Journal
MATERIALS
Volume 11, Issue 9, Pages -Publisher
MDPI
DOI: 10.3390/ma11091666
Keywords
mesomorphic materials; metallo-mesogens; silver complexes; pi-pi stacking; crystalline solids
Categories
Funding
- I-DISCOVER USDA Program HSI NIFA [2014-38422-22078]
- NSF Nanosystems Engineering Research Center on Nanotechnology-Enabled Water Treatment (NEWT) [EEC-1449500]
- NSF PREM [DMR-1205302]
- Ralph & Kathleen Ponce de Leon Endowment
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Organic semiconductor materials composed of pi-pi stacking aromatic compounds have been under intense investigation for their potential uses in flexible electronics and other advanced technologies. Herein we report a new family of seven pi-pi stacking compounds of silver(I) bis-N-(4-pyridyl) benzamide with varying counterions, namely [Ag(NPBA)2]X, where NPBA is N-(4-pyridyl) benzamine, X = NO3- (1), ClO4- (2), CF3SO3- (3), PF6- (4), BF4- (5), CH3PhSO3- (6), and PhSO3- (7), which form extended pi-pi stacking networks in one-dimensional (1D), 2D and 3D directions in the crystalline solid-state via the phenyl moiety, with average inter-ring distances of 3.823 angstrom. Interestingly, the counterions that contain pi-pi stacking-capable groups, such as in 6 and 7, can induce the formation of mesomorphic phases at 130 degrees C in dimethylformamide (DMF), and can generate highly branched networks at the mesoscale. Atomic force microscopy studies showed that 2D interconnected fibers form right after nucleation, and they extend from similar to 30 nm in diameter grow to reach the micron scale, which suggests that it may be possible to stop the process in order to obtain nanofibers. Differential scanning calorimetry studies showed no remarkable thermal behavior in the complexes in the solid state, which suggests that the mesomorphic phases originate from the mechanisms that occur in the DMF solution at high temperatures. An all-electron level simulation of the band gaps using NRLMOL (Naval Research Laboratory Molecular Research Library) on the crystals gave 3.25 eV for (1), 3.68 eV for (2), 1.48 eV for (3), 5.08 eV for (4), 1.53 eV for (5), and 3.55 eV for (6). Mesomorphic behavior in materials containing pi-pi stacking aromatic interactions that also exhibit low-band gap properties may pave the way to a new generation of highly branched organic semiconductors.
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