HIERARCHICAL CONTROL OF INTERNAL SUPERSTRUCTURE, DIAMETER, AND STABILITY OF SUPRAMOLECULAR AND MACROMOLECULAR COLUMNS GENERATED FROM TAPERED MONODENDRITIC BUILDING-BLOCKS
V. Percec et al., HIERARCHICAL CONTROL OF INTERNAL SUPERSTRUCTURE, DIAMETER, AND STABILITY OF SUPRAMOLECULAR AND MACROMOLECULAR COLUMNS GENERATED FROM TAPERED MONODENDRITIC BUILDING-BLOCKS, Macromolecules, 31(6), 1998, pp. 1745-1762
The synthesis of the first generation AB(3) monodendrons 3,4,5-tris[6-
alkyloxy-2-methylnaphthyloxy]benzoic acid (with decyl, dodecyl, tetrad
ecyl, and hexadecyl alkyl groups), ,4,5-tris[4-(4'-dodecyloxyphenyl)be
nzyloxy]benzoic acid, their omega-hydroxy(tetraethylene glycol) esters
, and the corresponding methacrylates and poly(methacrylate)s is descr
ibed. All monodendrons and the corresponding polymers self-assemble in
to supramolecular columns that self-organize in a columnar hexagonal (
Phi(h)) thermotropic liquid crystalline (LC) phase. The characterizati
on of their Phi(h) phase by a combination of differential scanning cal
orimetry (DSC), thermal optical polarized microscopy, and X-ray diffra
ction experiments demonstrated an intracolumnar microsegregated model
for these supramolecular structures. The role and the contribution of
the aliphatic, aromatic, oligooxyethylenic, and polymethacrylate fragm
ents to the formation and the control of the external diameter, the in
ternal structure, and the stability of these supramolecular columns an
d of the Phi(h) phase were quantitatively evaluated and demonstrated t
hat the contribution of the aromatic component dominates over that of
the other structural components both in the control of column diameter
and in thermodynamic stability of the resulted Phi(h) phase.