)²H-F¹.

12c

(0.9

g,

0.303

mmol),

(3,4,5)¹(3,5)¹H-F¹.

9c

(0.72

g,

0.499

mmol),

HO(CH₂)₂(CF₂)₆F (0.13 g, 0.363 mmol), DCC (0.09 g,

0.436 mmol), 4-PPy (catalytic), CH₂Cl₂(12 mL). CC (SiO₂,

CH₂Cl₂). Glassy transparent solid (0.48 g, 48%). ¹H NMR

(CDCl₃): d 7.21 (2 H, d, ³J = 2.4 Hz), 6.75 (1 H, t, ³J =

2.4 Hz), 6.62 (4 H, d, ³J = 2.0 Hz), 6.53 (8 H, s), 6.52 (2 H, t,

HO(CH₂)₂(CF₂)₆F (0.22 g, 0.5999 mmol), DCC (0.14 g,

0.698 mmol), 4-PPy (catalytic), CH₂Cl₂(10 mL). CC (SiO₂,

CH₂Cl₂). White solid (0.41 g, 46%). ¹H NMR (CDCl₃): d 7.21

(2 H, d, ³J = 2.2 Hz), 6.75 (1 H, t, ³J = 2.2 Hz), 6.54 (4 H, s),

3

4.87 (4 H, s), 4.56 (2 H, t, J = 6.4 Hz), 3.88 (12 H, m), 2.53

3

³J = 2.0 Hz), 4.93 (4 H, s), 4.83 (8 H, s), 4.54 (2 H, t, J =

(2 H, m), 1.72 (12 H, m), 1.22 (108 H, m), 0.80 (18 H, t, J =

6.6 Hz), 3.87 (24 H, m), 2.53 (2 H, m), 1.71 (24 H, m), 1.18

(216 H, m), 0.80 (36 H, t, J = 6.8 Hz). ¹³C NMR (CDCl₃):

6.8 Hz). ¹³C NMR (CDCl₃): d 165.84, 160.08, 153.33, 152.87,

142.73, 138.32, 130.97, 108.40, 106.24, 73.42, 70.79, 69.10,

56.74, 31.91, 29.69, 29.64, 29.36, 26.04, 22.60, 14.10. ¹⁹F NMR

(CDCl₃): d ꢀ80.60 (3F, t, ³J = 9.25 Hz), ꢀ113.40 (2F, t,

³J = 15.0 Hz), ꢀ121.72 (2F, s), ꢀ122.73 (2F, s), ꢀ123.38

(2F, m), ꢀ126.02 (2F, m). Elemental analysis calcd for

3

d 165.89, 160.21, 153.30, 152.87, 138.57, 137.99, 131.44,

127.08, 124.61, 108.52; 106.43, 106.24, 101.46, 73.40, 70.59,

70.49, 69.08, 56.96, 31.91, 29.75, 29.65, 29.36, 26.05, 22.67,

14.10. ¹⁹F NMR (CDCl₃): d ꢀ80.60 (3F, t, ³J = 9.25 Hz),

ꢀ113.34 (2F, t, ³J = 15.0 Hz), ꢀ121.67 (2F, s), ꢀ122.68

(2F, s), ꢀ123.40 (2F, m), ꢀ125.99 (2F, m). Elemental analysis

C

₁₀₁H₁₆₅F₁₃O₁₀(MW = 1786.36 g mol^ꢀ1): C 67.91, H 9.31;

c

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New J. Chem., 2012, 36, 452–468 465

View Online

calcd for C₂₀₁H₃₃₃F₁₃O₂₀(MW = 3316.76 g mol^ꢀ1): C 72.79,

H 10.12; found: C 72.88, H 10.04%. MALDI-TOF (M + Na⁺)

calcd for m/z 3316.49(100%), 3315.49(86.3%), 23 317.49(73.3%);

ꢀ121.81 (4F, s), ꢀ122.81 (4F, s), ꢀ123.49 (4F, m), ꢀ126.07

(4F, m). Elemental analysis calcd for C₆₇H₉₀F₂₆O₈(MW =

1517.39 g mol^ꢀ1): C 53.03, H 5.98; found: C 53.34, H 6.28%.

MALDI-TOF (M + Na⁺) calcd for m/z 1516.62(100%),

found 3339.82 g mol^ꢀ1

.

1517.63(76.2%), 1518.63(30.2%); found 1540.56 g mol^ꢀ1

.

