A variable temperature
single crystal X-ray diffraction study revealed
an unusual thermal expansion property of an organic salt, imidazolium
4-hydroxybenzene carboxylate, which exhibits colossal negative and
positive axial thermal expansion along the crystallographic b axis and approximately along the a axis,
respectively. The hydrogen bonded, two-dimensional square grid type
of the flexible network in the crystal structure of the salt resembles
a fencing structure that undergoes scissor-like motion resulting the
abnormal thermal behavior. Thermal expansion induced by a scissor
motion of the hydrogen bonded network in a multicomponent crystalline
organic compound has not been reported before, although this mechanism
is mentioned to elucidate colossal thermal expansion in some inorganic
framework materials.
Switching from positive to negative axial thermal expansion in pure organic materials is reported for the first time. This rare phenomenon has been rationalized based on the packing of molecules in crystal structures and transverse thermal vibrations of atoms in the molecule. Unique packing of the molecules in the crystal structure contributes to the restricted movement of molecules along the c axis. Subsequently, contraction of molecular dimensions with increasing temperature, due to transverse vibrations of some atoms, assists with the switch from Positive Thermal Expansion (PTE) to Negative Thermal Expansion (NTE).
Rare area negative thermal expansion of a new mixed metal mixed organic MOF has been described using an “elevator-platform” analogy induced by O–H⋯O hydrogen bonding.
Thermal expansion of a new mixed-metal
mixed-linker metal organic
framework (MOF) has been studied by variable temperature single crystal
X-ray diffraction. Origin of axial positive, negative, and zero thermal
expansion in the MOF has been elucidated by analyzing the crystal
structures. Flexibility in coordination of ligands around the metal
ions induces axial NTE and PTE in the 2D layers of the MOF. On the
other hand, thickness of the 2D layers in the crystal structure remains
unchanged along one of the principal axes resulting in rare ZTE. O···O
Distances of O–H···O hydrogen bonding between
the 2D layers in the crystal structure remain almost unaffected with
increasing temperature.
The structural alteration of semiconducting polymer backbones can improve the optoelectronic properties of organic semiconductors and enhance field-effect mobilities. In our efforts towards improving the performance of organic field-effect transistors (OFETs), we are reporting a donor–acceptor polymer containing thieno[3,2-b]pyrrole (TP) donor and a furan-flanked diketopyrrolopyrrole (DPP) electron acceptor, which yielded an asymmetric poly(methylthienopyrrolo)furanyl)diketopyrrolopyrrol) P(FDPP-TP) organic semiconducting polymer. The introduction of a furan spacer improved thermally induced crystallinity and molecular packing, as confirmed by grazing incidence X-ray diffraction (XRD) and tapping-mode atomic force microscopy (TMAFM). The tested OFET devices gave maximum hole mobility of 0.42 cm2 V−1 s−1 with threshold voltages around 0 V for bottom-gate bottom-contact device configuration.
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