ABSTRACT:The mechanisms for the reaction of CH 3 SSCH 3 with OH radical are investigated at the QCISD(T)/6-311þþG(d,p)//B3LYP/6-311þþG(d,p) level of theory. Five channels have been obtained and six transition state structures have been located for the title reaction. The initial association between CH 3 SSCH 3 and OH, which forms two low-energy adducts named as CH 3 S(OH)SCH 3 (IM1 and IM2), is confirmed to be a barrierless process, The SAS bond rupture and HAS bond formation of IM1 lead to the products P1(CH 3 SH þ CH 3 SO) with a barrier height of 40.00 kJ mol À1 . The reaction energy of Path 1 is À74.04 kJ mol À1 . P1 is the most abundant in view of both thermodynamics and dynamics. In addition, IMs can lead to the products P2 (CH 3 S þ CH 3 SOH), P3 (H 2 O þ CH 2 S þ CH 3 S), P4 (CH 3 þ CH 3 SSOH), and P5 (CH 4 þ CH 3 SSO) by addition-elimination or hydrogen abstraction mechanism. All products are thermodynamically favorable except for P4 (CH 3 þ CH 3 SSOH). The reaction energies of Path 2, Path 3, Path 4, and Path 5 are À28.42, À46.90, 28.03, and À89.47 kJ mol À1 , respectively. Path 5 is the least favorable channel despite its largest exothermicity (À89.47 kJ mol À1 ) because this process must undergo two barriers of TS5 (109.0 kJ mol À1 ) and TS6 (25.49 kJ mol À1 ). Hopefully, the results presented in this study may provide helpful information on deep insight into the reaction mechanism.
A series of donor-acceptor (D-A) tricoordinated organoboron derivatives (1-10) have been systematically investigated for thermally activated delayed fluorescent (TADF)-based organic light-emitting diode (OLED) materials. The calculated results show that the designed molecules exhibit small singlet-triplet energy gap (E ST) values. Density functional theory (DFT) analysis indicated that the designed molecules display an efficient separation between donor and acceptor fragments because of a small overlap between donor and acceptor fragments on HOMOs and LUMOs. Furthermore, the delayed fluorescence emission color can be tuned effectively by introduction of different polycyclic aromatic fragments in parent molecule 1. The calculated results show that molecules 2, 3, and 4 possess more significant Stokes shifts and red emission with small E ST values. Nevertheless, other molecules exhibit green (1, 7, and 8), light green (6 and 10), and blue (5 and 9) emissions. Meanwhile, they are potential ambipolar charge transport materials except that 4 and 10 can serve as electron and hole transport materials only, respectively. Therefore, we proposed a rational way for the design of efficient TADF materials as well as charge transport materials for OLEDs simultaneously.
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