(3,5)¹H-F². To the solution of 7a (0.54 g, 1.13 mmol),

4 (0.82 g, 0.937 mol) and PPh₃(0.30 g, 1.13 mmol) in dry

THF (10 mL) under argon DIAD (0.22 mL, 1.13 mmol) in

10 mL of THF was added dropwise at 0 1C. The reaction was

reﬂuxed for 72 h. The solvent was removed by evaporation

and the residue was partitioned between CH₂Cl₂(100 mL) and

water (100 mL), the organic extract was washed with NH₄Cl

(100 mL) and brine (100 mL), dried over MgSO₄, ﬁltered and

the solvent was evaporated to dryness. The crude product was

puriﬁed by CC (SiO₂, 7 : 3 CH₂Cl₂/hexane) to yield a white

The preparation of (3,5)²H-F²,(3,4)¹(3,5)¹H-F²,(3,4,5)¹(3,5)¹H-F²,

(3,5)³H-F², (3,4)¹(3,5)²H-F², and (3,4,5)¹(3,5)²H-F²followed

the procedure used for the preparation of (3,5)¹H-F².

(3,5)²H-F². 10a (0.77 g, 0.728 mmol), 4 (0.53 g, 0.606 mol),

PPh₃(0.19 g, 0.728 mmol), THF (10 mL), DIAD (0.14 mL,

0.728 mmol). CC (SiO₂, 7 : 3 CH₂Cl₂/hexane). White glassy

1

3

solid (0.71 g, 61%). H NMR (CDCl₃): d 8.25 (1 H, t, J =

1.3 Hz), 7.82 (2 H, d, ³J = 1.3 Hz), 6.66 (2 H, d, ³J = 2.0 Hz),

3

6.57 (1 H, t, J = 2.0 Hz), 6.53 (4 H, d, J = 2.0 Hz), 6.38

(2 H, t, ³J = 2.0 Hz), 5.05 (2 H, s), 4.96 (4 H, s), 4.64 (4 H, t,

³J = 6.4 Hz), 3.91 (8 H, t, J = 6.6 Hz), 2.61 (4 H, m), 1.74

1

3

solid (0.89 g, 71%). H NMR (CDCl₃): d 8.27 (1 H, t, J =

1.5 Hz), 7.85 (2 H, d, ³J = 1.5 Hz), 6.57 (2 H, d, ³J = 2.2 Hz),

3

6.42 (1 H, t, J = 2.2 Hz), 5.07 (2 H, s), 4.65 (4 H, t, J =

6.4 Hz), 3.94 (4 H, t, ³J = 6.6 Hz), 2.63 (4 H, m), 1.77 (4 H, m),

1.26 (36 H, m), 0.88 (6 H, t, ³J = 6.7 Hz). ¹³C NMR (CDCl₃):

d 165.01, 160.63, 158.92, 137.94, 131.26, 120.59, 105.75,

101.02, 70.53, 68.11, 57.24, 31.90, 29.65, 29.60, 29.34, 26.04,

22.67, 14.08. ¹⁹F NMR (CDCl₃): d ꢀ80.72 (6F, t, ³J =

9.25 Hz), ꢀ113.50 (4F, t, ³J = 15.0 Hz), ꢀ121.81 (4F, s),

ꢀ122.82 (4F, s), ꢀ123.49 (4F, m), ꢀ126.12 (4F, m). Elemental

analysis calcd for C₅₅H₆₆F₂₆O₇(MW = 1333.07 g mol^ꢀ1):

C 49.55, H 4.99; found: C 49.78, H 5.27%. MALDI-TOF

(M + Na⁺) calcd for m/z 1332.44(100%), 1333.44(61.5%),

(8 H, m), 1.24 (72 H, m), 0.86 (12 H, t, ³J = 6.9 Hz). ¹³C NMR

(CDCl₃): d 164.98, 160.51, 160.23, 158.83, 138.77, 138.09,

131.25, 123.24, 120.53, 106.40, 105.69, 101.74, 100.76, 70.39,

70.17, 68.04, 57.26, 31.90, 29.65, 29.60, 29.34, 26.02, 22.67,

14.09. ¹⁹F NMR (CDCl₃): d ꢀ80.70 (6F, t, ³J = 9.25 Hz),

ꢀ113.48 (4F, t, ³J = 15.0 Hz), ꢀ121.80 (4F, s), ꢀ122.81 (4F, s),

ꢀ123.49 (4F, m), ꢀ126.10 (4F, m). Elemental analysis calcd

for C₉₃H₁₂₆F₂₆O₁₁: (MW = 1913.95 g mol^ꢀ1) C 58.36, H 6.64;

found: C 58.61; H 6.87%. MALDI-TOF (M + Na⁺) calcd for

m/z 1913.89(100%), 1912.89(94.5%), 1914.90(52.3%); found

1936.97 g mol^ꢀ1

.

