Fullerene
fragments, referred to as buckybowls, are garnering interest
due to their distinctive molecular shapes and optoelectronic properties.
Here, we report the synthesis and characterization of a novel C70 subunit, diindeno[4,3,2,1-fghi:4′,3′,2′,1′-opqr]perylene, that is substituted with either triethylsilyl(TES)-ethynyl
or 2,4,6-triisopropylphenyl groups at the meta-positions.
The resulting compounds (1 and 2) display
a bowl-to-bowl inversion at room temperature. Notably, the substituent
groups on the meta-positions alter both the geometric
and the electronic properties as well as the crystal packing of the
buckybowls. In contrast to the 2,4,6-triisopropylphenyl groups in 2, the TES-ethynyl groups in 1 lead to enhanced
bond length alternation, resulting in weaker aromaticity of the six-membered
rings of the buckybowl skeleton. 1 forms one-dimensional
(1D) concave-in-convex stacking columns, and when 1 is
blended with C70, the buckybowls encapsulate C70 and result in two-dimensional cocrystals. Organic field-effect transistor
(OFET) measurements demonstrate that 1 displays a hole
mobility of 0.31 cm2 V–1 s–1, and the 1-C70 cocrystal exhibits ambipolar
transport characteristics with electron and hole mobilities approaching
0.40 and 0.07 cm2 V–1 s–1, respectively. This work demonstrates the potential of buckybowls
for the development of organic semiconductors.
For pure acetylene manufacturing and natural gas purification, the development of porous materials displaying highly selective C 2 H 2 /CH 4 and CO 2 /CH 4 separation is greatly important but remains a major challenge. In this work, a plausible strategy involving solvent-induced effects and using the flexibility of the ligand conformation to make two In(III) metal−organic frameworks (MOFs) is developed, showing topological diversity and different stability. The X-shaped tetracarboxylic ligand H 4 TPTA ([1,1′:3′,1″-terphenyl]-4,4′,4″,6′-tetracarboxylic acid) was selected to construct two new heteroid In MOFs, namely, {[showing a pts topology with a large channel that is not conducive to fine gas separation. By contrast, with the reduction of SBU from uninucleated In to an {In-OH-In} n chain, MOF 2 has a (4, 6)connected net with the fsc topology with an ∼5 Å suitable micropore to confine matching small gas. The permanent porosity of MOF 2 leads to the preferential adsorption of C 2 H 2 over CO 2 with superior C 2 H 2 /CH 4 (332.3) and CO 2 /CH 4 (31.2) separation selectivities. Meanwhile, the cycling dynamic breakthrough experiments showed that the high-purity C 2 H 2 (>99.8%) capture capacities of MOF 2 were >1.92 mmol g −1 from a binary C 2 H 2 /CH 4 mixture, and its separation factor reached 10.
The lanthanum(III) complexes tris(3,5-diphenylpyrazolato-κ(2)N,N')tris(tetrahydrofuran-κO)lanthanum(III) tetrahydrofuran monosolvate, [La(C(15)H(11)N(2))(3)(C(4)H(8)O)(3)]·C(4)H(8)O, (I), and tris(3,5-diphenyl-1,2,4-triazolato-κ(2)N(1),N(2))tris(tetrahydrofuran-κO)lanthanum(III), [La(C(14)H(10)N(3))(3)(C(4)H(8)O)(3)], (II), both contain La(III) atoms coordinated by three heterocyclic ligands and three tetrahydrofuran ligands, but their coordination geometries differ. Complex (I) has a mer-distorted octahedral geometry, while complex (II) has a fac-distorted configuration. The difference in the coordination geometries and the existence of asymmetric La-N bonding in the two complexes is associated with intramolecular C-H...N/O interactions between the ligands.
Adsorption separation of paraffin and olefin is an industrially important process, while developing a highly stable and paraffin-selective adsorbent remains challenging. Herein, a pcu-topology (primitive cubic) robust pillared MOF, termed...
Efficient
gas separation and purification play a vital role in
the current advanced development of industry, and the application
of MOF adsorbents in this area with highly technical materials shows
obvious advantages. On the basis of reticular chemistry, the 4-c lvt
MOF adsorbent [CuDTTA]·3DMF·CH3CN has been constructed
(CuDTTA; H2DTTA = 2,5-bis(1H-1,2,4-triazol-1-yl)terephthalic
acid). CuDTTA reveals a multiple-micropore system and high-density
active sites decorated on the channel surfaces, which are conducive
to its extraordinary selectivity of CO2/CH4 and
C2H2/CH4 (29 and 166, 1:1). In combination
with an analysis of Q
st values, CuDTTA
possesses the synergistic effect of size sieving and abundant functional
sites, significantly improving the gas adsorption and separation performance.
Meanwhile, the results also reveal that functional sites have a stronger
binding affinity toward C2H2 with respect to
CO2. Such a conclusion renders CuDTTA to be a promising
adsorbent material for industrial applications.
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