The
functionalization of semiconducting single-walled carbon nanotubes
(SWNTs) with sp
3
defects that act as luminescent exciton
traps is a powerful means to enhance their photoluminescence quantum
yield (PLQY) and to add optical properties. However, the synthetic
methods employed to introduce these defects are currently limited
to aqueous dispersions of surfactant-coated SWNTs, often with short
tube lengths, residual metallic nanotubes, and poor film-formation
properties. In contrast to that, dispersions of polymer-wrapped SWNTs
in organic solvents feature unrivaled purity, higher PLQY, and are
easily processed into thin films for device applications. Here, we
introduce a simple and scalable phase-transfer method to solubilize
diazonium salts in organic nonhalogenated solvents for the controlled
reaction with polymer-wrapped SWNTs to create luminescent aryl defects.
Absolute PLQY measurements are applied to reliably quantify the defect-induced
brightening. The optimization of defect density and trap depth results
in PLQYs of up to 4% with 90% of photons emitted through the defect
channel. We further reveal the strong impact of initial SWNT quality
and length on the relative brightening by sp
3
defects.
The efficient and simple production of large quantities of defect-tailored
polymer-sorted SWNTs enables aerosol-jet printing and spin-coating
of thin films with bright and nearly reabsorption-free defect emission,
which are desired for carbon nanotube-based near-infrared light-emitting
devices.
The chemistry of dicationic diboranes with two BII atoms that are engaged in direct B−B bonding is by enlarge unexplored, although these molecules have intriguing properties due to their combined Lewis acidic and electron‐donor properties. Unsymmetric dicationic diboranes are extremely rare, but especially attractive due to their polarized B−B bond. In this work we report the directed synthesis of several stable unsymmetric dicationic diboranes by reaction between the electron‐rich ditriflato‐diborane B2(hpp)2(OTf)2 (hpp=1,3,4,6,7,8‐hexahydro‐2H‐pyrimido[1,2‐α]pyrimidinate) and phosphino‐pyridines, establishing B−N and B−P bonds with the diborane concomitant with triflate elimination. In the case of 2‐((ditertbutylphosphino)methyl)pyridine, the B−N bond is formed instantly, but the B−P bond formation requires (due to steric constraints) several days at ambient conditions for completion, creating an intermediate that could be used for frustrated Lewis pair (FLP)‐like chemistry. Here we test its reaction with an aldehyde, and propose a new type of FLP‐like chemistry.
The introduction of electron‐donating, bridging guanidinate substituents in diborane(4) compounds allows the synthesis of a variety of new cationic diborane(4) compounds. In this work, strategies for the directed synthesis of cationic di‐ and tetraboron compounds are presented, leading to the synthesis and complete characterization of several new compounds with distinct structural motifs, all exhibiting BII atoms directly bound to each other. Hence, we report on tetracationic donor‐acceptor cyclophanes with diboron donor linkers and organic π‐acceptor units, on paddlewheel‐type cationic diboranes, and on unsymmetrically‐substituted monocationic diboranes.
Starting with diboranes with two electron-rich bridging bicyclic guanidinate substituents, we report in this work the rational synthesis of new dicationic symmetrically-and unsymmetrically-substituted diboranes in S N 1-type substitution reactions in which triflato or bromo substituents are replaced by neutral Lewis bases. The scope of such substitution reactions and their rate are analyzed with different pyridine derivatives of variable Lewis basicity. The first substitution step, leading to a mono-cationic diborane with one anionic substituent (triflate or bromide) and one neutral Lewis base, proceeds much faster than the second substitution step leading to a dicationic diborane with two neutral Lewis bases. The different time scales for the substitution steps could be used to conveniently synthesize in one-pot reactions several dicationic, unsymmetrically-substituted diboranes with two different neutral Lewis bases.
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