1334.45(19.2%); found 1356.59 g mol^ꢀ1

.

(3,4)¹(3,5)¹H-F². 10b (0.62 g, 0.586 mmol), 4 (0.61 g,

0.703 mol), PPh₃(0.18 g, 0.703 mmol), THF (15 mL), DIAD

(0.14 mL, 0.703 mmol). CC (SiO₂, 7 : 3 CH₂Cl₂/hexane). White

(3,4)¹H-F²and (3,4,5)¹H-F²were prepared according to the

procedure used for 8b.

(3,4)¹H-F². 7b⁰(0.79 g, 1.56 mmol), 4 (1.13 g, 1.29 mmol),

K₂CO₃(1.07 g, 1.75 mmol), DMF (30 mL). CC (SiO₂, 7 : 3

CH₂Cl₂/hexane). White solid (0.71 g, 41%). ¹H NMR

(CDCl₃): d 8.18 (1 H, t, ³J = 1.5 Hz), 7.77 (2 H, d, ³J =

1.5 Hz), 6.85 (3 H, m), 4.97 (2 H, s), 4.57 (4 H, t, ³J = 6.4 Hz),

3.92 (4 H, m), 2.56 (4 H, m), 1.75 (4 H, m), 1.18 (36 H, m), 0.80

glassy solid (0.48 g, 43%). H NMR (CDCl₃): d 8.19 (1 H, t,

1

³J = 1.5 Hz), 7.77 (2 H, d, ³J = 1.5 Hz), 6.87 (2 H, dd,

3

³J = 1.3 Hz, J = 8.1 Hz), 6.84 (2 H, d, J = 1.3 Hz), 6.79

(2 H, d, ³J = 8.1 Hz), 6.61 (2 H, d, ³J = 2.0 Hz), 6.51 (1 H, t,

³J = 2.0 Hz), 5.00 (2 H, s), 4.86 (4 H, s), 4.59 (4 H, t, J =

3

6.4 Hz), 3.91 (8 H, m), 2.56 (4 H, m), 1.71 (8 H, m), 1.18 (72 H, m),

0.80 (12 H, t, ³J = 6.8 Hz). ¹³C NMR (CDCl₃): d 164.99,

160.29, 158.84, 149.30, 149.10, 138.07, 131.26, 129.07, 123.23,

120.53, 113.68, 113.57, 106.33, 101.70, 70.66, 70.26, 69.31,

69.23, 57.26, 31.92, 29.69, 29.63, 29.36, 26.02, 22.68, 14.09.

3

(6 H, t, J = 6.9 Hz). ¹³C NMR (CDCl₃): d 165.05, 160.63,

158.94, 149.35, 131.18, 128.19, 123.11, 120.62, 113.56, 113.51,

70.67, 69.26, 57.23, 31.92, 29.69, 29.62, 29.36, 26.04, 22.63,

14.09. ¹⁹F NMR (CDCl₃): d ꢀ80.69 (6F, t, ³J = 9.25 Hz),

ꢀ113.49 (4F, t, ³J = 15.0 Hz), ꢀ121.80 (4F, s), ꢀ122.80

(4F, s), ꢀ123.48 (4F, m), ꢀ126.09 (4F, m). Elemental analysis

calcd for C₅₅H₆₆F₂₆O₇(MW = 1333.07 g mol^ꢀ1): C 49.55, H

4.99; found: C 49.66, H 5.07%. MALDI-TOF (M + Na⁺)

calcd for m/z 1332.44(100%), 1333.44(61.5%), 1334.45(19.2%);

3

¹⁹F NMR (CDCl₃): d ꢀ80.70 (6F, t, J = 9.25 Hz), ꢀ113.48

(4F, t, ³J = 15.0 Hz), ꢀ121.79 (4F, s), ꢀ122.79 (4F, s),

ꢀ123.61 (4F, m), ꢀ126.15 (4F, m). Elemental analysis calcd

for C₉₃H₁₂₆F₂₆O₁₁(MW = 1913.95 g mol^ꢀ1): C 58.36, H 6.64;

found: C 58.64, H 6.68%. MALDI-TOF (M + Na⁺) calcd for

m/z 1913.89(100%), 1912.89(94.5%), 1914.90(52.3%); found

found 1356.21 g mol^ꢀ1

.

1938.05 g mol^ꢀ1

.

(3,4,5)¹H-F². 7c⁰(0.88 g, 1.29 mmol), 4 (0.94 g, 1.08 mmol),

K₂CO₃(1.8 g, 12.95 mmol), DMF (15 mL). CC (SiO₂, 7 : 3

(3,4,5)¹(3,5)¹H-F². 10c (1.17 g, 0.82 mmol), 4 (0.6 g,

0.684 mol), PPh₃(0.21 g, 0.82 mmol), THF (15 mL), DIAD

(0.16 mL, 0.82 mmol). CC (SiO₂, 1 : 1 CH₂Cl₂/hexane). White

1

CH₂Cl₂/hexane). White glassy solid (0.57 g, 35%). H NMR

(CDCl₃): d 8.19 (1 H, t, ³J = 1.5 Hz), 7.78 (2 H, d, ³J = 1.5 Hz),

6.55 (2 H, s), 4.95 (2 H, s), 4.57 (4 H, t, ³J = 6.4 Hz), 3.88 (6 H,

m), 2.54 (4 H, m), 1.72 (6 H, m), 1.18 (54 H, m), 0.80 (9 H, t, ³J =

6.8 Hz). ¹³C NMR (CDCl₃): d 165.02, 158.64, 153.39, 138.29,

131.23, 130.64, 122.91, 120.57, 106.18, 73.43, 70.92, 69.12, 57.26,

31.92, 29.75, 29.64, 29.36; 26.01, 22.68, 14.09. ¹⁹F NMR (CDCl₃):

1

glassy solid (0.85 g, 54%). H NMR (CDCl₃): d 8.20 (1 H, t,

3

³J = 1.3 Hz), 7.78 (2 H, d, J = 1.3 Hz), 6.63 (2 H, d, J =

2.0 Hz), 6.55 (4 H, m), 6.53 (1 H, s); 5.01 (2 H, s), 4.87 (4 H, s),

4.58 (4 H, t, ³J = 6.4 Hz), 3.88 (12 H, m), 2.56 (4 H, m),

3

1.72 (12 H, m), 1.18 (108 H, m), 0.80 (18 H, t, J = 6.8 Hz).

¹³C NMR (CDCl₃): d 164.98, 160.26, 158.83, 153.31, 138.00,

3

d ꢀ80.69 (6F, t, J = 9.25 Hz), ꢀ113.50 (4F, t, J = 15.0 Hz),

c

466 New J. Chem., 2012, 36, 452–468

This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientiﬁque 2012

View Online

131.42, 131.28, 123.21, 120.52, 106.36, 106.22, 101.67, 73.42,

70.90, 70.60, 69.10, 57.29, 31.92, 29.75, 29.65, 29.36, 26.06, 22.63,

14.09. ¹⁹F NMR (CDCl₃): d ꢀ80.69 (6F, t, ³J = 9.25 Hz),

ꢀ113.48 (4F, t, ³J = 15.0 Hz), ꢀ121.80 (4F, s), ꢀ122.79 (4F, s),

ꢀ123.61 (4F, m), ꢀ126.10 (4F, m). Elemental analysis calcd

for C₁₁₇H₁₇₄F₂₆O₁₃(MW = 2282.58 g mol^ꢀ1): C 61.56, H

7.68; found: C 61.80, H 7.59%. MALDI-TOF (M + Na⁺)

calcd for m/z 2282.26(100%), 2281.25(75%), 2283.26(68%);

(CDCl₃): d 164.93, 160.23, 158.85, 153.32, 139.00, 138.28,

138.09, 131.53, 131.31, 123.24, 120.53, 117.49, 106.38,

106.22, 106.32, 101.75, 101.56, 73.42, 70.58, 70.39, 70.11,

69.14, 57.26, 31.92, 29.69, 29.65, 29.40, 26.13, 22.67, 14.09.

3

¹⁹F NMR (CDCl₃): d ꢀ80.67 (6F, t, J = 9.25 Hz), ꢀ113.48

(4F, t, ³J = 15.0 Hz), ꢀ121.76 (4F, s), ꢀ122.77 (4F, s),

ꢀ123.44 (4F, m), ꢀ126.07 (4F, m). Elemental analysis calcd

for C₂₁₇H₃₄₂F₂₆O₂₃(MW = 3812.98 g mol^ꢀ1): C 68.35, H

9.04; found: C 68.52, H 9.29%. MALDI-TOF (M + Na⁺)

calcd for m/z 3812.52(100%), 3813.53(88.4%), 3811.52(84%);

found 2306.36 g mol^ꢀ1

.

(3,5)³H-F². 13a (0.95 g, 0.428 mmol), 4 (0.31 g, 0.354 mol),

PPh₃(0.11 g, 0.428 mmol), THF (10 mL), DIAD (0.08 mL,

0.428 mmol). CC (SiO₂, 7 : 3 CH₂Cl₂/hexane). White glassy

found 3836.39 g mol^ꢀ1

.

1

3

solid (0.52 g, 48%). H NMR (CDCl₃): d 8.18 (1 H, t, J =

0.5 Hz), 7.76 (2 H, d, ³J = 0.5 Hz), 6.60 (4 H, d, ³J = 2.0 Hz),

Acknowledgements

3

I.B., B.H., C.B., G.M., D.G., and B.D. thank the CNRS, the

University of Strasbourg, the University of Hull and the

European Union (RTN project ‘‘Supramolecular Liquid

Crystal Dendrimers-LCDD, HPRNCT 2000 00016, 2000–

2004) for support and funding.

6.51 (2 H, t, J = 2.0 Hz), 6.47 (11 H, m), 6.32 (4 H, t, J =

2.0 Hz), 5.00 (2 H, s), 4.90 (4 H, s), 4.86 (8 H, s), 4.56 (4 H, t,

³J = 6.4 Hz), 3.82 (16 H, t, ³J = 6.6 Hz), 2.54 (4 H, m),

3

1.67 (16 H, m), 1.21 (144 H, m), 0.81 (24 H, t, J = 6.5 Hz).

¹³C NMR (CDCl₃): d 164.95, 160.48, 160.13, 158.82, 138.96,

138.83, 138.17, 131.24, 127.14, 123.15, 120.52, 106.39, 106.30,

105.70, 101.54, 100.74, 73.39, 70.39, 70.13, 68.04, 57.23, 31.91,

29.65, 29.62, 29.33, 26.03, 22.65, 14.09. ¹⁹F NMR (CDCl₃):

d ꢀ80.71 (6F, t, ³J = 9.25 Hz), ꢀ113.47 (4F, t, ³J = 15.0 Hz),

ꢀ121.79 (4F, s); ꢀ122.79 (4F, s), ꢀ123.46 (4F, m), ꢀ126.08

(4F, m). Elemental analysis calcd for C₁₆₉H₂₄₆F₂₆O₁₉(MW =

3075.71 g mol^ꢀ1): C 65.99, H 8.06; found: C 65.81, H 8.27%.

MALDI-TOF (M + Na⁺) calcd for m/z 3074.79(100%),

Notes and references

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3075.79(94%), 3076.8(60.8%); found 3098.35 g mol^ꢀ1

.

(3,4)¹(3,5)²H-F². 13b (1.2 g, 0.54 mmol), 4 (0.39 g, 0.45 mol),

PPh₃(0.14 g, 0.54 mmol), THF (15 mL), DIAD (0.11 mL,

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solid (0.51 g, 37%). H NMR (CDCl₃): d 8.27 (1 H, t, J =

1.3 Hz), 7.85 (2 H, d, ³J = 1.3 Hz), 6.95 (4 H, dd, ³J = 1.8 Hz,

3

³J = 8.3 Hz), 6.91 (4 H, d, J = 1.8 Hz), 6.87 (4 H, d, J =

8.3 Hz), 6.69 (6 H, m), 6.60 (1 H, t, ³J = 2.4 Hz), 6.57 (2 H, t,

³J = 2.4 Hz), 5.09 (2 H, s), 4.99 (4 H, s), 4.93 (8 H, s), 4.63

(4 H, t, ³J = 6.4 Hz), 3.99 (16 H, m), 2.61 (4 H, m), 1.81 (16 H, m),

1.27 (144 H, m), 0.88 (24 H, t, ³J = 6.7 Hz). ¹³C NMR

(CDCl₃): d 164.95, 161.58, 160.22, 158.99, 149.27, 149.07,

138.93, 137.83, 131.25, 129.14, 126.41, 125.76, 123.04,

120.54, 113.66, 113.59, 106.39, 106.25, 101.23, 70.65, 70.22,

69.99, 69.29, 69.22, 57.84, 31.91, 29.69, 29.63, 29.36, 26.02,

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ꢀ113.48 (4F, t, ³J = 15.0 Hz), ꢀ121.79 (4F, s), ꢀ122.79 (4F, s),

ꢀ123.47 (4F, m), ꢀ126.08 (4F, m). Elemental analysis calcd for

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found: C 65.74, H 8.25%. MALDI-TOF (M + Na⁺) calcd for

m/z 3074.79(100%), 3075.79(94%), 3076.8(60.8%); found

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3

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c

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Article Doi

Self-assembly and liquid-crystalline supramolecular organizations of semifluorinated block co-dendritic supermolecules

DOI: 10.1039/c1nj20530g

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Article abstract of DOI:10.1039/c1nj20530g

Full text of DOI:10.1039/c1nj20530g

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